WEALTH FROM OCEANS FLAGSHIP
Metals in the Waters and Sediments of Port Curtis, Queensland
Brad M. Angel, Chad V. Jarolimek, Joshua J. King, Leigh T. Hales, Stuart L. Simpson, Robert F. Jung, Simon C. Apte
May 2012
PRINT ISBN: 978 0 643 10816 5 WEB ISBN: 978 0 643 10817 2
CSIRO Wealth from Oceans Flagship CSIRO Land and Water Citation Angel, B.M., Jarolimek, C.V., King, J.J., Hales, L.T., Simpson, S.L., Jung, R.F. and Apte, S.C. (2012). Metal Concentrations in the Waters and Sediments of Port Curtis, Queensland. CSIRO Wealth from Oceans Flagship Technical Report. Copyright and Disclaimer © 2012 CSIRO To the extent permitted by law, all rights are reserved and no part of this publication covered by copyright may be reproduced or copied in any form or by any means except with the written permission of CSIRO. Important Disclaimer CSIRO advises that the information contained in this publication comprises general statements based on scientific research. The reader is advised and needs to be aware that such information may be incomplete or unable to be used in any specific situation. No reliance or actions must therefore be made on that information without seeking prior expert professional, scientific and technical advice. To the extent permitted by law, CSIRO (including its employees and consultants) excludes all liability to any person for any consequences, including but not limited to all losses, damages, costs, expenses and any other compensation, arising directly or indirectly from using this publication (in part or in whole) and any information or material contained in it.
CONTENTS
Acknowledgments ...... iv Executive Summary ...... v 1 Introduction ...... 1 2 Methods ...... 2 2.1 Background ...... 2 2.2 General analytical procedures ...... 2 2.3 Sample collection procedures...... 5 2.4 Analytical methods ...... 7 2.5 QA/QC ...... 9 3 Results and discussion ...... 10 3.1 General water quality parameters ...... 10 3.2 Dissolved trace metals ...... 12 3.3 Total metal concentrations in waters ...... 15 3.4 Metals in benthic sediments ...... 18 3.5 Metals associated with suspended solids ...... 26 4 General discussion ...... 32 4.1 Dissolved metals ...... 32 5 Conclusions ...... 34 6 Recommendations ...... 35 7 References ...... 36 Appendix A Maps showing the site sampled in the Southern Narrows and marine sites south‐east of Port Curtis ...... 38 Appendix B Quality Control Data ...... 39 Appendix C Dissolved metal concentrations in waters between the Southern Narrows and Rodds Bay ... 55 Appendix D Total metal concentrations in waters between the Southern Narrows and Rodds Bay ...... 58 Appendix E TSS‐bound metals between the Southern Narrows and Rodds Bay ...... 61 Appendix F Particulate metal concentrations measured in the total and <63 µm benthic sediment fractions between the Southern Narrows and Rodds Bay ...... 66
[Trace metal concentrations in Port Curtis] | i
FIGURES
Figure 1. Sites in Port Curtis where water and sediment samples were collected (6‐8 December 2011) ...... 3 Figure 2. A more detailed map showing the main sampling sites in Port Curtis (6‐8 December 2011) and their proximity to the LNG construction sites ...... 4 Figure 3. Total suspended sediment concentrations (TSS) at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 10 Figure 4. Dissolved aluminium concentrations from all depths at sites between the Southern Narrows to Rodds Bay. Note that an outlier concentration of 334 µg/L measured at 0.5 m depth at Site 3 is not plotted, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 13 Figure 5. Dissolved copper concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 14 Figure 6. Dissolved nickel concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 14 Figure 7. The relationship between the concentrations of total aluminium and total suspended solids measured in water samples...... 18 Figure 8. Total particulate arsenic concentrations of benthic sediment samples collected at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 20 Figure 9. Graphs showing the relationship between copper, lead, nickel and zinc in the <63 µm and total fractions of benthic sediment samples ...... 21 Figure 10. TSS‐bound aluminium concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 26 Figure 11. TSS‐bound copper concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 27 Figure 12. TSS‐bound nickel concentration from all depths at sites between the Southern Narrows to Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 27 Figure 13. TSS‐bound zinc concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the ii |Trace metal concentrations in Port Curtis
dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay ...... 28 Figure 14. Graphs showing the relationship between copper, nickel and zinc bound to TSS and the <63 µm fraction of sediment ...... 31
TABLES
Table 1. Details of samples collected ...... 6 Table 2. Water samples: general data ...... 11 Table 3. Dissolved metal concentrations measured in the water samples ...... 16 Table 4. Total metal concentrations measured in the water samples ...... 17 Table 5. Percentages of silt (<63 µm) in the benthic sediment samples ...... 20 Table 6. Comparison of total metal concentrations measured in benthic sediment samples from Port Curtis in the current study and reported previously by Jones et al. (2005) ...... 21 Table 7. Total metal concentrations in sediments ...... 22 Table 8. Total metal concentrations in sediments (continued) ...... 23 Table 9. Total metal concentrations in the <63 µm sediment fractions ...... 24 Table 10. Total metal concentrations in the <63 µm sediment fractions (continued) ...... 25 Table 11. Suspended sediments: particulate metals concentrations ...... 29 Table 12. Suspended sediments: particulate metals concentrations continued ...... 30 Table 13 Comparison of dissolved metal concentrations measured in the current study with previous data from Port Curtis and with other locations...... 33
[Trace metal concentrations in Port Curtis] | iii
ACKNOWLEDGMENTS
The authors thank Dr Scott Wilson, Mr Dylan Charlesworth and their colleagues at the Central Queensland University (CQU) Campus, Gladstone for logistical support and provision of laboratory and field sampling facilities. John Mitchell, Skipper of the two boats used in this study is thanked for his assistance during field work. Steven Leahy and Ian Hamilton from CSIRO Land and Water are thanked for their assistance with sample processing. Graeme Batley, Jenny Stauber, Andy Steven and Sarah Wood (all CSIRO) are thanked for reviewing earlier drafts of this report and for providing constructive comments. This work was funded by Gladstone Ports Corporation.
iv |Trace metal concentrations in Port Curtis
EXECUTIVE SUMMARY
Following recent concerns about the impacts of dredging in Gladstone Harbour, Gladstone Ports Corporation (GPC) requested assistance from CSIRO to accurately determine the concentrations of metals in the waters and sediments of Port Curtis. The CSIRO group at Lucas Heights, Sydney has extensive experience in low level metals analysis and the assessment of contaminant impacts on aquatic systems. The CSIRO laboratory is fully equipped with state‐ of‐the‐art instrumentation and has a dedicated trace metals clean laboratory which is National Association of Testing Authorities, Australia (NATA) accredited. Its range of sensitive analytical techniques allows the accurate determination of dissolved metal concentrations in marine waters at sub‐μg/L concentrations. There are few laboratories in Australia that possess this capability. The group has worked in Port Curtis previously as part of the Cooperative Research Centre (CRC) for Coastal Zone, Estuary and Waterway Management and has produced a number of peer reviewed publications which detail metal contaminant concentrations in Port Curtis (Jones et al., 2005, Angel et al., 2010). This report describes a study of water and sediment quality within Port Curtis. The study was funded by GPC but conducted independently by CSIRO. Water and sediment samples were collected over the period 6‐8 December 2011 at 21 sites across the Port Curtis region. The study design was based on a sampling campaign conducted by CSIRO in 2003 and 2004 (Angel et al. 2010). Sampling and analysis was conducted using internationally‐accepted protocols and state‐of‐the art QA/QC procedures including the use of Certified Reference Materials. The study gives a three‐day snapshot of trace metal concentrations in Gladstone Harbour. A detailed interpretation of the data was provided including comparison to existing trace metals data for Port Curtis and other coastal locations impacted by anthropogenic activities. The data from the current study were also compared to water and sediment quality guidelines for marine waters (ANZECC/ARMCANZ 2000) that currently apply in Australia.
The findings of the study were as follows: 1. The concentrations of dissolved arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, lead and zinc were below the ANZECC/ARMCANZ marine water quality guideline trigger values that apply in Australia at all 21 sites sampled and the concentrations were relatively low compared to other industrialised harbours. 2. Dissolved aluminium concentrations were above the ANZECC/ARMCANZ (2000) environmental concern level (ECL) of 0.5 µg/L at the majority of sites sampled. It should be noted that there is no reliable guideline value for aluminium in marine waters in Australia and the ECL value is a highly conservative value based on very limited toxicity data. There are no water quality guidelines that apply for aluminium in marine waters in Europe or North America. From the current data set, it was not possible to attribute a specific source of the dissolved aluminium. 3. The dissolved copper concentrations measured in Port Curtis in December 2011 were lower than the ANZECC/ARMCANZ guideline value of 1.3 µg/L. However, the dissolved copper concentrations were noticeably higher than the concentrations measured in the CSIRO surveys in December 2003 and 2004, indicating increased inputs of these metals from various sources, and the concentrations at some sites were only marginally lower than the ANZECC/ARMCANZ guideline value. Dissolved cadmium and zinc concentrations were comparable to those measured in 2003/2004 by CSIRO. 4. A comparison of some of the dissolved metals in Port Curtis and other industrialised harbours around the world (see Table 13 of the main report) shows that Port Curtis compares favourably with most other
[Trace metal concentrations in Port Curtis] | v
harbours and has relatively low metal concentrations despite the large amount of industrial activity and shipping.
5. Apart from arsenic, the concentrations of particulate metals in benthic (seabed) sediments were below the ANZECC/ARMCANZ sediment quality guideline values. Particulate arsenic concentrations exceeded the ANZECC/ARMCANZ ISQG‐low trigger value in two samples from the Narrows and one site off Quoin Island. Previous studies indicate that the source of this arsenic is natural (geological formation in the area) and is not associated with anthropogenic inputs. 6. Metal concentrations in suspended sediments were not elevated and were comparable to the concentrations of metals in the <63 µm (fine) fraction of benthic sediments. This is consistent with the resuspension of fine sediments into the water column. 7. The study did not detect any ‘hot spots’ of metal concentrations. There was no detectable elevation of metal concentrations at sites where dredging was being conducted. Recommendations for future work are also provided in Section 6 of the report.
vi |Trace metal concentrations in Port Curtis
1 INTRODUCTION
Following recent concerns about the impacts of dredging in Gladstone Harbour, Queensland, Gladstone Ports Corporation (GPC) requested assistance from CSIRO to accurately determine the concentrations of metals in the waters and sediments of Port Curtis. The CSIRO group at Lucas Heights, Sydney has extensive experience in low level metals analysis and the assessment of contaminant impacts on aquatic systems. The CSIRO laboratory is fully equipped with state‐of‐the‐art instrumentation and has a dedicated trace metals clean laboratory. which is National Association of Testing Authorities, Australia (NATA) accredited. Its range of sensitive analytical techniques allows the accurate determination of dissolved metal concentrations in marine waters at sub‐μg/L concentrations. There are few laboratories in Australia that possess this capability. The group has worked in Port Curtis previously as part of the Cooperative Research Centre (CRC) for Coastal Zone, Estuary and Waterway Management and has produced a number of peer reviewed publications which detail metal contaminant concentrations in Port Curtis (Jones et al. 2005, Angel et al. 2010). This report describes a study of water and sediment quality in Port Curtis in December 2011 and gives a three‐day snapshot of trace metal concentrations. The study was funded by GPC but conducted independently by CSIRO. The study design was based on a previous sampling by CSIRO in 2003 and 2004 (Angel et al. 2010). Sampling and analysis was conducted using internationally‐accepted protocols and state‐of‐the art QA/QC procedures including the use of Certified Reference Materials. A detailed interpretation of the data is provided including comparison to existing trace metals data for Port Curtis and other coastal locations impacted by anthropogenic activities. The data from the current study were also compared to water and sediment quality guidelines for marine waters (ANZECC/ARMCANZ, 2000) that currently apply in Australia.
[Trace metal concentrations in Port Curtis] | 1
2 METHODS
2.1 BACKGROUND
The study design was based on the sampling campaigns conducted by Angel et al. (2010) in 2003 and 2004. Sites for water and sediment sample collection were chosen to cover the general area of Port Curtis, the southern Narrows and Rodds Bay, with more detailed sampling at sites close to the current dredging and liquefied natural gas (LNG) construction zones (Figure 1 and 2, Appendix A). Depth profile samples at various points in the water column (typically surface, mid‐depth and near bottom) were collected at selected sites. We had initially planned to also sample two sites on the eastern side of Facing Island including the offshore dredge spoil dumping grounds, however, safety considerations arising from the poor weather conditions at the time of sampling prevented the sampling of these sites. Instead, additional samples were collected from within the Harbour. The sampling program was executed by trained CSIRO staff with logistical support from staff from Central Queensland University (CQU). CSIRO provided ultraclean sampling bottles, filtration apparatus, and water sampling equipment. Two survey boats, a grab sampler for sediment collection and laboratory facilities for sample processing (e.g. filtrations) were provided by the Centre for Environmental Management, CQU. The water and sediment sampling was performed between 6 and 8 December 2011. The sampling was conducted over a number of tidal cycles and there were periods of rainfall on 6 December whilst conditions were fine on 7 and 8 December. Full details of the sampling locations, water samples collected and sampling dates are given in Table 1. For the purpose of quality control, field blanks to assess background contamination and site duplicates were collected from at approximately 10% of the sample sites to assess background contamination and site variability respectively. Detailed descriptions of the field and laboratory protocols employed in the study are given in the ensuing sections.
Dissolved mercury was not included in this study as the concentrations in Port Curtis were expected to be very low (low ng/L) and would require costly specialist sampling and analysis. Mercury is known to biomagnify in food webs so measuring mercury concentrations in biota (Jones et al. 2005) is a far more effective means of assessing the risks posed by this metal.
2.2 GENERAL ANALYTICAL PROCEDURES
The analysis of trace metals at sub‐μg/L concentrations in marine waters is acknowledged to be technically challenging and necessitates the application of rigorous protocols during sample container preparation, sample collection and analysis, to ensure the accuracy of results. State‐ of‐the‐art protocols, as outlined by USEPA (1996) and Apte et al. (2002) were used throughout this work. Full details of the methods used are given below.
All plastic ware was acid‐washed prior to use with a minimum soak for 24 hours in 10% v/v nitric acid (Merck, analytical reagent grade). One‐litre low‐density polyethylene (Nalgene)
2 |Trace metal concentrations in Port Curtis
bottles were used for water sample collection. Prior to use, the bottles were rigorously cleaned using a three‐stage sequence. First, the bottles and caps were submerged for a minimum of two hours in 2% Extran detergent solution, followed by rinsing with copious amounts of deionised water (Milli‐Q, 18 MΩ/cm, Millipore, Australia). The bottles were then soaked for a minimum of 24 hours in 10% nitric acid (Merck, AR grade) contained in a covered plastic tank. They were then rinsed five times with Milli‐Q (MQ) high purity water and filled with 1% high purity nitric acid (Merck Tracepur) in MQ water, capped and left to stand for at least 48 hours. After this time, the bottles were rinsed five times with MQ water, ‘double‐ bagged’ in two polyethylene zip‐lock bags, and stored in sealed containers to avoid contamination.
Figure 1. Sites in Port Curtis where water and sediment samples were collected (6‐8 December 2011)
[Trace metal concentrations in Port Curtis] | 3
Figure 2. A more detailed map showing the main sampling sites in Port Curtis (6‐8 December 2011) and their proximity to the LNG construction sites
4 |Trace metal concentrations in Port Curtis
2.3 SAMPLE COLLECTION PROCEDURES
2.3.1 Water sample collection
All water samples were collected by CSIRO staff using rigorous ‘clean hands/dirty hands’ sampling protocols to avoid sample contamination (USEPA 1996, Angel et al. 2010, Ahlers et al. 1990). This included the wearing of clean vinyl gloves for the handling of all sample bottles, and sampling equipment and storage of all equipment in zip‐lock bags when not in use. Surface water samples were collected from 31 sites using a purpose‐built Perspex pole sampler. The ‘clean‐hands’ person was responsible for handling the 1 L Nalgene bottles, which involved removing bottles from zip‐lock bags and carefully placing them into a holder installed on the Perspex pole sampler. The ‘dirty hands’ person then used the pole sampler to collect samples by rapidly submerging the sample bottle on the pole to 0.5 m water depth to collect the sample. Each bottle was rinsed with the sample by first collecting an initial sample and then emptying it from the bottle by lifting the pole sampler and inverting. The submersion was then repeated to collect the actual sample. The ‘clean hands’ person then removed the bottle from the pole sampler, replaced the lid, replaced the bottle back into two zip‐lock bags and stored them in the on‐board laboratory refrigerator until sample processing and preservation. Water samples from the middle and near‐bottom water depth were collected at selected sites using a Niskin water sampler. The Niskin sampler had been previously cleaned by soaking in 2% nitric acid and washed with deionised water. The Niskin sampler was conditioned for at least 15 minutes at each depth of water collection. After this time the operator moved the sampler up one metre and back down to the sample depth and the messenger weight was deployed to trigger the closure of the sampler. The sampler was then returned to the deck of the boat and the ‘dirty hands’ operator activated the tap while the ‘clean hands’ operator rinsed the low density polyethylene bottles (Nalgene) with the dispensed sample and then filled them. The ‘clean hands’ person then replaced the bottles back into two zip‐lock bags and transferred them into the on‐board laboratory refrigerator until sample processing and preservation. When not in use (e.g. between sites and during overnight storage), the Niskin sampler was stored in a clean plastic bag housed within a plastic container.
Measurements of salinity, pH, and turbidity were performed on subsamples of waters collected with the pole‐ and Niskin‐ samplers immediately after water samples were collected onboard the boat. The salinity was measured using a LF 320 WTW conductivity meter (Weilheim, Germany) and electrode (TetraCon 325, WTW). The pH was measured using a Wissenschaftlich‐Technische Werkstattan (WTW, Weilheim, Germany) meter equipped with a pH probe (Orion sure‐flow combination pH 9165BN) calibrated at regular intervals with pH 4.0 and 7.0 buffer (Orion Pacific, Sydney, NSW, Australia) solutions. The turbidity was measured using an Analite 156 Turbidimeter (Mc Van Instruments, Victoria, Australia) equipped with a nephelometer probe, and calibrated daily using deionised water and a freshly prepared 40 NTU formazin standard.
[Trace metal concentrations in Port Curtis] | 5
Table 1. Details of samples collected
Site Name Sample depth (m) Date Time Site Coordinates Water Sediment Southing Easting Site 1, 0.5 m 0.5 5 6‐Dec‐11 13:40 23.6713 151.12967 Site 1, 2 m, Site Duplicate 1 2 5 6‐Dec‐11 14:10 23.6713 151.12967 Site 1, 2 m, Site Duplicate 2 2 5 6‐Dec‐11 14:20 23.6713 151.12967 Site 1, 4 m 4 5 6‐Dec‐11 14:00 23.6713 151.12967 Site 2, 0.5 m 0.5 4.5 6‐Dec‐11 14:55 23.69922 151.14312 Site 3, 0.5 m 0.5 10.5 6‐Dec‐11 15:30 23.7391 151.1643 Site 3, 5 m 5 10.5 6‐Dec‐11 15:35 23.7391 151.1643 Site 3, 10 m 10 10.5 6‐Dec‐11 15:40 23.7391 151.1643 Site 4, 0.5 m 0.5 4 6‐Dec‐11 16:10 23.75898 151.17196 Site 4, 0.5 m 0.5 4 7‐Dec‐11 10:35 23.75898 151.17196 1Site 5, 0.5 m 0.5 6 7‐Dec‐11 14:35 23.76782 151.18552 Site 5, 1.5 m 1.5 6 7‐Dec‐11 14:43 23.76782 151.18552 Site 5, 3.5 m 3.5 6 7‐Dec‐11 14:48 23.76782 151.18552 Site 5, 5.5 m 5.5 6 7‐Dec‐11 14:52 23.76782 151.18552 Site 6, 0.5 m 0.5 7 7‐Dec‐11 15:03 23.7707 151.1876 Site 6, 6 m 6 7 7‐Dec‐11 15:03 23.7707 151.1876 Site 7, 0.5 m, Site Duplicate 1 0.5 4 7‐Dec‐11 15:26 23.77869 151.16849 Site 7, 0.5 m, Site Duplicate 2 0.5 4 7‐Dec‐11 15:30 23.77869 151.16849 Site 8, 0.5 m 0.5 4.5 6‐Dec‐11 16:40 23.78181 151.1823 Field blank 2 (Site 8) ‐ ‐ 6‐Dec‐11 16:50 23.78181 151.1823 Site 9, 0.5 m 0.5 7.5 7‐Dec‐11 10:55 23.78945 152.19295 Site 9, 3 m 3 7.5 7‐Dec‐11 11:05 23.78945 152.19295 Site 9, 6 m 6 7.5 7‐Dec‐11 11:10 23.78945 152.19295 Site 10, 0.5 m, Site Duplicate 1 0.5 4 7‐Dec‐11 9:55 23.8062 151.17707 Site 10, 0.5 m, Site Duplicate 2 0.5 4 7‐Dec‐11 10:00 23.8062 151.17707 Field blank 3 (Site 10) ‐ ‐ 7‐Dec‐11 10:15 23.8062 151.17707 Site 11, 0.5 m 0.5 6.5 6‐Dec‐11 11:55 23.79891 151.20704 1Site 12, 0.5 m 0.5 6 7‐Dec‐11 14:20 23.80333 151.22534 Site 13, 0.5 m 0.5 4 6‐Dec‐11 11:25 23.7993 151.22569 Field blank 1 (Site 13) ‐ ‐ 6‐Dec‐11 11:35 23.7993 151.22569 Site 14, 0.5 m 0.5 3.5 7‐Dec‐11 11:40 23.81188 151.22654 Site 15, 0.5 m 0.5 10.5 7‐Dec‐11 13:57 23.82026 151.25314 Site 16, 0.5 m, Site Duplicate 1 0.5 3.5 6‐Dec‐11 10:30 23.83427 151.26223 Site 16, 0.5 m, Site Duplicate 2 0.5 3.5 6‐Dec‐11 10:40 23.83427 151.26223 Site 17, 0.5 m 0.5 13.5 7‐Dec‐11 13:37 23.82202 151.28621 Site 18, 0.5 m 0.5 7 8‐Dec‐11 10:30 23.92665 151.36468 Site 19, 0.5 m 0.5 7.5 8‐Dec‐11 9:40 23.98 151.4342 Site 20, 0.5 m, Site Duplicate 1 0.5 5 8‐Dec‐11 8:26 24.06734 151.64541 Site 20, 0.5 m, Site Duplicate 2 0.5 5 8‐Dec‐11 8:29 24.06734 151.64541 Field blank 4 (Site 20) ‐ ‐ 8‐Dec‐11 8:29 24.06734 151.64541 Site 21, 0.5 m 0.5 11 8‐Dec‐11 8:54 24.01025 151.583 1No benthic sediment sample collected
6 |Trace metal concentrations in Port Curtis
2.3.2 Water sample pretreatment
On return to the Centre for Environmental Management (CEM) laboratory at the CQU Gladstone campus, water samples for trace metals analyses were filtered through acid‐washed 0.45 µm Millipore membrane filters using polycarbonate filtration apparatus (Sartorius) using a vacuum generated by an electric pump. All filtration assemblies were rigorously cleaned before processing each sample by first filtering 100 mL volumes of 10% v/v nitric acid (Merck, Tracepur) solution followed by two volumes of approximately 150 mL of deionised water, and finally, a 50 mL volume of sample. The 50 mL volume of sample was swirled in the top and bottom compartments of the filtration rig to pretreat the filtration rig, before being poured into the filtrate receiving bottle, shaken to pretreat the bottle, and discarded to waste. The sample was then filtered and preserved by addition of 2 mL/L concentrated nitric acid (Merck, Tracepur). The volume of sample filtered through each filter depended on the turbidity and was generally between 450‐800 mL. Samples for suspended solids‐bound metals and total suspended sediments (TSS) analyses were acquired by filtering known volumes of water through pre‐weighed 0.45 µm Millipore membrane filters cleaned using the same procedure as above. The upper compartment of the filtration apparatus and the filter were then rinsed with approximately 20 mL of MQ water to remove salts and rinse suspended solids from the apparatus onto the filter. The filters were placed into acid‐washed polycarbonate vials for transfer to CSIRO laboratories, Sydney, after which they were oven dried at 60oC, cooled to room temperature, and weighed to determine the mass of the dry filter and suspended solid. This procedure was repeated three times to ensure the mass was consistent, after which, the filters were stored at room temperature until required for analysis. The TSS concentration (mg/L) of the water samples was determined gravimetrically by dividing the difference in the mass of the filter before and after filtration by the volume of sample filtered.
2.3.3 Benthic sediment sampling
Benthic sediments were collected at each sample site (Table 1) using a stainless steel Van Veen grab sampler attached to an onboard winch system. The grab had an area of approximately 400 cm2 (20 cm × 20 cm) and typical grab depth of 10 cm. Each of the sediments was collected after all water samples were collected at each site so that sediment disturbance would not affect the water samples. Approximately 300 g of sediment from the 0‐2 cm surface layer was transferred from the grab sampler into zip‐lock bags using a clean plastic spatula. Following collection, samples were ‘triple‐bagged’ and placed in the onboard refrigerator to keep them cool in the field. Upon return to the CEM laboratory, the sediments were stored at 4°C.
2.4 ANALYTICAL METHODS
Water and sediment samples were subsequently transported to the CSIRO laboratory at Lucas Heights, Sydney, by courier and analysed for a range of trace metals. Full details are given in the following sections.
[Trace metal concentrations in Port Curtis] | 7
2.4.1 Dissolved metals analyses
A sub‐sample of each water sample was taken for direct metals analysis using inductively coupled atomic emission spectrometry (ICPAES) (Varian730 ES) (in‐house method C‐229) and operating instructions recommended by the manufacturer. The instrument was calibrated using matrix‐matched standards. The marine water samples were also subjected to complexation and solvent extraction prior to the analysis of cadmium, cobalt, copper, lead, nickel and zinc in order to achieve lower detection limits by removing the salt matrix and pre‐concentrating the metals (in‐house method C‐208). The extraction procedure allowed the pre‐concentration of metals by a factor of 25, making them easier to quantify. The method used a dithiocarbamate complexation/solvent extraction spectrometric method based on the procedure described by Magnusson and Westerlund (1981). The major differences were the use of a combined sodium bicarbonate buffer/ammonium pyrrolidine dithiocarbamate reagent (Apte and Gunn 1987) and 1,1,1‐trichloroethane as the extraction solvent in place of Freon. In brief, sample aliquots (250 mL) were buffered to pH 5 by addition of the combined reagent and extracted with two X 10 mL portions of triple‐distilled trichloroethane. The extracts were combined and the metals back‐extracted into 1 mL of concentrated nitric acid (Merck Tracepur). The back extracts were diluted to a final volume of 10 mL by addition of deionised water and analysed by inductively coupled plasma‐mass spectrometry (ICPMS) (Agilent, 7500CE) (in‐house method C‐209), using the operating conditions recommended by the manufacturer. Dissolved arsenic concentrations were determined by hydride‐generation atomic absorption spectrometry, using procedures based on the standard methods described by APHA (1998) (in‐ house method C‐212). Samples were first digested by addition of potassium persulfate (1% mass/volume final concentration) and heating to 120°C for 30 minutes in an autoclave. Hydrochloric acid (Merck, Tracepur), (3 M final concentration) was then added to the samples. Pentavalent arsenic was then pre‐reduced to arsenic (III) by addition of potassium iodide (1% m/v final concentration) and ascorbic acid (0.2% m/v final concentration) and left standing for at least 30 minutes at room temperature prior to analysis. Arsenic concentrations were then measured by hydride‐generation atomic absorbance spectrometry (AAS) using a Varian VGA system operating under standard conditions recommended by the manufacturer. Arsenic (III) in solution was reduced to arsine by borohydride, which was stripped with nitrogen gas into a silica tube, electrically heated at 925°C. Heating converted arsine into arsenic vapour whose atomic adsorption was measured. The analysis provides total dissolved arsenic concentrations in marine waters.
2.4.2 Total suspended solids analyses
The dry pre‐weighed 0.45 µm filter membranes (Millipore) containing the suspended solids were subjected to a microwave‐assisted aqua‐regia digestion (in‐house method C‐223). This procedure involved the transfer of the dried filter membranes into pre‐cleaned microwave accelerated reaction system (MARS) express digestion vessels to which 9 mL of concentrated nitric acid (Merck, Tracepur) and 3 mL of concentrated hydrochloric acid (Merck, Tracepur) were added. The digestion vessels were heated in a MARS digestion system (in‐house method CE‐223). Once cool, digests were diluted to a final volume of 40 mL with deionised water. The concentration of metals in the final digest solutions was analysed using a combination of ICP‐ AES (Varian 730 ES) and ICP‐MS (Agilent 7500 CE) (in‐house methods C‐229 and C‐209
8 |Trace metal concentrations in Port Curtis
respectively). The spectrometers were operated under the standard operating conditions recommended by the manufacturer.
2.4.3 Sediment fractionation
Each sediment sample was homogenised with a clean plastic spatula in a clean plastic container. A portion of known mass was then wet‐sieved (<63 µm) into another clean plastic container so that there was two portions of each sample (total and <63 µm). Each portion was oven‐dried at 90°C for 48 hours, followed by 100°C for 2 hours, cooled in a desiccator and weighed to determine the <63 µm sediment fraction. Then a mortar and pestle were used to grind each fraction of the sediments to a fine powder in preparation for analysis of sediment‐ bound metals.
2.4.4 Total particulate metals analyses in sediments
Approximately 0.5 g of each dry total and <63 µm sediment powder was accurately weighed and subjected to a microwave‐assisted aqua‐regia digestion (in‐house method C‐223). This procedure involved the dried powder being transferred into a pre‐cleaned microwave‐assisted reaction system (MARS, CEM Milestone) express digestion vessels to which 9 mL of concentrated nitric acid (Merck Tracepur) and 3 mL of concentrated hydrochloric acid (Merck Tracepur) was added. The digestion vessels were heated in the MARS digestion system using in‐house method CE‐223. Once cool, digests were diluted to a final volume of 40 mL with deionised water. The concentration of metals in the final digest solutions was analysed using a combination of ICP‐AES (Varian 730 ES) and ICP‐MS (Agilent 7500 CE) (in‐house methods C‐229 and C‐209 respectively). The spectrometers were operated under the standard operating conditions recommended by the manufacturer. The concentrations of 21 trace elements were quantified in the sediment samples.
2.5 QA/QC
Rigorous field and laboratory quality assurance procedures were adopted in this study. Field blanks, field duplicate samples, method blanks, certified reference materials, spike recovery tests and method duplicates were an integral part of the field sampling and laboratory analysis quality control scheme. To check on the precision of the analytical procedures, at least 10% of the water and sediment samples were analysed in duplicate. To check on potential matrix interferences at least 10% of the filtered water samples had spike recoveries performed. Detection limits (3 sigma) were calculated using within‐batch blank concentration data derived over the course of the sample analyses. This approach gives a more realistic assessment of limits of detection than reliance on historical data which is the approach used in the majority of routine analytical laboratories. To confirm analytical accuracy, portions of certified reference materials from the National Research Council of Canada (NRC) were analysed with each batch of samples, whenever a suitable reference material was available. Reference standards have certified concentrations of elements for a range of sample matrices such as seawater and sediment, allowing the performance of the analytical procedures to be assessed by a comparison of the results obtained with the certified concentrations. The following reference materials were used: CASS‐4 and CASS‐5 for metals in saline waters, and PACS‐2 for particulate metals in sediments.
[Trace metal concentrations in Port Curtis] | 9
3 RESULTS AND DISCUSSION
3.1 GENERAL WATER QUALITY PARAMETERS
General water quality parameter (total suspended solids, turbidity, pH and salinity) measurements are shown in Table 2. The pH of water samples in the study were in the narrow range of 7.80 to 8.21. Salinity also varied over a narrow range of 33.3 to 36.7 PSU. The turbidity varied from 1.2 to 22.5 nephelometric turbidity units (NTU) and was within the range reported by the Department of Environment and Resource Management (DERM) for Port Curtis (DERM 2012). Total suspended solids (TSS) concentrations were variable and in the range 3‐74 mg/L. Turbidity and TSS are closely related physical variables and as expected, there was a statistically significant correlation between the two variables (r=0.662, p<0.05). TSS concentrations are depicted graphically in Figure 3. The highest TSS concentrations were observed in the dredge zone. TSS concentrations were generally higher than measured in the previous CSIRO field studies conducted in 2003 and 2004 (Figure 3) but this could be due to multiple factors such as different weather conditions, increased shipping activity in the Harbour and dredging. Apart from the depth profile taken at Site 9, there was little evidence of TSS increasing with depth.
80 .
60
40
20 Mean harbour, 2003 & 2004 Total suspended solids (mg/L) solids (mg/L) suspended Total 0 0123456789101112131415161718192021 Site (Narrows to Rodd's Bay)
Figure 3. Total suspended sediment concentrations (TSS) at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
10 |Trace metal concentrations in Port Curtis
Table 2. Water samples: general data
Site Name pH Salinity (PSU) Turbidity (NTU) Suspended solids (mg/L) Site 1, 0.5 m 7.81 34.1 7.3 14.4 Site 1, 2 m, Duplicate 1 7.88 34.3 12.0 21.1 Site 1, 2 m, Duplicate 2 7.89 34.5 9.0 17.7 Site 1, 4 m 7.85 34.2 8.2 14.9 Site 2, 0.5 m 7.94 34.1 6.9 34.8 Site 3, 0.5 m 8.00 33.8 13.0 17.5 Site 3, 5 m 7.98 33.8 12.0 22.0 Site 3, 10 m 7.97 34.1 11.5 21.7 Site 4, 0.5 m 8.03 36.6 8.5 22.9 Site 4, 0.5 m 7.97 34.7 20.5 66.6 Site 5, 0.5 m 7.98 36.6 17.3 61.3 Site 5, 1.5 m 7.98 36.7 17.5 57.3 Site 5, 3.5 m 7.97 36.7 21.4 43.5 Site 5, 5.5 m 7.95 36.5 21.6 48.8 Site 6, 0.5 m 7.92 36.6 20.1 44.9 Site 6, 6 m 7.93 36.5 20.4 24.0 Site 7, 0.5 m, Duplicate 1 8.03 36.5 9.5 21.5 Site 7, 0.5 m, Duplicate 2 8.03 36.4 8.0 ‐ Site 8, 0.5 m 8.01 37.1 8.7 23.0 Site 9, 0.5 m 8.00 35.7 15.1 59.8 Site 9, 3 m 8.01 35.8 22.5 69.1 Site 9, 6 m 8.02 35.7 17.5 73.6 Site 10, 0.5 m, Duplicate 1 8.00 34.5 13 6.7 Site 10, 0.5 m, Duplicate 2 8.02 34.7 13.4 24.8 Site 11, 0.5 m 8.00 33.6 13.9 49.9 Site 12, 0.5 m 8.00 36.3 14.0 47.9 Site 13, 0.5 m 8.05 33.3 10.6 37.5 Site 14, 0.5 m 8.04 35.6 18.2 46.9 Site 15, 0.5 m 7.93 35.9 9.2 52.0 Site 16, 0.5 m, Duplicate 1 7.80 33.5 15.2 11.6 Site 16, 0.5 m, Duplicate 2 7.83 33.6 15 10.7 Site 17, 0.5 m 8.05 35.7 7.9 33.7 Site 18, 0.5 m 8.20 34.0 4.3 15.1 Site 19, 0.5 m 8.19 33.9 3.0 20.3 Site 20, 0.5 m, Duplicate 1 8.16 33.5 1.8 15.6 Site 20, 0.5 m, Duplicate 2 8.16 33.5 1.2 3.1 Site 21, 0.5 m 8.21 33.4 1.7 5.2
[Trace metal concentrations in Port Curtis] | 11
3.2 DISSOLVED TRACE METALS
The results for field blanks and duplicates and full details of QA/QC for analyses are presented in Appendix B. The data for reference materials, spike recoveries and blanks were all within acceptable limits indicating satisfactory analytical performance. Dissolved metals data are shown in Table 3 and are also presented graphically (see Appendix C and Figures 4, 5 and 6). The metal concentrations in all samples were below the ANZECC/ARMCANZ guideline trigger values that apply for 95% species protection in marine waters.
The following general trends were noted in the data:
(i) There was no consistent relationship between sample depth and concentration for any of the dissolved metals measured in the current study. This likely indicates that Port Curtis is well mixed by the strong tidal currents.
(ii) There was no indication of localised elevation of dissolved trace metal concentrations in the region of the Harbour that is currently being dredged.
(iii) Depth profile samples showed no consistent trends apart from at Site 3 (close to the mouth of Graham’s Creek Inlet) where the concentrations of several metals (aluminium, cadmium, cobalt, copper, manganese, nickel, lead and zinc) were higher in the surface water sample compared to the middle and bottom samples. This trend may be caused by runoff from Graham’s Creek.
(iv) The concentrations of dissolved aluminium, iron, lead and zinc displayed no discernible trends across Port Curtis. Dissolved nickel concentrations increased from south to north. Dissolved arsenic concentrations increased from north to south. The lowest cadmium and copper concentrations were observed at the southern‐most sites.
(v) Dissolved cobalt and manganese concentrations were highest in the samples collected from the Narrows indicating a source of these metals in this region. This trend in manganese concentrations is consistent with data reported in the previous CSIRO study (Angel et al. 2010) which also indicated that the Narrows could be a source of dissolved nickel.
(vi) Dissolved aluminium concentrations were in the range 1.0‐21.1 µg/L at all but one site (Site 3, 0.5 m), which had a suspected outlier concentration of 334 µg/L. The dissolved aluminium did not exhibit a clear trend in the study area. All dissolved aluminium concentrations were above 0.5 µg/L, which is the Environmental Concern Level (ECL) in the Australia/New Zealand marine water quality guidelines (ANZECC/ARMCANZ 2000). Note that the ECL is not formally considered as a guideline value because of its low reliability.. (vii) The dissolved copper was in the range 0.078‐1.06 µg/L (Table 3 and 4, Appendix B and C). Dissolved copper concentrations were broadly elevated in the harbour compared to Sites 18‐21 outside the harbour, probably because of multiple sources. The average (± standard deviation) dissolved copper concentration measured in Port Curtis in the current study was 0.82±0.0.09 µg/L, which was marginally higher than the concentrations of 0.53±0.08
12 |Trace metal concentrations in Port Curtis
and 0.50±0.20 µg/L measured in the harbour in 2003 and 2004, respectively (Angel et al., 2010). However, in the current study, more sites were sampled in the inner harbour and less in the outer harbour than the study by Angel et al. (2010), which may explain the higher average harbour concentration. Nevertheless, it is of note that dissolved copper appears to be higher in the current study than when measured in Port Curtis in December 2003 and 2004 and some concentrations were only marginally lower than the trigger value (Angel et al. 2010).
(viii) The concentration of dissolved nickel ranged from 0.16 to 0.82 µg/L. The dissolved nickel was lowest at Sites 18‐21 outside the harbour, and exhibited a trend of increasing concentration as the sites were closer to the Narrows, with the highest concentration measured at the most northerly site in the Narrows. This trend is similar to that measured by Angel et al. (2010), and is likely to indicate a natural source of nickel in the Narrows. The average (± S.D.) dissolved nickel measured in the harbour in the current study was 0.52±0.10 µg/L, which was marginally higher than the concentrations of 0.35±0.06 and 0.33±0.14 µg/L measured in the harbour in 2003 and 2004, respectively (Angel et al. 2010). However, in the current study more sites were sampled in the inner harbour and less in the outer harbour than the study by Angel et al. (2010), which may explain the higher average harbour concentration.
10
8 .
g/L) g/L) 6 μ
4
Dissolved Al ( 2 ANZECC/ARMCANZ ECL
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
Figure 4. Dissolved aluminium concentrations from all depths at sites between the Southern Narrows to Rodds Bay. Note that an outlier concentration of 334 µg/L measured at 0.5 m depth at Site 3 is not plotted, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
[Trace metal concentrations in Port Curtis] | 13
1500 ANZECC/ARMCANZ 95% trigger value
1200 .
900
600
Mean harbour, 2003 & 2004 300 Dissolved Cu (ng/L) Dissolved Cu (ng/L)
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
Figure 5. Dissolved copper concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
1000 ANZECC/ARMCANZ 95% trigger value = 70 μg/L
800 .
600
400
Mean harbour, 2003 & 2004
Dissolved Ni (ng/L) Ni (ng/L) Dissolved 200
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
Figure 6. Dissolved nickel concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
14 |Trace metal concentrations in Port Curtis
3.3 TOTAL METAL CONCENTRATIONS IN WATERS
Total metal concentrations are presented in Table 4 and graphically in Appendix D. These data are included in this report to allow comparison with other studies that did not measure dissolved metal concentrations. Total metal concentrations are poor indicators of metal toxicity as they are largely determined by the particulate metals content of the sample which is generally far less bioavailable than metals that are in dissolved forms.
Calculations indicated that for aluminium, iron, manganese and lead, 98, 99, 89 and 94% respectively of the total metal concentration could be attributed to metals within the suspended sediment fraction. Cobalt, chromium and zinc had similar TSS contributions with mean percentages of 80, 75 and 77%, respectively. Arsenic, copper and nickel had the lowest partitioning to the TSS fraction with mean percentages of 29, 45 and 46%, respectively. The dependence of total metal concentrations on TSS is illustrated for the case of aluminium in Figure 13. As can be seen, there is a strong relationship between total aluminium concentration and TSS (r=0.84).
[Trace metal concentrations in Port Curtis] | 15
Table 3. Dissolved metal concentrations measured in the water samples
Sample description Al As Cd Co Cr Cu Fe Mn Ni Pb Zn (µg/L (µg/L (ng/L (ng/L (µg/L (ng/L (µg/L (µg/L (ng/L (ng/L (ng/L
) ) ) ) ) ) ) ) ) ) ) Field blank 1 (Site 13) <1 <0.09 <3 <2 0.4 <15 <1.5 <0.1 <32 <16 93 Field blank 2 (Site 8) <1 <0.09 <3 <2 <0.4 <15 <1.5 <0.1 <32 <16 101 Field blank 3 (Site 10) <1 <0.09 <3 <2 <0.4 46 <1.5 <0.1 36 <16 141 Field blank 4 (Site 20) <1 <0.09 <3 <2 <0.4 <15 <1.5 <0.1 41 <16 170 Site 1, 0.5 m 2 0.79 3 153 <0.4 588 <1.5 5.4 746 <16 109 Site 1, 2 m, Duplicate 1 1 0.77 3 161 <0.4 630 <1.5 5.2 808 <16 139 Site 1, 2 m, Duplicate 2 2 0.68 5 144 <0.4 590 <1.5 4.3 725 <16 259 Site 1, 4 m 3 0.68 4 171 <0.4 643 <1.5 5.6 823 16 266 Site 2, 0.5 m 2 0.82 3 93 <0.4 769 1.5 2.2 706 <16 120 Site 3, 0.5 m 330 1.03 8 144 <0.4 1060 214 6.5 662 85 623 Site 3, 5 m 3 0.91 6 51 <0.4 921 1.6 0.8 626 16 152 Site 3, 10 m 3 0.79 3 50 <0.4 767 <1.1 0.6 508 <16 231 Site 4, 0.5 m 5 1.02 5 30 <0.4 995 <1.5 0.2 557 <16 1620 Site 4, 0.5 m 3 0.91 5 45 <0.4 824 <1.5 0.4 591 <16 225 Site 5, 0.5 m 2 0.84 4 72 <0.4 886 <1.5 2 612 <16 306 Site 5, 1.5 m 21 0.92 4 75 <0.4 938 12 2 640 17 504 Site 5, 3.5 m 2 0.82 4 68 <0.4 915 <1.5 2 651 20 406 Site 5, 5.5 m 2 0.90 5 66 <0.4 926 <1.5 1 621 <16 330 Site 6, 0.5 m 1 0.92 3 64 <0.4 880 <1.5 1 565 <16 303 Site 6, 6 m 1 0.97 6 62 <0.4 857 <1.5 1 584 <16 726 Site 7, 0.5 m, 6 0.95 4 61 <0.4 849 <1.5 3 531 <16 261 Duplicate 1 Site 7, 0.5 m, 5 1.04 5 55 <0.4 806 <1.5 2 533 <16 214 Duplicate 2 Site 8, 0.5 m 3 0.96 5 39 <0.4 790 <1.5 0.5 525 <16 200 Site 9, 0.5 m 5 0.92 5 29 <0.4 843 1.8 0.4 706 <16 348 Site 9, 3 m 4 0.94 4 24 <0.4 815 <1.5 <0.1 749 <16 365 Site 9, 6 m 3 0.90 6 22 <0.4 766 <1.5 <0.1 635 <16 265 Site 10, 0.5 m, 4 1.00 4 51 <0.4 788 <1.5 1.7 479 <16 232 Duplicate 1 Site 10, 0.5 m, 4 1.05 4 52 <0.4 786 <1.5 1.7 722 <16 353 Duplicate 2 Site 11, 0.5 m 4 1.06 9 24 <0.4 801 <1.5 <0.1 488 <16 201 Site 12, 0.5 m 4 0.98 4 53 <0.4 837 <1.5 1.9 516 <16 325 Site 13, 0.5 m 4 1.12 5 34 <0.4 625 <1.5 0.4 359 <16 149 Site 14, 0.5 m 5 1.00 4 35 <0.4 911 <1.5 0.9 552 <16 531 Site 15, 0.5 m 4 0.96 3 24 <0.4 752 <1.5 0.2 475 <16 243 Site 16, 0.5 m, 5 1.00 6 35 <0.4 792 <1.5 1.7 345 <16 331 Duplicate 1 Site 16, 0.5 m, 4 1.07 3 38 <0.4 907 <1.5 2.0 423 <16 255 Duplicate 2 Site 17, 0.5 m 4 1.05 3 24 <0.4 645 <1.5 0.8 443 <16 203 Site 18, 0.5 m 4 1.15 <3 23 <0.4 149 <1.5 0.1 200 <16 439 Site 19, 0.5 m 3 1.24 <3 25 <0.4 120 <1.5 <0.1 217 <16 18
16 |Trace metal concentrations in Port Curtis
Sample description Al As Cd Co Cr Cu Fe Mn Ni Pb Zn (µg/L (µg/L (ng/L (ng/L (µg/L (ng/L (µg/L (µg/L (ng/L (ng/L (ng/L
) ) ) ) ) ) ) ) ) ) ) Site 20, 0.5 m, 2 1.14 <3 37 <0.4 127 <1.5 1 212 19 27 Duplicate 1 Site 20, 0.5 m, 2 1.27 <3 39 <0.4 151 <1.5 1 216 <16 40 Duplicate 2 Site 21, 0.5 m 2 1.03 <3 12 <0.4 78 <1.5 <0.1 163 <16 20 2.3‐ 7000 1500 95% trigger value1 ‐ 5500 1000 27.4 1300 ‐ 802 4400 4.5 0 0 1ANZECC/ARMCANZ, 2000 trigger value for 95% species protection in marine waters
Table 4. Total metal concentrations measured in the water samples
Sample name Al As Cd Co Cr Cu Fe Mn Ni Pb Zn (µg/L) Field blank 1 (Site 13) <8 <0.01 <0.02 <0.01 0.30 <0.17 2 <0.02 <0.03 <0.04 0.30 Field blank 2 (Site 8) <8 <0.01 <0.02 <0.01 <0.04 <0.17 <1.7 <0.02 <0.03 <0.04 0.24 Field blank 3 (Site 10) <8 <0.01 <0.02 <0.01 0.31 <0.17 <1.7 <0.02 <0.03 0.06 0.25 Field blank 4 (Site 20) <8 <0.01 <0.02 <0.01 <0.04 <0.17 <1.7 <0.02 <0.03 <0.04 0.35 Site 1, 0.5 m 590 1.04 <0.02 0.34 1.09 0.90 581 16.2 1.21 0.18 1.08 Site 1, 2 m, Duplicate 1 790 1.10 <0.02 0.45 1.39 1.11 801 20.7 1.44 0.26 1.53 Site 1, 2 m, Duplicate 2 410 0.96 <0.02 0.34 0.99 0.90 551 16.5 1.14 0.17 1.00 Site 1, 4 m 850 0.94 <0.02 0.37 1.21 0.92 642 17.0 1.34 0.18 1.29 Site 2, 0.5 m 370 1.06 <0.02 0.31 0.89 1.07 482 13.5 1.02 0.15 0.95 Site 3, 0.5 m 950 1.30 <0.02 0.36 1.04 1.59 774 15.8 1.02 0.29 1.56 Site 3, 5 m 760 1.29 <0.02 0.36 1.26 1.54 792 15.6 1.10 0.24 1.55 Site 3, 10 m 930 1.18 <0.02 0.37 1.33 1.48 841 18.4 1.06 0.25 2.45 Site 4, 0.5 m 610 1.43 <0.02 0.35 1.12 1.68 771 17.8 1.01 0.24 2.95 Site 4, 0.5 m 1240 1.62 0.03 0.61 1.96 2.05 1350 25.9 9.49 0.45 3.34 Site 5, 0.5 m 1200 1.37 <0.02 0.49 1.71 1.89 1100 18.4 1.26 0.38 2.06 Site 5, 1.5 m 1530 1.41 <0.02 0.48 1.94 2.01 1190 19.1 1.39 0.40 2.40 Site 5, 3.5 m 1060 1.48 <0.02 0.55 1.70 2.14 1250 23.3 1.34 0.44 2.25 Site 5, 5.5 m 1310 1.66 <0.02 0.65 2.15 2.70 1500 27.8 1.41 0.70 2.74 Site 6, 0.5 m 1470 1.59 <0.02 0.61 2.04 2.18 1520 25.9 1.30 0.54 2.33 Site 6, 6 m 690 1.35 <0.02 0.35 1.16 1.54 751 13.4 0.98 0.27 1.91 Site 7, 0.5 m, Duplicate 1 420 1.28 <0.02 0.31 0.89 1.29 601 16.5 0.96 0.18 1.23 Site 7, 0.5 m, Duplicate 2 520 1.41 <0.02 0.33 1.09 1.36 651 17.1 0.92 0.20 1.50 Site 8, 0.5 m 980 1.39 <0.02 0.39 1.36 1.50 911 18.6 1.05 0.27 1.79 Site 9, 0.5 m 820 1.58 <0.02 0.51 1.59 1.79 1060 23.9 1.40 0.34 2.16 Site 9, 3 m 1680 1.83 <0.02 0.76 2.50 2.32 1720 36.0 1.83 0.55 3.65 Site 9, 6 m 2120 1.80 <0.02 0.74 2.62 2.21 1730 33.6 1.78 0.53 3.39 Site 10, 0.5 m, Duplicate 1 300 1.13 <0.02 0.15 0.61 0.99 291 7.4 0.63 0.07 0.59 Site 10, 0.5 m, Duplicate 2 320 1.22 <0.02 0.17 0.63 1.00 311 7.7 0.91 0.08 0.78 Site 11, 0.5 m 920 1.68 <0.02 0.51 1.50 1.80 1140 26.0 1.13 0.36 2.29 Site 12, 0.5 m 1360 1.52 <0.02 0.47 1.69 1.71 1070 21.9 1.17 0.32 2.21 Site 13, 0.5 m 870 1.53 <0.02 0.36 1.28 1.29 871 17.3 0.81 0.27 1.62 Site 14, 0.5 m 1050 1.53 <0.02 0.44 1.57 1.81 981 20.9 1.20 0.29 2.42
[Trace metal concentrations in Port Curtis] | 17
Sample name Al As Cd Co Cr Cu Fe Mn Ni Pb Zn (µg/L) Site 15, 0.5 m 1200 1.46 <0.02 0.43 1.57 1.53 1000 19.4 1.06 0.27 1.81 Site 16, 0.5 m, Duplicate 1 430 1.24 <0.02 0.20 0.78 1.27 421 11.5 0.62 0.14 1.32 Site 16, 0.5 m, Duplicate 2 450 1.27 <0.02 0.19 0.75 1.28 421 11.7 0.65 0.14 1.04 Site 17, 0.5 m 590 1.32 <0.02 0.22 0.95 1.00 501 10.2 0.74 0.14 0.94 Site 18, 0.5 m 200 1.43 <0.02 0.13 0.70 <0.17 301 7.3 0.38 0.12 0.71 Site 19, 0.5 m 510 1.66 <0.02 0.17 1.03 <0.17 451 9.9 0.49 0.13 0.19 Site 20, 0.5 m, Duplicate 1 130 1.23 <0.02 0.08 0.48 <0.17 111 4.7 0.30 <0.04 <0.11 Site 20, 0.5 m, Duplicate 2 130 1.34 <0.02 0.08 0.47 <0.17 111 4.5 0.29 <0.04 <0.11 Site 21, 0.5 m 90 1.10 <0.02 0.04 0.40 <0.17 91 2.4 0.22 <0.04 <0.11
3000
2500 Total Al = 23.9 x TSS 2 2000 R = 0.70
1500
Total Al (µg/L) 1000
500
0 0 20406080100 Total suspended solids (mg/L)
Figure 7. The relationship between the concentrations of total aluminium and total suspended solids measured in water samples.
3.4 METALS IN BENTHIC SEDIMENTS
The results for duplicates and full details of QA/QC for sediment analyses are given in Appendix B. The data for reference materials, spike recoveries and blanks were all within acceptable limits indicating satisfactory sampling and analysis. Sediment grab samples were not obtained from Sites 5 and 12 owing to the rocky nature of the sea bed at these sites and lack of fine sediment. The percentage of silt in the sediments collected at each site is shown in Table 5. The silt content was very variable and ranged from 0.2‐96% and indicated the heterogeneous nature of sediment content in the region, which ranged from very silty to very sandy. There was up to 15% relative standard deviation
18 |Trace metal concentrations in Port Curtis
difference between sample duplicates highlighting the heterogeneity of sediments even at the same site.
Total particulate metal concentrations are presented in Table 7 and 8. Graphical plots of the particulate metals data are presented in Appendix F. For most metals there was no discernible trend between concentration and location. The exceptions were: Particulate cobalt – highest in samples collected from the Narrows Particulate barium – highest in the area of current dredging activities
Sediment quality guidelines (ANZECC/ARMCANZ 2000), based predominantly on ecotoxicological data are available for ten metals and are applied to metals in the total sediment fraction. Two guideline values exist for each metal: the ISQG‐low trigger value (TV) and an ISQG‐high values, where ISQG refers to the interim sediment quality guideline. Sediments that have metal concentrations exceeding the ISQG‐low TV are deemed worthy of further investigation, as not all of the metals may be in bioavailable forms. The ISQG‐high values give an indication of metal concentrations where toxic effects would be expected. All metals were below the guideline TV, except for arsenic which marginally exceeded the TV of 20 µg/g at three sites (two in the Narrows and one site off Quoin Island), but never exceeded the corresponding high value. The particulate arsenic data are presented graphically in Figure 8. The two sites in the Southern Narrows have previously been shown to exceed the TV and this is most likely a reflection of the local geology which is naturally‐enriched in arsenic (Jones et al. 2005). A comparison of the sediment‐bound metal concentrations measured in Port Curtis in the current study and those reported by Jones et al. (2005) for studies in 2001 and 2002 are shown in Table 6. Most metals were either similar to or lower than those reported by Jones et al. (2005). Particulate cadmium concentrations were consistently higher in the current study, but were well below TV (ANZECC/ARMCANZ, 2000).
Particulate metal concentrations in the <63 µm sediment fractions are shown in Tables 9 and 10. Graphical plots of the particulate metals data are presented in Appendix F. For most metals there was no discernible trend between concentration and location. The exceptions were: Particulate barium – highest in the area of current dredging activities Particulate strontium – highest concentrations observed at the southern‐most sites. The particulate metal concentrations were nearly always higher in the <63 µm fraction because smaller sediment particles have a higher surface area and subsequent number of binding sites available for metals. A comparison of the particulate metal concentrations between the <63 µm and total fractions is illustrated for copper, lead, nickel and zinc in Figure 9.
[Trace metal concentrations in Port Curtis] | 19
60 ANZECC/ARMCANZ ISQG-high value =70 μg/g . 50
40
30 ANZECC/ARMCANZ ISQC-low value 20
Total Sediment-As (µg/g) (µg/g) Sediment-As Total 10
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
Figure 8. Total particulate arsenic concentrations of benthic sediment samples collected at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
Table 5. Percentages of silt (<63 µm) in the benthic sediment samples
Site % silt (<63 µm)
Site 1 1.4 Site 2 site Duplicate 1 39 Site 2 site Duplicate 2 29 Site 3 50 Site 4 27 Site 6 site Duplicate 1 52 Site 6 site Duplicate 2 65 Site 7 96 Site 8 27 Site 9 3.0 Site 10 site Duplicate 1 20 Site 10 site Duplicate 2 14 Site 11 8.0 Site 13 5.4 Site 14 site Duplicate 1 28 Site 14 site Duplicate 2 14 Site 15 8 Site 16 87 Site 17 6.6 Site 18 site Duplicate 1 0.2 Site 18 site Duplicate 2 0.2 Site 19 8.7 Site 20 40 Site 21 43
20 |Trace metal concentrations in Port Curtis
Table 6. Comparison of total metal concentrations measured in benthic sediment samples from Port Curtis in the current study and reported previously by Jones et al. (2005)
Study As Cd Cr Cu Hg Ni Pb Zn (µg/g) Current study Minimum concentration 7 0.11 7 4 0.02 4 3 8 Current study Maximum concentration 33 0.44 32 22 0.05 16 12 57 Current study Mean 13 0.24 15 10 0.03 8 7 29 Jones et al., 2005 Minimum concentration 6 <0.1 13 4 0.001 4 5 11 Jones et al., 2005 Maximum concentration 36 0.24 85 44 0.055 33 18 113 Jones et al., 2005 Mean 18 0.10 50 18 0.01 14 30 32 1Triggervalue 20 1.5 80 65 0.15 21 50 200 1ISQG high value 70 10 370 270 1 52 220 410 1ANZECC/ARMCANZ, 2000 ISQG values
45 15
36 12
27 9
18 6 TSS-Pb (µg/g) TSS-Pb
9 3 <63 um sediment-Cu (µg/g) sediment-Cu um <63
0 0 0 9 18 27 36 45 03691215 Total sediment-Cu (ug/g) Total sediment-Pb (ug/g)
45 120 . 36 100
80 27 60 18
TSS-Ni (µg/g) 40
9 20 <63 um sediment-Zn (µg/g) (µg/g) sediment-Zn um <63
0 0 0 9 18 27 36 45 0 20 40 60 80 100 120 Total sediment-Ni (ug/g) Total sediment-Zn (ug/g)
Figure 9. Graphs showing the relationship between copper, lead, nickel and zinc in the <63 µm and total fractions of benthic sediment samples
[Trace metal concentrations in Port Curtis] | 21
Table 7. Total metal concentrations in sediments
Site Fraction Ag Al As Ba Be Cd Co Cr Cu Fe Ga Hg (µg/g) Site 1 Total 0.01 1720 25 13 0.22 0.16 19 13 2 19500 2 <0.02 Site 2 Duplicate 1 Total 0.04 8430 54 10 0.79 0.38 30 24 7 62600 8 <0.02 Site 2 Duplicate 2 Total 0.03 6370 50 10 0.71 0.35 31 22 5 58200 7 <0.02 Site 3 Total 0.03 9850 9 11 0.49 0.23 10 16 10 16900 5 <0.02 Site 4 Total 0.03 10800 7 14 0.36 0.20 8 13 7 14000 5 <0.02 Site 6 Duplicate 1 Total 0.02 9280 10 54 0.42 0.16 6 20 15 31900 6 <0.02 Site 6 Duplicate 2 Total 0.03 18600 8 64 0.48 0.19 6 22 19 25900 8 <0.02 Site 7 Total 0.06 21200 11 82 0.73 0.38 13 25 21 28600 8 <0.02 Site 8 Total 0.05 19800 12 31 0.56 0.30 11 21 11 23100 7 <0.02 Site 9 Total 0.02 4400 15 16 0.23 0.19 12 7 4 13500 2 <0.02 Site 10 Duplicate 1 Total 0.03 11600 12 21 0.49 0.27 18 17 7 24500 6 <0.02 Site 10 Duplicate 2 Total 0.03 6680 12 13 0.43 0.22 17 13 6 22300 5 <0.02 Site 11 Total 0.02 3820 20 9 0.26 0.30 10 8 4 18000 3 0.02 Site 13 Total 0.01 4050 9 9 0.22 0.11 8 7 4 12300 3 <0.02 Site 14 Duplicate 1 Total 0.03 9110 7 18 0.31 0.22 8 13 11 16900 5 <0.02 Site 14 Duplicate 2 Total 0.03 13400 7 26 0.31 0.23 7 14 9 16500 5 <0.02 Site 15 Total 0.02 4390 14 11 0.29 0.18 10 8 6 14400 2 0.02 Site 16 Total 0.07 26900 15 29 0.78 0.44 11 32 22 28900 10 0.05 Site 17 Total 0.03 6040 33 10 0.37 0.26 14 10 5 22400 4 <0.02 Site 18 Duplicate 1 Total 0.01 2150 9 4 0.17 0.08 3 5 0.1 4970 1 <0.02 Site 18 Duplicate 2 Total 0.01 2340 8 6 0.18 0.09 3 6 0.2 5180 1 <0.02 Site 19 Total 0.01 2960 6 4 0.18 0.09 3 7 1 5090 2 <0.02 Site 20 Total 0.03 9130 13 10 0.52 0.21 6 16 3 15300 4 <0.02 Site 21 Total 0.05 17800 9 17 0.63 0.29 6 25 4 16000 6 <0.02 Trigger value1 1 ‐20 ‐‐2 ‐ 80 65 ‐‐0.15 ISQG high value1 3.70 ‐ 70 ‐ ‐ 10 ‐ 370 270 ‐ ‐ 1 1ANZECC/ARMCANZ, 2000 ISQG values
22 |Trace metal concentrations in Port Curtis
Table 8. Total metal concentrations in sediments (continued)
Site Fraction Mn Mo Ni Pb Sb Se Sr Tl V Zn (µg/g) Site 1 Total 1130 1 8 5 0.28 0.08 76 0.03 59 16 Site 2 Duplicate 1 Total 535 2 14 13 0.25 0.17 224 0.05 112 53 Site 2 Duplicate 2 Total 522 2 14 12 0.24 0.15 267 0.04 114 50 Site 3 Total 400 1 10 6 0.17 0.15 83 0.06 36 31 Site 4 Total 358 0.4 7 5 0.08 0.12 59 0.06 30 25 Site 6 Duplicate 1 Total 74 1 6 12 0.19 0.42 28 0.05 66 18 Site 6 Duplicate 2 Total 104 1 7 10 0.18 0.51 34 0.09 52 24 Site 7 Total 365 1 14 10 0.17 0.20 50 0.10 52 45 Site 8 Total 484 1 12 6 0.19 0.16 202 0.09 50 34 Site 9 Total 1330 1 5 4 0.14 0.10 235 0.02 37 19 Site 10 Duplicate 1 Total 433 1 9 7 0.19 0.14 30 0.09 47 40 Site 10 Duplicate 2 Total 322 1 6 8 0.17 0.13 43 0.08 42 38 Site 11 Total 896 1 6 5 0.13 0.13 349 0.02 42 18 Site 13 Total 407 0.4 4 3 0.12 0.05 97 0.02 27 18 Site 14 Duplicate 1 Total 290 0.5 7 5 0.12 0.11 56 0.04 37 30 Site 14 Duplicate 2 Total 348 1 7 4 0.13 0.10 95 0.06 39 28 Site 15 Total 659 1 6 5 0.23 0.15 486 0.03 33 21 Site 16 Total 484 1 16 11 0.19 0.27 179 0.13 52 57 Site 17 Total 960 1 7 6 0.35 0.12 576 0.03 48 22 Site 18 Duplicate 1 Total 175 0.1 2 2 0.05 0.02 181 0.01 11 6 Site 18 Duplicate 2 Total 163 0.1 2 2 0.05 0.02 167 0.01 11 6 Site 19 Total 150 0.2 3 3 0.09 0.07 137 0.03 12 7 Site 20 Total 169 1 7 6 0.12 0.15 274 0.08 24 22 Site 21 Total 197 1 11 7 0.12 0.17 241 0.12 32 28 Trigger value1 ‐‐ 21 50 2 ‐‐‐‐200 ISQG high value1 ‐ ‐ 52 220 25 ‐ ‐ ‐ ‐ 410 1ANZECC/ARMCANZ, 2000 ISQG values
[Trace metal concentrations in Port Curtis] | 23
Table 9. Total metal concentrations in the <63 µm sediment fractions
Site Fraction Ag Al As Ba Be Cd Co Cr Cu Fe Ga Hg (µg/g) Site 1 <63 µm 0.05 5275 15 9 0.36 1.68 18 13 7 14223 2 0.36 Site 2 Duplicate 1 <63 µm 0.08 35600 14 33 1.13 0.68 14 46 23 37400 13 0.08 Site 2 Duplicate 2 <63 µm 0.06 34400 13 31 1.02 0.84 13 44 21 34300 12 0.08 Site 3 <63 µm 0.07 28800 13 24 1.00 0.74 15 38 23 33800 8 0.11 Site 4 <63 µm 0.06 25900 9 28 0.90 0.79 13 34 22 30100 10 0.13 Site 6 Duplicate 1 <63 µm 0.03 23800 5 58 0.50 0.30 6 25 22 23700 9 0.06 Site 6 Duplicate 2 <63 µm 0.03 28500 8 68 0.61 0.39 8 29 22 28300 10 0.07 Site 7 <63 µm 0.04 21000 12 84 0.70 0.45 12 25 22 28900 8 0.05 Site 8 <63 µm 0.07 29100 14 25 1.05 0.74 16 38 24 36700 12 0.05 Site 9 <63 µm 0.06 19000 24 48 0.71 1.47 21 23 23 32800 9 0.31 Site 10 Duplicate 1 <63 µm 0.07 23000 10 23 0.83 0.94 12 30 24 28200 9 0.16 Site 10 Duplicate 2 <63 µm 0.05 23200 10 23 0.86 0.64 12 32 26 29600 10 0.14 Site 11 <63 µm 0.06 27600 12 28 0.89 0.78 16 34 25 31100 11 0.09 Site 13 <63 µm 0.06 26000 21 54 0.89 1.34 17 30 23 38400 10 0.32 Site 14 Duplicate 1 <63 µm 0.05 21800 10 28 0.72 0.79 14 25 31 31900 8 0.14 Site 14 Duplicate 2 <63 µm 0.05 23700 12 32 0.75 0.88 14 27 28 33000 10 0.17 Site 15 <63 µm 0.05 22700 14 30 0.81 0.82 14 29 23 28400 9 0.16 Site 16 <63 µm 0.04 16700 14 22 0.74 0.90 10 26 22 25900 8 0.17 Site 17 <63 µm 0.05 20900 15 25 0.75 0.67 12 27 21 26400 8 0.09 Site 18 Duplicate 1 <63 µm 0.04 16700 16 22 0.67 6.43 11 33 8.5 22600 10 1.92 Site 18 Duplicate 2 <63 µm 0.04 16400 13 17 0.76 1.94 10 33 8.8 21800 8 0.51 Site 19 <63 µm 0.06 29400 13 23 0.91 0.77 11 45 10 26800 10 0.13 Site 20 <63 µm 0.05 25300 14 22 0.95 0.53 8 37 7 26000 9 0.08 Site 21 <63 µm 0.03 14400 11 16 0.78 0.49 7 30 8 20500 6 0.10 Trigger value1 1.00 ‐ 20 ‐‐2 ‐80 65 ‐‐0.15 ISQG high value1 3.70 ‐ 70 ‐ ‐ 10 ‐ 370 270 ‐ ‐ 1 1ANZECC/ARMCANZ, 2000 ISQG values
24 |Trace metal concentrations in Port Curtis
Table 10. Total metal concentrations in the <63 µm sediment fractions (continued)
Site Fraction Mn Mo Ni Pb Sb Se Sr Tl V Zn (µg/g) Site 1 <63 µm 1654 2 11 7 0.17 0.90 136 0.05 42 23 Site 2 Duplicate 1 <63 µm 322 1 26 14 0.20 0.36 53 0.19 67 67 Site 2 Duplicate 2 <63 µm 260 1 26 13 0.23 0.35 53 0.18 61 64 Site 3 <63 µm 198 1 22 13 0.24 0.33 46 0.16 64 65 Site 4 <63 µm 221 1 19 12 0.20 0.32 49 0.15 59 59 Site 6 Duplicate 1 <63 µm 95 1 8 15 0.16 0.34 25 0.11 45 29 Site 6 Duplicate 2 <63 µm 172 1 12 13 0.17 0.45 32 0.14 52 38 Site 7 <63 µm 374 1 14 11 0.17 0.20 42 0.11 55 46 Site 8 <63 µm 309 1 22 13 0.24 0.35 55 0.14 65 64 Site 9 <63 µm 1520 2 17 11 0.22 0.71 122 0.10 80 56 Site 10 Duplicate 1 <63 µm 250 1 17 12 0.26 0.34 41 0.12 58 59 Site 10 Duplicate 2 <63 µm 263 1 17 13 0.27 0.33 43 0.14 64 62 Site 11 <63 µm 851 1 20 12 0.17 0.64 76 0.15 60 66 Site 13 <63 µm 798 1 17 13 0.28 0.35 108 0.11 77 63 Site 14 Duplicate 1 <63 µm 440 1 15 11 0.16 0.34 50 0.11 62 61 Site 14 Duplicate 2 <63 µm 551 1 15 11 0.18 0.30 69 0.11 65 64 Site 15 <63 µm 734 1 17 12 0.20 0.54 98 0.13 55 57 Site 16 <63 µm 427 1 14 11 0.17 0.24 137 0.11 47 54 Site 17 <63 µm 607 1 16 11 0.20 0.59 127 0.12 52 53 Site 18 Duplicate 1 <63 µm 912 1 15 13 0.21 0.36 230 0.11 45 53 Site 18 Duplicate 2 <63 µm 417 1 14 12 0.24 0.38 189 0.13 49 41 Site 19 <63 µm 298 1 19 13 0.23 0.47 184 0.17 59 46 Site 20 <63 µm 251 1 17 13 0.15 0.28 89 0.16 43 44 Site 21 <63 µm 226 1 14 13 0.04 0.30 214 0.14 42 36 Trigger value1 ‐‐21 50 2 ‐‐‐‐200 ISQG high value1 ‐ ‐ 52 220 25 ‐ ‐ ‐ ‐ 410 1ANZECC/ARMCANZ, 2000 ISQG values
[Trace metal concentrations in Port Curtis] | 25
3.5 METALS ASSOCIATED WITH SUSPENDED SOLIDS
The results for duplicates and full details of QA/QC for analyses of suspended solids are given in Appendix B. The data for reference materials, spike recoveries and blanks were all within acceptable limits and indicate satisfactory sampling and analysis. Metals associated with suspended sediments may be potentially bioavailable to filter‐feeding organisms and their concentrations give some indication of exposure.
The concentrations of metals in the suspended solids fraction of the waters sampled (TSS‐metals) are shown in Tables 11 and 12 and graphically in Appendix E. The TSS‐ silver, cadmium and all but four mercury concentrations were below the limits of detection and are not discussed any further. The variation of TSS‐ metal concentrations across the sampling sites is illustrated for the cases of aluminium, copper, nickel and zinc in Figures 10 to 13 respectively.
In general, the TSS‐metal concentrations were comparable to the particulate metal concentrations of the <63 µm fraction of benthic sediments (see Figure 14 for example data). This is consistent with a significant proportion of the suspended sediment pool originating from the resuspension of fine benthic sediments.
Most TSS‐metals displayed no discernible trends across Port Curtis. However TSS‐copper concentrations were lowest at the Southern‐most sites, TSS‐ molybdenum, nickel, lead and zinc concentrations showed a gradual increase in concentration from south to north and TSS‐Strontium showed a gradual increase in concentration from north to south.
80000
. 60000
40000 TSS-Al (µg/g) (µg/g) TSS-Al
20000
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
Figure 10. TSS‐bound aluminium concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
.
26 |Trace metal concentrations in Port Curtis
50
. 40
30
TSS-Cu (µg/g) 20
10
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
Figure 11. TSS‐bound copper concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
40 . 30
20 TSS-Ni (µg/g) (µg/g) TSS-Ni
10
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
Figure 12. TSS‐bound nickel concentration from all depths at sites between the Southern Narrows to Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay .
[Trace metal concentrations in Port Curtis] | 27
120
. 90
60 TSS-Zn (µg/g) (µg/g) TSS-Zn
30
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
Figure 13. TSS‐bound zinc concentrations from all depths at sites between the Southern Narrows and Rodds Bay, where, represents sites in the Southern Narrows, represents sites adjacent to the dredge and construction sites, represents sites in the outer harbour and, represents marine sites outside the harbour between the Boyne River and Rodds Bay
28 |Trace metal concentrations in Port Curtis
Table 11. Suspended sediments: particulate metals concentrations
Sample description Ag Al As Ba Be Cd Co Cr Cu Fe (µg/g) Field blank 1 <2.4 <310 <0.5 <2.5 <0.06 <1.1 <0.5 <2.5 <11 <69 Field blank 2 <2.4 <310 <0.5 <2.5 <0.06 <1.1 <0.5 <2.5 <11 <69 Field blank 3 <2.4 <310 <0.5 <2.5 <0.06 <1.1 <0.5 <2.5 <11 <69 Field blank 4 <2.4 <310 <0.5 <2.5 <0.06 <1.1 <0.5 <2.5 <11 <69 Site 1, 0.5 m <2.4 40900 17 42 1.2 <1.1 13 58 21 39900 Site 1, 2 m, Duplicate 1 <2.4 37500 15 40 1.1 <1.1 14 54 23 37900 Site 1, 2 m, Duplicate 2 <2.4 23100 16 30 0.9 <1.1 11 41 17 31100 Site 1, 4 m <2.4 56900 17 59 1.3 <1.1 14 64 19 43000 Site 2, 0.5 m <2.4 10500 7 12 0.5 <1.1 6 18 <11 13700 Site 3, 0.5 m <2.4 35500 15 49 0.8 <1.1 12 45 30 32100 Site 3, 5 m <2.4 34700 17 46 0.8 <1.1 14 45 28 35900 Site 3, 10 m <2.4 42900 18 49 0.9 <1.1 15 49 33 38900 Site 4, 0.5 m <2.4 26100 18 34 0.7 <1.1 14 38 30 33600 Site 4, 0.5 m <2.4 18600 11 27 0.7 <1.1 8 26 18 20200 Site 5, 0.5 m <2.4 19600 9 28 0.5 <1.1 7 24 16 17900 Site 5, 1.5 m <2.4 26300 9 35 0.7 <1.1 7 29 19 20700 Site 5, 3.5 m <2.4 24300 15 46 0.7 <1.1 11 33 28 28800 Site 5, 5.5 m <2.4 26700 16 53 0.9 <1.1 12 39 36 30800 Site 6, 0.5 m <2.4 32800 15 52 1.1 <1.1 12 40 29 33800 Site 6, 6 m 3.3 28800 16 50 1.0 <1.1 12 38 29 31500 Site 7, 0.5 m, Duplicate 1 <2.4 19100 15 31 0.9 <1.1 12 30 20 28100 Site 7, 0.5 m, Duplicate 2 <2.4 10600 8 13 0.5 <1.1 6 17 12 13700 Site 8, 0.5 m <2.4 42500 18 52 1.0 <1.1 15 48 31 39600 Site 9, 0.5 m <2.4 13500 11 20 0.5 <1.1 8 22 16 17800 Site 9, 3 m <2.4 24300 13 28 0.8 <1.1 11 32 22 24900 Site 9, 6 m <2.4 28800 12 34 0.6 <1.1 10 32 20 23600 Site 10, 0.5 m, Duplicate 1 <2.4 45100 19 50 0.9 <1.1 15 52 31 44100 Site 10, 0.5 m, Duplicate 2 <2.4 13000 7 13 0.3 <1.1 5 15 <11 12600 Site 11, 0.5 m <2.4 18400 13 23 0.6 <1.1 10 25 20 22800 Site 12, 0.5 m <2.4 28300 11 34 0.7 <1.1 9 30 18 22400 Site 13, 0.5 m <2.4 23300 11 27 0.6 <1.1 9 27 18 23300 Site 14, 0.5 m <2.4 22300 11 25 0.5 <1.1 9 28 19 21000 Site 15, 0.5 m <2.4 23000 10 28 0.4 <1.1 8 25 15 19200 Site 16, 0.5 m, Duplicate 1 <2.4 36100 20 44 1.0 <1.1 14 45 41 36100 Site 16, 0.5 m, Duplicate 2 <2.4 42400 19 49 1.3 <1.1 15 47 35 39300 Site 17, 0.5 m <2.4 17600 8 18 0.5 <1.1 6 21 <11 14900 Site 18, 0.5 m <2.4 13500 19 17 0.8 <1.1 7 30 <11 19600 Site 19, 0.5 m <2.4 24900 21 25 0.8 <1.1 7 38 <11 22100 Site 20, 0.5 m, Duplicate 1 <2.4 8240 6 7 0.3 <1.1 3 14 <11 7300 Site 20, 0.5 m, Duplicate 2 <2.4 43500 24 40 1.2 <1.1 12 69 <11 35300 Site 21, 0.5 m <2.4 17700 13 17 0.8 <1.1 6 28 <11 17000
[Trace metal concentrations in Port Curtis] | 29
Table 12. Suspended sediments: particulate metals concentrations continued
Sample description Hg Mn Mo Ni Pb Sb Se Sr Tl V Zn (µg/g)
Field blank 1 <0.39 <0.7 <0.61 <2.5 <2.2 <0.10 <0.15 <0.4 <0.06 <0.8 <8.6 Field blank 2 <0.39 <0.7 <0.61 <2.5 <2.2 <0.10 <0.15 <0.4 <0.06 <0.8 <8.6 Field blank 3 <0.39 <0.7 <0.61 <2.5 <2.2 <0.10 <0.15 <0.4 <0.06 <0.8 <8.6 Field blank 4 <0.39 <0.7 <0.61 <2.5 <2.2 <0.10 <0.15 <0.4 <0.06 <0.8 <8.6 Site 1, 0.5 m <0.39 747 1.9 32 12 0.1 0.3 72 0.2 81 68 Site 1, 2 m, Duplicate 1 <0.39 739 1.9 30 12 0.2 0.3 67 0.1 77 66 Site 1, 2 m, Duplicate 2 <0.39 688 1.5 23 9 0.2 0.3 56 0.1 60 42 Site 1, 4 m <0.39 768 2.1 35 11 0.2 0.3 84 0.1 87 69 Site 2, 0.5 m <0.39 326 0.7 9 4 <0.10 0.2 115 <0.06 31 24 Site 3, 0.5 m 0.6 525 1.9 20 12 0.4 0.2 63 0.3 72 53 Site 3, 5 m 0.4 672 1.5 21 10 0.2 0.3 46 0.2 74 64 Site 3, 10 m <0.39 817 1.0 25 11 0.3 0.3 66 0.3 82 102 Site 4, 0.5 m <0.39 773 1.0 20 10 0.2 0.5 59 0.2 70 58 Site 4, 0.5 m <0.39 382 0.9 134 7 0.1 0.4 90 0.1 45 47 Site 5, 0.5 m <0.39 267 0.8 11 6 0.1 0.3 101 0.1 40 29 Site 5, 1.5 m <0.39 298 0.9 13 7 0.2 0.3 90 0.1 48 33 Site 5, 3.5 m <0.39 498 1.3 16 10 0.2 0.3 54 0.1 60 42 Site 5, 5.5 m <0.39 547 1.5 16 14 0.4 0.7 50 0.2 65 49 Site 6, 0.5 m <0.39 558 1.3 16 12 0.3 0.5 58 0.2 69 45 Site 6, 6 m <0.39 533 1.1 16 11 0.2 0.5 60 0.3 64 49 Site 7, 0.5 m, Duplicate 1 0.5 648 0.9 20 8 0.2 0.4 54 0.2 54 45 Site 7, 0.5 m, Duplicate 2 <0.39 326 <0.61 8 4 0.1 0.2 114 0.1 31 27 Site 8, 0.5 m <0.39 791 1.4 23 12 0.2 0.6 59 0.2 80 69 Site 9, 0.5 m <0.39 394 0.8 12 6 0.2 0.2 90 0.1 42 30 Site 9, 3 m <0.39 521 1.1 16 8 0.2 0.3 91 0.1 58 48 Site 9, 6 m <0.39 457 0.9 16 7 0.2 0.3 95 0.2 57 42 Site 10, 0.5 m, Duplicate 1 <0.39 852 1.5 22 9 0.2 0.2 83 0.2 83 53 Site 10, 0.5 m, Duplicate 2 <0.39 242 <0.61 8 3 <0.10 <0.15 115 <0.06 26 17 Site 11, 0.5 m <0.39 521 0.8 13 7 0.1 0.4 87 0.1 49 42 Site 12, 0.5 m <0.39 419 0.8 14 7 0.1 0.2 104 0.2 52 39 Site 13, 0.5 m <0.39 449 0.9 12 7 0.2 0.3 96 0.1 48 39 Site 14, 0.5 m <0.39 425 0.6 14 6 0.1 0.2 106 0.1 49 40 Site 15, 0.5 m <0.39 369 0.8 11 5 0.1 0.2 106 0.1 45 30 Site 16, 0.5 m, Duplicate 1 <0.39 843 1.4 24 11 0.3 0.5 92 0.2 83 85 Site 16, 0.5 m, Duplicate 2 <0.39 912 1.0 21 12 0.3 0.8 89 0.1 82 74 Site 17, 0.5 m <0.39 281 <0.61 9 4 0.1 0.3 118 0.1 35 22 Site 18, 0.5 m <0.39 477 0.8 12 7 0.2 0.4 231 0.2 41 18 Site 19, 0.5 m <0.39 486 1.1 14 6 0.2 0.6 255 0.3 45 9 Site 20, 0.5 m, Duplicate 1 <0.39 224 <0.61 6 <2.2 0.1 0.3 149 0.1 15 <8.6 Site 20, 0.5 m, Duplicate 2 <0.39 1070 2.5 25 10 0.1 0.8 174 0.4 70 <8.6 Site 21, 0.5 m 0.6 452 0.7 10 3 <0.10 0.8 242 0.3 33 <8.6
30 |Trace metal concentrations in Port Curtis
45 45
36 36
27 27
18 18 TSS-Ni (µg/g) TSS-Cu (µg/g) TSS-Cu
9 9
0 0 0 9 18 27 36 45 0 9 18 27 36 45 <63 µm sediment-Cu (ug/g) <63 µm sediment-Ni (ug/g)
120
100
80
60
TSS-Zn (µg/g) TSS-Zn 40
20
0 0 20406080100120 <63 µm sediment-Zn (ug/g)
Figure 14. Graphs showing the relationship between copper, nickel and zinc bound to TSS and the <63 µm fraction of sediment
[Trace metal concentrations in Port Curtis] | 31
4 GENERAL DISCUSSION
4.1 DISSOLVED METALS
A comparison of some of the dissolved metals in Port Curtis and other industrialised harbours around the world is shown in Table 13. Port Curtis compares favourably with most other harbours and has relatively low metal concentrations despite the large amount of industrial activity and shipping.
The dissolved aluminium concentrations were nearly all above the ANZECC/ARMCANZ 2000 Environmental Concern Level (ECL) of 0.5 µg/L. It should be pointed out that this is a low reliability value derived from the most sensitive toxicity data divided by an arbitrary application factor of 200. It is not formally considered as a guideline value. As part of the current revision of the Australian Water Quality Guidelines the marine aluminium trigger value (TV) is being updated. There are no water quality guidelines that apply to aluminium in marine waters in Europe or North America (USA and Canada).
Dissolved aluminium concentrations have previously been reported to be variable in Port Curtis and in exceedance of the ECL. CSIRO measured dissolved metal concentrations in 2003 and 2004 (Angel unpublished data) and found dissolved aluminium concentrations that ranged from <0.6 to 83 μg/L in the southern part of the Narrows and from <0.6 to 44 μg/L in mid Port Curtis Harbour. These data indicate that high and variable levels of dissolved aluminium have occurred for some time in the area. There are several potential sources of aluminium in the harbour including tidal and/or dredging‐induced resuspension of sediments containing aluminosilicates and nearby aluminium industries. One possibility for the high and variable dissolved aluminium concentrations is the resuspension of colloids containing aluminium that were less than the 0.45 µm pore size used to filter samples for dissolved metals analyses. Ultrafiltration or dialysis measurement techniques could be performed to exclude such colloids.
No fish toxicological data was used in the derivation of the marine ECL for aluminium and very few studies are available in the literature. Fish are also generally more sensitive to aluminium than freshwater aquatic invertebrates because it acts as a gill toxicant causing both ionoregulatory and respiratory effects (Gensemer and Playle, 1999). A study by Hyne and Wilson, (1997) using the Australian Bass, Macquaia novemaculeata in estuarine water (20‐25 PSU) found aluminium toxicity was strongly pH dependent between pH 4 and 8. No juvenile mortality was detected for dissolved aluminium concentrations up to 10 mg/L at water pH’s above pH 6, but 500 µg/L caused significant mortality at pH 4. Another previous study in seawater showed that aluminium was only toxic to a variety of fish species when the pH of the seawater was less than 6.7 at concentrations of 18 mg/L or greater (Pulley, 1950). It should also be noted that toxicity tests measure the toxicity soon after addition of aluminium and freshly prepared solutions have been shown to be more toxic (Pulley, 1950). Therefore, marine waters at approximately pH 8 may be much less toxic to fish than freshwaters at lower pH, which dominate the aluminium toxicological literature. As noted earlier, of the dissolved metals measured, copper was closest to its ANZECC/ARMNCANZ trigger value. The relatively high concentrations observed are consistent with our previous observations (Angel et al. 2010). There are a number of sources of copper in Port Curtis including release from antifouling paints applied to boats. Given the increased shipping activity in the Harbour it is likely that this source of copper has increased over recent years. It is therefore advisable to monitor copper speciation and assess the bioavailability of this metal. A number of speciation methods are available for this purpose.
The current study has provided a useful snapshot of metal concentrations in waters and sediments of the Port Curtis region. However there is a need to characterise how water quality changes with time. It must be stressed that variations in water quality in tropical and sub‐tropical systems often occur as pulse events. Event‐related sampling is required to capture information from these events.
32 |Trace metal concentrations in Port Curtis
It is evident from the absence of any localised elevation in the metal concentrations within the vicinity of the dredging area that the current dredging operations have not elevated dissolved metal concentrations in Port Curtis. This is most likely because the sediments being dredged have a relatively low metal content which is not mobilised into solution during dredging operations. It would be useful to conduct some follow‐ up laboratory studies on dredge material to further examine the mobility of metals when dredge material is suspended in seawater. This work could also cover the likelihood of contaminant mobilisation during dredge spoil disposal.
Table 13 Comparison of dissolved metal concentrations measured in the current study with previous data from Port Curtis and with other locations.
LOCATION DISSOLVED METAL CONCENTRATION, ng/L REFERENCE
Cadmium Copper Nickel Zinc
Port Curtis, Dec 2011 4 717 538 306 This study
Port Curtis Harbour 7.0 510 340 170 Angel et al., 2010 The Narrows 8.0 530 650 110 Angel et al., 2010 Port Jackson, Australia 6‐104 932‐2550 175‐1610 3270‐9660 Hatje et al. 2003 Apte and Day, Torres Straight & Gulf of Papua <1‐29 36‐986 940‐4600 ‐ 1998 Fabris and Port Phillip Bay, Australia <5‐70 400‐630 540‐1100 250‐1050 Monahan, 1995 Munksguard and Nine estuaries, northern Australia 1.4‐72 150‐5500 120‐4250 <10‐11300 Parry, 2001 Humber estuary, UK 80‐450 180‐10100 2500‐12000 3000‐20500 Comber et al. 1995 Baeyens et al. Scheldt estuary, Netherlands 15‐100 750‐1800 1000‐6800 1000‐10000 2005 Sanudo‐Wilhelmy San Francisco Bay estuary, USA 22‐123 315‐2230 140‐2410 160‐1960 et al. 1996 NSW coast 2.5 30 180 <22 Apte et al. 1998 Bruland et al. North Pacific Ocean 0.3‐112 ‐ ‐ 15‐520 1994 ANZECC/ARMCANZ Australian Guideline values (95% species protection)1 5500 1300 70000 15000 2000 1ANZECC/ARMCANZ (2000) 95% values with 50% confidence
[Trace metal concentrations in Port Curtis] | 33
5 CONCLUSIONS
1. The concentrations of dissolved arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, lead and zinc were below the ANZECC/ARMCANZ marine water quality guideline trigger values that apply in Australia at all 21 sites sampled and the concentrations were relatively low compared to other industrialised harbours. 2. Dissolved aluminium concentrations were above the ANZECC/ARMCANZ (2000) environmental concern level (ECL) of 0.5 µg/L at the majority of sites sampled. It should be noted that there is no reliable guideline value for aluminium in marine waters in Australia and the ECL value is a highly conservative value based on very limited toxicity data. There are no water quality guidelines that apply for aluminium in marine waters in Europe or North America. From the current data set, it was not possible to attribute a specific source of the dissolved aluminium. 3. The dissolved copper concentrations measured in Port Curtis in December 2011 were lower than the ANZECC/ARMCANZ guideline value of 1.3 µg/L. However, the dissolved copper concentrations were noticeably higher than the concentrations measured in the CSIRO surveys in December 2003 and 2004, indicating increased inputs of these metals from various sources, and the concentrations at some sites were only marginally lower than the ANZECC/ARMCANZ guideline value. Dissolved cadmium and zinc concentrations were comparable to those measured in 2003/2004 by CSIRO. 4. A comparison of some of the dissolved metals in Port Curtis and other industrialised harbours around the world (Table 13) shows that Port Curtis compares favourably with most other harbours and has relatively low metal concentrations despite the large amount of industrial activity and shipping.
5. Apart from arsenic, the concentrations of particulate metals in benthic sediments were below the ANZECC/ARMCANZ sediment quality guideline values. Particulate arsenic concentrations exceeded the ANZECC/ARMCANZ ISQG‐low trigger value in two samples from the Narrows and one site off Quoin Island. Previous studies indicate that the source of this arsenic is natural (geological formation in the area) and is not associated with anthropogenic inputs. 6. Metal concentrations in suspended sediments were not elevated and were comparable to the concentrations of metals in the <63 µm (fine) fraction of benthic sediments. This is consistent with the resuspension of fine sediments into the water column. 7. The study did not detect any ‘hot spots’ of metal concentrations. There was no detectable elevation of metal concentrations at sites where dredging was being conducted.
34 |Trace metal concentrations in Port Curtis
6 RECOMMENDATIONS
1. The forms of dissolved aluminium (speciation) in the waters of the Port Curtis region and their bioavailability/toxicity should be examined. It is possible that a large proportion of the dissolved aluminium is present in a non‐bioavailable form, but this needs to be investigated. 2. Given that the dissolved copper concentrations were only marginally lower than the ANZECC/ARMCANZ guideline value at some sites in Port Curtis and have previously been measured above the guideline by DERM (November 2011), it is advisable to follow the ANZECC/ARMCANZ framework for metals in aquatic systems and characterise the chemical forms of dissolved copper (speciation) and their bioavailability/toxicity. It is likely that a significant proportion of the copper is associated with organic matter and will not exert toxic effects on marine life. 3. It is recognised that the current study only provides a snapshot of water quality as it was conducted over a period of three days. It is desirable to characterise temporal variations in dissolved metal concentrations (e.g. pulse events) by conducting regular surveys ideally under different tidal and climatic conditions. 4. Given the public concerns around fish disease in the Gladstone region, it is recommended that tissue metal concentrations in fish are analysed. This should be conducted on both healthy and diseased specimens, if available. 5. Previous water quality programs in the Port Curtis region have used total metal concentrations. It is strongly recommended in the ANZECC/ARMCANZ decision tree framework that dissolved metals be used for monitoring of trace metals. Dissolved concentrations give a better indication of metal bioavailability and toxicity. Monitoring of dissolved concentrations should be adopted in Port Curtis. We note that Vision Environment QLD have recently commenced monthly water quality surveys to address these issues. 7. The actual dissolved trace metal concentrations at the dredge spoil dumping sites should be characterised.
[Trace metal concentrations in Port Curtis] | 35
7 REFERENCES
Ahlers, W.W., Reid, M.R., Kim, J.P. and Hunter, K.A. (1990). Contamination‐free sample collection and handling protocols for trace elements in natural waters. Australian Journal of Marine and Freshwater Research 41, 713‐720. Angel, B., Hales, L.T., Simpson, S.L, Apte, S.C, Chariton, A., Shearer, D. and Jolley, D.F. (2010). Spatial variability of cadmium, copper, manganese, nickel and zinc in the Port Curtis Estuary, Queensland, Australia. Marine and Freshwater Research 61, 170‐183. ANZECC/ARMCANZ (2000). Australian and New Zealand Guidelines for Fresh and Marine Water Quality. Volume 1. The Guidelines, Australian and New Zealand Environment and Conservation Council and Agriculture and Resource Management Council of Australia and New Zealand, Canberra, ACT, Australia. Apte, S.C. and Gunn, A.M. (1987). Rapid determination of copper, nickel, lead and cadmium in small samples of estuarine waters by liquid/liquid extraction and electrothermal atomic absorption spectrometry. Analytica Chimica Acta 193, 147‐156. Apte, S. C., Batley, G. E., Szymczak, R., Rendell, P. S., Lee, R. and Waite, T. D. (1998). Baseline trace metal concentrations in New South Wales coastal waters. Marine and Freshwater Research 49, 203‐214. Apte, S.C. and Day, G.M. (1998). Dissolved metal concentrations in the Torres Strait and Gulf of Papua. Marine Pollution Bulletin 30, 298‐304. Apte, S.C., Batley, G.E. and Maher, W.A. (2002). Monitoring of trace metals and metalloids in natural waters. In: Handbook of Environmental Monitoring. Burden, F., Forstner, U., Guenther, A., and McKelvie, I., Eds, McGraw Hill, New York, Chapter 6. Baeyens, W., Goeyens, M., Monteny, F. and Elskens, M. (1998). Effect of organic complexation on the behaviour of dissolved cadmium, copper, and zinc in the Scheldt estuary. Hydrobiologia 366, 15‐43. Bruland, K.W., Orians, K.J. and Cowen, J.P. (1994). Reactive trace metals in the stratified central North Pacific. Geochimica et Cosmochimica Acta 58, 3171‐3182. Comber, S.D.W., Gunn, A.M. and Whalley, C. (1995). Comparison of the partitioning of trace metals in the Humber and Mersey Estuaries. Marine Pollution Bulletin 30, 851‐860. DERM (2011). Water Quality of Port Curtis and Tributaries. Supplementary Report based on data collected in the week of 26th September 2011. Queensland Department of Environment and Resource Management report, 39 pages. Fabris, G.L. and Monahan, C.A. (1995). Characterisation of toxicants in waters from Port Phillip Bay: metals. Technical Report No. 18, CSIRO Port Phillip Bay Environmental Study. Technical Report No. 18, Melbourne, Australia. Gensemer, R. W., Playle, R. C., (1999). The bioavailability and toxicity of aluminium in aquatic environments. Critical Reviews in Environmental Science and Technology 29, 315–450. Hatje, V., Apte, S.C., Hales, L.T. and Birch, G.F. (2003). Dissolved trace metal distributions in Port Jackson estuary (Sydney Harbour), Australia. Marine Pollution Buletin 46, 719‐730. Hyne, R. V., Wilson, S. W., (1997). Toxicity of acid‐sulphate soil leachate and aluminium to the embryos and larvae of Australian Bass, Maquaria Novemaculeata in estuarine water. Environ. Poll. 97. 221‐227. Jones, M‐A., Stauber, J.L., Apte, S.C., Simpson, S.L., Vincente‐Beckett, V., Johnson, R. and Duivenvoorden, L. (2005). A risk assessment approach to contaminants in Port Curtis, Queensland, Australia. Marine Pollution Bulletin 51, 448‐458.
36 |Trace metal concentrations in Port Curtis
Magnusson, B. and Westerlund, S. (1981). Solvent extraction procedures combined with back‐extraction for trace metal determinations by atomic absorption spectrometry. Analytica Chimica Acta 131, 63‐72. Munksgaard, N.C. and Parry, D.L. (2001). Trace metals, arsenic and lead isotopes in dissolved and particulate phases of North Australian coastal and estuarine seawater. Marine Chemistry 75, 165‐184. Pulley, T. E., (1950). The effect of aluminium chloride in small concentration on various marine organisms. The Texas Journal of Science 2, 405‐411. Sanudo‐Wilhelmy, S.A., Rivera‐Duarte, I. and Flegal, A.R. (1996). Distribution of colloidal trace metals in the San Fransisco Bay estuary. Geochimica et Cosmochimica Acta 60, 4933‐4944. USEPA (1996). Sampling ambient water for trace metals at EPA water quality criteria levels. Method 1669. US Environmental Protection Agency, Office of Water Engineering and Analysis Division (4303), Washington DC 20460.
[Trace metal concentrations in Port Curtis] | 37
Appendix A Maps showing the site sampled in the Southern Narrows and marine sites south‐east of Port Curtis
38 |Trace metal concentrations in Port Curtis
Appendix B Quality Control Data
Table B1: Limits of detection for dissolved metals
LABORATORY I.D. Al As Cd Co Cr Cu Fe Mn Ni Pb Zn (µg/L) (µg/L) (ng/L) (ng/L) (µg/L) (ng/L) (µg/L) (µg/L) (ng/L) (ng/L) (ng/L) Limit of Detection (3σ) 1 0.09 3 2 0.4 15 1.5 0.1 32 16 9
[Trace metal concentrations in Port Curtis] | 39
Table B2: Certified reference material (CASS‐4) for dissolved metals analyses
LABORATORY I.D. As Cd Co Cu Mn Ni Pb Zn (µg/L) (ng/L) (ng/L) (ng/L) (µg/L) (ng/L) (ng/L) (ng/L) CASS‐4, 14/12/11 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ 2.8 ‐‐‐ ‐‐‐ ‐‐‐ CASS‐4, 14/12/11 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ 2.8 ‐‐‐ ‐‐‐ ‐‐‐ CASS‐4, 14/12/11 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ 2.8 ‐‐‐ ‐‐‐ ‐‐‐ CASS‐4, 14/12/11 ‐‐‐ 24 25 535 ‐‐‐ 275 <16 347 CASS‐4, 11/01/11 ‐‐‐ 25 25 532 ‐‐‐ 284 <16 370 CASS‐4, 14/02/12 1.14 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ CASS‐4, 14/02/12 1.18 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ CASS‐4, 14/02/12 1.04 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ CASS‐4, 15/02/12 1.16 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ CASS‐4, 15/02/12 0.90 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Mean CASS‐4 (n=5) 1.09 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ Mean CASS‐4 (n=2) ‐‐‐ 24 25 533 ‐‐‐ 279 <16 359 Mean CASS‐4 (n=3) ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ 2.8 ‐‐‐ ‐‐‐ ‐‐‐
Certified value ‐ CASS‐4 1.11 26 26 592 3 314 <16 381 % recovery 98 94 96 90 101 89 ‐ 94
Table B3: Certified reference material (CASS‐5) for dissolved metals analyses
LABORATORY I.D. Cd Co Cu Ni Pb Zn (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) CASS‐5, 14/12/11 21 85 347 305 <16 691 CASS‐5, 23/01/12 17 87 351 336 <16 623 CASS‐5, 24/01/12 21 90 371 333 <16 726
Mean CASS‐5 (n=3) 19 88 356 325 <16 680
Certified value ‐ CASS‐5 22 95` 380 330 <16 719 % recovery 90 92 94 98 ‐ 95
40 |Trace metal concentrations in Port Curtis
Table B4: Dissolved metals analyses: replicate determinations
Site Al As Cd Co Cr Cu Fe Mn Ni Pb Zn (µg/L) (µg/L) (ng/L) (ng/L) (µg/L) (ng/L) (µg/L) (µg/L) (ng/L) (ng/L) (ng/L)
Site 16, 0.5 m, Site Dup 1 ‐‐‐ 1.05 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 16, 0.5 m, Site Dup 1 ‐‐‐ 0.96 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 16, 0.5 m, Site Dup 1 ‐‐‐ 1.00 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 13, 0.5 m ‐‐‐ ‐‐‐ 6 34 ‐‐‐ 638 ‐‐‐ ‐‐‐ 373 13 163
Site 13, 0.5 m ‐‐‐ ‐‐‐ 5 34 ‐‐‐ 611 ‐‐‐ ‐‐‐ 345 13 136
Site 13, 0.5 m ‐‐‐ ‐‐‐ 5 34 ‐‐‐ 625 ‐‐‐ ‐‐‐ 359 13 149
Site 11, 0.5 m 4 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.8 <0.1 ‐‐‐ ‐‐‐ ‐‐‐
Site 11, 0.5 m 4 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.8 <0.1 ‐‐‐ ‐‐‐ ‐‐‐
Site 11, 0.5 m 4 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.8 <0.1 ‐‐‐ ‐‐‐ ‐‐‐
Site 3, 5 m ‐‐‐ 0.94 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 3, 5 m ‐‐‐ 0.88 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 3, 5 m ‐‐‐ 0.91 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 10, 0.5 m, Site Dup 1 5 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.9 1.7 ‐‐‐ ‐‐‐ ‐‐‐
Site 10, 0.5 m, Site Dup 1 4 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.4 1.7 ‐‐‐ ‐‐‐ ‐‐‐
Site 10, 0.5 m, Site Dup 1 4 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.7 1.7 ‐‐‐ ‐‐‐ ‐‐‐
Site 9, 6 m ‐‐‐ 0.88 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 9, 6 m ‐‐‐ 0.92 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 9, 6 m ‐‐‐ 0.90 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 6, 6 m 1 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 0.9 0.7 ‐‐‐ ‐‐‐ ‐‐‐
Site 6, 6 m 1 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.1 0.7 ‐‐‐ ‐‐‐ ‐‐‐
Site 6, 6 m 1 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 1.0 0.7 ‐‐‐ ‐‐‐ ‐‐‐
Site 6, 0.5 m ‐‐‐ 0.89 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 6, 0.5 m ‐‐‐ 0.96 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 6, 0.5 m ‐‐‐ 0.92 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 20, 0.5 m, Site Dup 2 2 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 0.9 1.2 ‐‐‐ ‐‐‐ ‐‐‐
Site 20, 0.5 m, Site Dup 2 2 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 0.8 1.2 ‐‐‐ ‐‐‐ ‐‐‐
Site 20, 0.5 m, Site Dup 2 2 ‐‐‐ ‐‐‐ ‐‐‐ <1 ‐‐‐ 0.8 1.2 ‐‐‐ ‐‐‐ ‐‐‐
Site 19, 0.5 m ‐‐‐ ‐‐‐ <1.3 25 ‐‐‐ 121 ‐‐‐ ‐‐‐ 221 11 19
Site 19, 0.5 m ‐‐‐ ‐‐‐ <1.3 25 ‐‐‐ 120 ‐‐‐ ‐‐‐ 213 11 17
Site 19, 0.5 m ‐‐‐ ‐‐‐ <1.3 25 ‐‐‐ 120 ‐‐‐ ‐‐‐ 217 11 18
Site 18, 0.5 m ‐‐‐ ‐‐‐ 1.3 23 ‐‐‐ 152 ‐‐‐ ‐‐‐ 204 11 445
Site 18, 0.5 m ‐‐‐ ‐‐‐ 1.3 23 ‐‐‐ 147 ‐‐‐ ‐‐‐ 197 11 432
Site 18, 0.5 m ‐‐‐ ‐‐‐ 1.3 23 ‐‐‐ 149 ‐‐‐ ‐‐‐ 200 11 439
[Trace metal concentrations in Port Curtis] | 41
Table B5: Spike recovery data for the dissolved metals analyses
Site Al As Cd Co Cr Cu Fe Mn Ni Pb Zn Recovery (%)
Site 16, 0.5 m, Dup 2 ‐‐‐ 87 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 1, 0.5 m 96 ‐‐‐ 96 96 100 99 100 96 97 104 95
Site 8, 0.5 m 95 ‐‐‐ 94 95 98 97 100 98 93 104 91
Site 14, 0.5 m ‐‐‐ 100 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 12, 0.5 m 93 ‐‐‐ ‐‐‐ ‐‐‐ 100 ‐‐‐ 98 98 ‐‐‐ ‐‐‐ ‐‐‐
Site 7, 0.5 m, Dup 1 ‐‐‐ 88 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐
Site 7, 0.5 m, Dup 2 ‐‐‐ ‐‐‐ 106 103 ‐‐‐ 104 ‐‐‐ ‐‐‐ 99 102 108
Site 20, 0.5 m, Dup 1 105 ‐‐‐ 99 98 107 94 102 105 96 102 102
Site 20, 0.5 m, Dup 2 ‐‐‐ ‐‐‐ 97 96 ‐‐‐ 98 ‐‐‐ ‐‐‐ 93 100 100
Site 21, 0.5 m ‐‐‐ ‐‐‐ 102 99 ‐‐‐ 99 ‐‐‐ ‐‐‐ 95 101 99
Field Blank 3 100 ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐‐‐ ‐ ‐ ‐
Particulate Metals QC Data Table B6: Limits of detection for sediment analyses
Ag Al As Ba Be Cd Co Cr Cu Fe Ga Hg (µg/g, dry weight) LOD (3σ) 0.002 10 1 0.1 0.02 0.03 0.02 0.4 1 4 1 0.02
Mn Mo Ni Pb Sb Se Sr Tl V Zn
LOD (3σ) 0.3 0.04 1 1 0.004 0.04 0.1 0.01 0.3 1
42 |Trace metal concentrations in Port Curtis
Table B7. Sediment metals PACS‐2 certified reference material analyses
Sample ID/digestion ID: Ag Al As Ba Be Cd Co Cr Cu Fe Hg
µg/g dry weight
PACS‐2 (CUR‐2‐4) 1.26 19500 24 484 0.46 2.46 8.7 52 295 30700 3.19
PACS‐2 (CUR‐2‐5) 1.11 15600 24 407 0.38 2.22 8.6 47 292 29100 3.06
PACS‐2 (CUR‐3‐4) 1.15 16200 24 450 0.39 2.43 8.2 47 295 30100 3.01
PACS‐2 (CUR‐3‐5) 1.21 15400 23 354 0.38 2.46 8.3 46 297 29900 3.40
PACS‐2 (CUR‐4‐4) 1.17 14600 24 369 0.35 2.43 8.0 45 290 29800 3.21
PACS‐2 (CUR‐4‐5) 1.20 17900 24 437 0.39 2.62 8.7 49 289 30300 3.19
PACS‐2 (CUR‐5‐4) 1.30 18200 24 461 0.42 2.48 8.8 49 292 30500 2.74
PACS‐2 (CUR‐5‐5) 1.22 14600 23 332 0.35 2.42 8.5 46 295 29400 2.88
PACS‐2 Average (n=8) 1.20 16500 24 412 0.39 2.44 8.5 48 293 29975 3.08
In‐house reference value 1.16 16700 26 ‐‐‐ 0.43 2.45 9.5 51 299 31200 2.91
% Recovery 104 99 92 ‐‐‐ 91 100 89 93 98 96 106
Sample ID/digestion ID: Mn Mo Ni Pb Sb Se Sr Tl V Zn
µg/g dry weight
PACS‐2 (CUR‐2‐4) 255 4.9 32 168 8.34 1.01 69 0.46 81 343
PACS‐2 (CUR‐2‐5) 238 4.8 30 169 7.36 0.98 61 0.42 71 333
PACS‐2 (CUR‐3‐4) 241 4.9 31 170 6.98 0.98 62 0.42 72 338
PACS‐2 (CUR‐3‐5) 238 5.0 31 168 8.11 1.03 60 0.44 70 338
PACS‐2 (CUR‐4‐4) 235 5.0 31 165 8.25 0.90 59 0.40 70 336
PACS‐2 (CUR‐4‐5) 245 5.1 32 166 7.85 0.96 65 0.42 75 332
PACS‐2 (CUR‐5‐4) 249 5.1 32 167 9.02 0.93 70 0.44 77 339
PACS‐2 (CUR‐5‐5) 234 5.0 30 164 8.10 0.93 62 0.43 68 334
PACS‐2 Average (n=8) 242 5.0 31 167 8.00 0.96 64 0.43 73 337
In‐house reference value 253 5.0 32 170 8.01 0.99 69 ‐‐‐ 82 345
% Recovery 96 100 97 98 100 97 92 ‐‐‐ 89 98
[Trace metal concentrations in Port Curtis] | 43
Table B8. Total sediment metals replicate analyses
Site Ag Al As Ba Be Cd Co Cr Cu Fe Ga Hg (µg/g, dry weight) Site 2 0.04 8450 53 10 0.78 0.39 31 24 7 62300 8 <0.02 Site 2 0.04 8400 54 11 0.80 0.37 29 24 7 62900 8 <0.02 Site 2 0.04 8430 54 10 0.79 0.38 30 24 7 62600 8 <0.02 Site 4 0.03 12800 6 15 0.37 0.21 8 14 7 14400 5 <0.02 Site 4 0.03 8850 7 12 0.35 0.19 8 12 8 13600 4 <0.02 Site 4 0.03 10800 7 14 0.36 0.20 8 13 7 14000 5 <0.02 Site 6 0.03 17200 9 65 0.5 0.21 6 21 19 25700 7 <0.02 Site 6 0.03 17100 8 64 0.5 0.18 6 21 19 25200 7 <0.02 Site 6 0.04 21500 8 64 0.5 0.19 6 24 19 26900 8 <0.02 Site 6 0.03 18600 8 64 0.5 0.19 6 22 19 25900 8 <0.02 Site 7 0.05 17000 11 81 0.7 0.36 13 23 20 27500 7 <0.02 Site 7 0.06 23300 12 83 0.7 0.38 13 26 21 29300 9 <0.02 Site 7 0.06 23200 11 83 0.7 0.39 13 26 21 28900 9 <0.02 Site 7 0.06 21200 11 82 0.7 0.38 13 25 21 28600 8 <0.02 Site 10 0.06 20100 10 21 0.79 0.86 12 28 24 26500 9 0.17 Site 10 0.08 25800 10 25 0.87 1.02 13 32 24 29900 10 0.15 Site 10 0.07 23000 10 23 0.83 0.94 12 30 24 28200 9 0.16 Site 11 0.01 3310 19 9 0.25 0.29 11 8 4 18300 3 <0.02 Site 11 0.02 3330 20 9 0.30 0.31 10 8 4 18200 2 0.02 Site 11 0.02 4820 19 10 0.24 0.30 10 8 5 17600 3 <0.02 Site 11 0.02 3820 20 9 0.26 0.30 10 8 4 18000 3 0.02 Site 14 0.03 13300 8 26 0.31 0.23 7 14 9 16500 5 <0.02 Site 14 ‐‐‐ 13400 7 26 ‐‐‐ ‐‐‐ ‐‐‐ 14 9 16500 5 ‐‐‐ Site 14 0.03 13400 7 26 0.31 0.23 7 14 9 16500 5 <0.02 Site 15 0.02 4790 14 11 0.3 0.18 9 9 6 14600 3 <0.02 Site 15 0.02 3980 14 11 0.3 0.17 10 8 7 14100 2 0.02 Site 15 0.02 4390 14 11 0.3 0.18 10 8 6 14400 2 0.02 Site 17 0.03 5330 34 8 0.4 0.28 15 10 6 23100 4 <0.02 Site 17 0.02 6750 32 11 0.3 0.24 13 11 5 21600 4 <0.02 Site 17 0.03 6040 33 10 0.4 0.26 14 10 5 22400 4 <0.02 Site 18 0.01 2030 8 5 0.2 0.09 3 6 0.3 5070 1 <0.02 Site 18 0.01 2640 9 6 0.2 0.09 3 6 0.1 5300 1 <0.02 Site 18 0.01 2340 8 6 0.2 0.09 3 6 0.2 5180 1 <0.02
44 |Trace metal concentrations in Port Curtis
Table B9. Total sediment metals, replicate analyses
Site Mn Mo Ni Pb Sb Se Sr Tl V Zn (µg/g, dry weight) Site 2 531 2 14.5 12 0.24 0.18 224 0.05 112 53 Site 2 539 2 14.3 13 0.25 0.17 225 0.05 113 53 Site 2 535 2 14.4 13 0.25 0.17 224 0.05 112 53 Site 4 343 0.4 7.6 5 0.04 0.13 61 0.06 31 26 Site 4 373 0.4 6.9 4 0.12 0.11 57 0.05 29 24 Site 4 358 0.4 7.2 5 0.08 0.12 59 0.1 30 25 Site 6 105 1 7.3 10 0.18 0.50 33 0.08 52 23 Site 6 103 1 6.7 10 0.16 0.51 33 0.08 51 23 Site 6 106 1 7.5 11 0.20 0.51 34 0.10 54 26 Site 6 104 1 7.2 10 0.18 0.51 34 0.09 52 24 Site 7 365 1 13.1 9 0.19 0.18 47 0.08 50 42 Site 7 365 1 15.2 11 0.16 0.21 51 0.11 54 46 Site 7 363 1 14.6 11 0.16 0.20 51 0.10 53 46 Site 7 365 1 14.3 10 0.17 0.20 50 0.10 52 45 Site 10 243 1 16.0 11 0.25 0.32 39 0.1 54 56 Site 10 256 1 17.4 12 0.27 0.36 42 0.1 62 61 Site 10 250 1 16.7 12 0.26 0.34 41 0.1 58 59 Site 11 897 1 5.9 5 0.10 0.13 339 0.02 42 18 Site 11 900 1 5.9 5 0.12 0.13 340 0.02 42 18 Site 11 891 1 5.9 4 0.16 0.13 369 0.02 43 18 Site 11 896 1 5.9 5 0.13 0.13 349 0.02 42 18 Site 14 346 1 6.5 4 0.13 0.10 95 0.06 39 28 Site 14 349 ‐‐‐ 6.7 4 ‐‐‐ ‐‐‐ 96 ‐‐‐ 39 28 Site 14 348 1 6.6 4 0.13 0.10 95 0.06 39 28 Site 15 646 1 6.5 5 0.21 0.16 468 0.03 35 21 Site 15 671 1 6.2 4 0.24 0.13 503 0.03 32 21 Site 15 659 1 6.4 5 0.23 0.15 486 0.03 33 21 Site 17 1258 1 7.9 6 0.39 0.12 595 0.03 49 22 Site 17 661 1 6.9 7 0.30 0.12 557 0.03 47 22 Site 17 960 1 7.4 6 0.35 0.12 576 0.03 48 22 Site 18 157 0.1 2.0 2 0.05 0.02 168 0.01 11 6 Site 18 169 0.1 2.1 2 0.06 0.02 166 0.02 12 6 Site 18 163 0.1 2.0 2 0.05 0.02 167 0.01 11 6
[Trace metal concentrations in Port Curtis] | 45
Table B11 Sediment metals in the <63 µm fraction, replicate analyses: (Sites 2 to 8) (
Site Ag Al As Ba Be Cd Co Cr Cu Fe Ga Hg (µg/g, dry weight) Site 2 0.08 38400 15 36 1.18 0.62 15 48 23 37800 14 0.08 Site 2 0.08 38700 14 36 1.17 0.63 15 48 24 38000 14 0.08 Site 2 0.09 32400 14 30 1.03 0.77 14 44 23 36600 13 0.07 Site 2 ‐‐‐ 32800 14 31 ‐‐‐ ‐‐‐ ‐‐‐ 45 22 37300 12 ‐‐‐ Site 2 0.08 35600 14 33 1.13 0.68 14 46 23 37400 13 0.08 Site 3 0.06 28500 14 23 0.99 0.62 15 38 23 33400 11 0.11 Site 3 0.08 29100 13 25 1.01 0.86 16 38 24 34100 5 0.11 Site 3 0.07 28800 13 24 1.00 0.74 15 38 23 33800 8 0.11 Site 4 0.06 18000 10 22 0.86 0.88 13 29 21 26700 8 0.13 Site 4 0.06 35800 10 35 1.00 0.77 14 40 23 33900 13 0.13 Site 4 0.05 23900 9 26 0.85 0.73 12 33 22 29700 10 0.13 Site 4 0.06 25900 9 28 0.90 0.79 13 34 22 30100 10 0.13 Site 8 0.05 21200 13 19 0.94 0.58 15 32 24 32300 9 0.07 Site 8 0.09 32900 13 28 1.17 0.90 16 41 25 38700 13 0.04 Site 8 0.07 33100 14 28 1.05 0.74 16 41 25 39000 13 0.05 Site 8 0.07 29100 14 25 1.05 0.74 16 38 24 36700 12 0.05 Site 6 0.03 23900 5 59 0.50 0.28 6 25 22 23700 9 0.05 Site 6 0.03 23600 6 58 0.50 0.33 6 25 21 23600 9 0.06 Site 6 0.03 23800 5 58 0.50 0.30 6 25 22 23700 9 0.06 Site 6 0.03 31000 9 69 0.65 0.39 8 31 23 29300 11 0.07 Site 6 0.03 26100 8 67 0.58 0.39 7 28 22 27300 9 0.06 Site 6 0.03 28600 8 68 0.61 0.39 8 29 22 28300 10 0.07 Site 7 0.04 23800 12 86 0.73 0.49 13 26 22 29300 9 0.06 Site 7 0.04 18100 12 82 0.67 0.42 12 24 22 28500 7 0.05 Site 7 0.04 21000 12 84 0.70 0.45 12 25 22 28900 8 0.05
46 |Trace metal concentrations in Port Curtis
Table B11 Sediment metals in the <63 µm fraction, replicate analyses: (Sites 2 to 8)
Site Mn Mo Ni Pb Sb Se Sr Tl V Zn (µg/g, dry weight) Site 2 322 1 27.2 14 0.20 0.39 54 0.2 69 69 Site 2 325 1 27.0 14 0.20 0.36 54 0.2 70 70 Site 2 319 1 25.4 14 0.20 0.32 52 0.2 65 64 Site 2 322 ‐‐‐ 25.6 14 ‐‐‐ ‐‐‐ 52 ‐‐‐ 66 65 Site 2 322 1 26.3 14 0.20 0.36 53 0.2 67 67 Site 3 198 1 22.5 13 0.24 0.34 45 0.2 64 65 Site 3 197 1 22.1 13 0.24 0.32 46 0.2 64 65 Site 3 198 1 22.3 13 0.24 0.33 46 0.2 64 65 Site 4 211 1 16.5 11 0.21 0.31 46 0.1 52 53 Site 4 235 1 21.5 13 0.19 0.35 53 0.2 67 67 Site 4 218 1 18.8 12 0.20 0.30 48 0.1 57 57 Site 4 221 1 18.9 12 0.20 0.32 49 0.1 59 59 Site 8 295 1 19.6 13 0.23 0.35 52 0.1 56 58 Site 8 315 1 23.5 14 0.26 0.36 57 0.2 69 66 Site 8 317 1 23.6 14 0.24 0.35 57 0.1 69 67 Site 8 309 1 22.2 13 0.24 0.35 55 0.1 65 64 Site 6 95 1 7.9 15 0.16 0.34 26 0.11 46 29 Site 6 95 1 7.7 15 0.15 0.35 25 0.11 45 29 Site 6 95 1 7.8 15 0.16 0.34 25 0.11 45 29 Site 6 175 1 12.2 13 0.17 0.46 33 0.15 54 40 Site 6 169 1 10.9 12 0.16 0.44 31 0.13 50 37 Site 6 172 1 11.5 13 0.17 0.45 32 0.14 52 38 Site 7 370 1 14.9 13 0.17 0.22 43 0.12 57 47 Site 7 377 1 13.6 10 0.17 0.18 41 0.10 53 45 Site 7 374 1 14.2 11 0.17 0.20 42 0.11 55 46
[Trace metal concentrations in Port Curtis] | 47
Table B12. Sediment metals in the <63 µm fraction, replicate analyses: (Sites 11‐18) (
Site Ag Al As Ba Be Cd Co Cr Cu Fe Ga Hg (µg/g, dry weight) Site 11 0.06 26400 12 27 0.87 0.75 16 33 26 31000 10 0.09 Site 11 0.05 26200 12 27 0.92 0.78 17 33 25 30900 11 0.10 Site 11 0.06 30200 12 30 0.88 0.80 15 35 25 31300 11 0.09 Site 11 0.06 27600 12 28 0.89 0.78 16 34 25 31100 11 0.09 Site 13 0.05 26700 22 54 0.89 1.28 17 30 24 38100 11 0.31 Site 13 0.07 25300 21 54 0.90 1.40 16 29 23 38700 10 0.33 Site 13 0.06 26000 21 54 0.89 1.34 17 30 23 38400 10 0.32 Site 14 0.04 16400 13 27 0.73 0.84 13 24 26 30200 8 0.19 Site 14 0.04 16200 13 27 0.71 0.82 14 24 26 30100 8 0.19 Site 14 0.08 40600 13 46 0.85 1.05 15 36 30 39600 14 0.18 Site 14 0.05 24400 13 33 0.76 0.91 14 28 27 33300 10 0.18 Site 15 0.04 16900 13 26 0.82 0.75 13 26 23 26000 8 0.16 Site 15 0.06 28500 14 34 0.80 0.89 14 33 24 30900 11 0.15 Site 15 0.05 22700 14 30 0.81 0.82 14 29 23 28400 9 0.16 Site 16 0.04 15100 14 21 0.71 0.84 11 25 21 24900 8 0.17 Site 16 0.05 18400 14 22 0.78 0.95 10 27 22 26900 9 0.18 Site 16 0.04 16700 14 22 0.74 0.90 10 26 22 25900 8 0.17 Site 17 0.05 20700 15 25 0.73 0.67 12 27 21 26300 8 0.09 Site 17 0.05 21100 15 25 0.76 0.68 12 28 21 26500 8 0.08 Site 17 0.05 20900 15 25 0.75 0.67 12 27 21 26400 8 0.09 Site 18 0.04 13800 15 20 0.65 4.50 10 29 8 20200 10 1.26 Site 18 0.04 17700 12 16 0.81 0.69 9 35 9 22600 7 0.15 Site 18 0.04 17700 12 16 0.82 0.64 9 35 9 22600 7 0.13 Site 18 0.04 16400 13 17 0.76 1.94 10 33 9 21800 8 0.51
48 |Trace metal concentrations in Port Curtis
Table B13. Sediment metals in the <63 µm fraction: replicate analyses: (Sites 11‐18) Mn to Zn (All concentrations are in units of µg/g)
Site Mn Mo Ni Pb Sb Se Sr Tl V Zn (µg/g, dry weight) Site 11 859 1 20.0 12 0.21 0.63 75 0.1 59 66 Site 11 853 1 19.6 12 0.21 0.65 75 0.1 58 65 Site 11 841 1 20.6 12 0.07 0.63 78 0.2 63 67 Site 11 851 1 20.1 12 0.17 0.64 76 0.1 60 66 Site 13 799 1 17.4 13 0.27 0.37 109 0.1 77 64 Site 13 796 1 16.8 13 0.30 0.33 106 0.1 77 62 Site 13 798 1 17.1 13 0.28 0.35 108 0.1 77 63 Site 14 581 1 13.1 10 0.19 0.28 72 0.1 61 60 Site 14 576 1 13.2 12 0.18 0.30 72 0.1 60 60 Site 14 608 1 19.7 12 0.20 0.29 82 0.1 76 73 Site 14 588 1 15.3 11 0.19 0.29 75 0.1 66 64 Site 15 727 1 15.9 11 0.19 0.57 96 0.1 50 53 Site 15 741 1 18.8 12 0.20 0.52 100 0.1 60 62 Site 15 734 1 17.4 12 0.20 0.54 98 0.1 55 57 Site 16 428 1 13.9 11 0.17 0.24 138 0.1 45 52 Site 16 426 1 15.0 11 0.17 0.24 136 0.1 48 55 Site 16 427 1 14.5 11 0.17 0.24 137 0.1 47 54 Site 17 609 1 16.3 11 0.19 0.59 127 0.1 53 53 Site 17 605 1 16.6 11 0.21 0.59 127 0.1 52 53 Site 17 607 1 16.4 11 0.20 0.59 127 0.1 52 53 Site 18 681 1 12.4 11 0.22 0.34 211 0.09 42 45 Site 18 283 1 15.0 12 0.24 0.39 178 0.14 52 39 Site 18 285 1 15.0 13 0.25 0.41 178 0.14 52 39 Site 18 417 1 14.1 12 0.24 0.38 189 0.13 49 41
[Trace metal concentrations in Port Curtis] | 49
Table B15. Sediment‐bound metals, spike recovery analysis: Ag to Hg
Site Fraction Ag As Ba Be Cd Co Cr Cu Ga Hg Recovery (%) Site 1 <63µm 97 95 88 92 101 93 94 95 91 106 Site 1 Total 94 96 95 101 100 93 95 95 95 97 Site 6 Total 90 98 97 92 90 107 100 102 96 102 Site 7 Total 84 98 96 94 90 108 100 102 96 97 Site 13 <63µm 95 96 90 96 101 102 96 98 93 104 Site 13 Total 95 99 96 103 101 101 97 98 96 97 Site 14 <63µm 101 97 93 103 104 100 97 100 96 97 Site 14 Total 92 99 95 101 100 102 97 99 96 97 Site 15 <63µm 102 97 93 92 103 98 97 100 94 98 Site 18 <63µm 99 97 93 95 108 94 98 100 95 101
Sediment‐bound metals spike recovery analysis: Mn to Zn
Site Fraction Mn Mo Ni Pb Sb Se Sr Tl V Zn Recovery (%) Site 1 <63µm ‐‐‐ 113 92 92 106 83 94 99 88 96 Site 1 Total ‐‐‐ 106 94 94 102 91 93 95 96 96 Site 6 Total 101 107 99 99 96 105 103 100 92 100 Site 7 Total 90 112 98 98 96 98 103 95 92 100 Site 13 <63µm ‐‐‐ 112 95 95 107 97 89 89 90 97 Site 13 Total 87 111 96 96 104 90 95 94 98 98 Site 14 <63µm 88 110 97 97 106 100 89 96 91 100 Site 14 Total 91 107 96 95 100 91 98 94 98 97 Site 15 <63µm 85 108 95 96 107 91 88 94 91 98 Site 18 <63µm 88 114 97 96 115 90 86 95 91 100
50 |Trace metal concentrations in Port Curtis
TSS Metals QC DATA
Table B16. TSS‐bound metals PACS‐2 certified reference material recovery analysis
LABORATORY I.D. Ag Al As Ba Be Cd Co Cr Cu Fe Hg (µg/g, dry weight) PACS‐2 (PT‐1‐9) 1.40 19300 28 509 0.44 2.15 9.0 58 279 30300 3.03 PACS‐2 (PT‐1‐10) 1.28 20600 28 515 0.44 2.14 8.9 59 276 30100 2.96 PACS‐2 (PT‐2‐4) 1.27 19200 26 489 0.42 2.08 8.7 56 272 29900 2.90 PACS‐2 (PT‐2‐4) 1.30 19300 27 489 0.41 2.04 9.0 58 283 29800 3.03 PACS‐2 (PT‐2‐5) 1.37 15800 27 425 0.38 2.21 8.9 54 283 28500 3.09 PACS‐2 (PT‐3‐4) 1.20 18800 27 512 0.40 2.00 8.6 55 265 30000 2.99 PACS‐2 (PT‐3‐5) 1.40 17300 27 480 0.41 1.99 8.8 56 282 29800 3.09 PACS‐2 average (n=7) 1.32 18600 27 488 0.42 2.09 8.9 56 277 29800 3.01 PACS‐2 in‐house value 1.16 16700 26 ‐0.43 2.45 9.5 51 299 31200 2.94 % recovery 113 111 107 ‐ 97 85 93 111 93 95 102
LABORATORY I.D. Mn Mo Ni Pb Sb Se Sr Tl V Zn (µg/g, dry weight) PACS‐2 (PT‐1‐9) 253 5.1 34 172 8.6 1.00 63 0.44 89 311 PACS‐2 (PT‐1‐10) 252 5.1 33 171 8.7 1.00 65 0.44 92 311 PACS‐2 (PT‐2‐4) 250 4.9 32 172 7.5 0.95 63 0.44 86 296 PACS‐2 (PT‐2‐4) 250 5.1 34 174 7.8 0.96 63 0.45 90 307 PACS‐2 (PT‐2‐5) 236 5.1 32 173 8.1 1.01 57 0.43 82 310 PACS‐2 (PT‐3‐4) 249 5.1 32 165 7.2 0.99 61 0.45 85 304 PACS‐2 (PT‐3‐5) 247 5.3 33 179 8.3 1.01 59 0.45 85 314 PACS‐2 average (n=7) 248 5.1 33 172 8.0 0.99 61 0.44 87 308 PACS‐2 in‐house value 253 5.0 32 170 8.0 0.99 69 ‐ 82 345 % recovery 98 102 102 101 100 100 89 ‐ 107 89
[Trace metal concentrations in Port Curtis] | 51
Table B17. TSS‐bound metals replicate analysis: Ag to Hg
Sample Ag Al As Ba Be Cd Co Cr Cu Fe Hg
(µg/g, dry weight)
Site 16, 0.5 m, Dup 2 <2.4 42500 20 49 1.2 <1.1 15 47 36 39100 <0.39 Site 16, 0.5 m, Dup 2 <2.4 42200 17 49 1.3 <1.1 15 46 34 39500 <0.39 Site 16, 0.5 m, Dup 2 <2.4 42400 19 49 1.3 <1.1 15 47 35 39300 <0.39 Site 1, 4 m <2.4 56600 17 59 1.3 <1.1 13 64 19 43200 <0.39 Site 1, 4 m <2.4 57200 18 58 1.2 <1.1 14 65 19 42900 <0.39 Site 1, 4 m <2.4 56900 17 59 1.3 <1.1 14 64 19 43000 <0.39 Site 3, 5 m <2.4 35000 18 46 0.8 <1.1 14 47 29 36000 0.40 Site 3, 5 m <2.4 34400 17 46 0.7 <1.1 14 44 27 35900 0.49 Site 3, 5 m <2.4 34700 17 46 0.8 <1.1 14 45 28 35900 0.44 Site 9, 6 m <2.4 28800 12 34 0.6 <1.1 10 32 19 23500 <0.39 Site 9, 6 m <2.4 28800 12 34 0.6 <1.1 10 32 20 23600 <0.39 Site 9, 6 m <2.4 28800 12 34 0.6 <1.1 10 32 20 23600 <0.39 Site 6, 6 m 3.29 28700 16 50 1.0 <1.1 12 38 29 31400 <0.39 Site 6, 6 m 3.41 28800 16 50 1.0 <1.1 12 38 28 31600 <0.39 Site 6, 6 m 3.35 28800 16 50 1.0 <1.1 12 38 29 31500 <0.39 Site 7, 0.5 m, Dup 1 <2.4 19300 16 30 0.8 <1.1 12 30 20 27700 <0.39 Site 7, 0.5 m, Dup 1 <2.4 18900 14 31 1.1 <1.1 12 30 21 28600 <0.39 Site 7, 0.5 m, Dup 1 <2.4 19100 15 31 0.9 <1.1 12 30 20 28100 0.51
52 |Trace metal concentrations in Port Curtis
Table B18. TSS‐bound metals replicate analysis: Mn to Zn
Sample Mn Mo Ni Pb Sb Se Sr Tl V Zn
(µg/g, dry weight)
Site 16, 0.5 m, Dup 2 912 0.7 23 12.0 0.27 0.44 89 0.09 84 75 Site 16, 0.5 m, Dup 2 913 1.4 20 11.6 0.34 1.14 89 0.10 80 72 Site 16, 0.5 m, Dup 2 912 1.0 21 11.8 0.30 0.79 89 0.10 82 74 Site 1, 4 m 764 2.1 35 11.3 0.21 0.30 84 0.15 88 65 Site 1, 4 m 772 2.1 35 11.1 0.21 0.35 84 0.10 86 73 Site 1, 4 m 768 2.1 35 11.2 0.21 0.32 84 0.12 87 69 Site 3, 5 m 675 1.9 22 10.6 0.17 0.36 46 0.20 73 64 Site 3, 5 m 668 1.1 21 10.1 0.18 0.15 46 0.21 75 63 Site 3, 5 m 672 1.5 21 10.3 0.18 0.25 46 0.21 74 64 Site 9, 6 m 458 0.9 15 7.0 0.15 0.26 95 0.16 57 43 Site 9, 6 m 456 1.0 16 7.1 0.16 0.26 95 0.15 57 42 Site 9, 6 m 457 0.9 16 7.1 0.15 0.26 95 0.15 57 42 Site 6, 6 m 535 1.0 17 11.1 0.19 0.61 60 0.31 65 50 Site 6, 6 m 531 1.1 16 10.4 0.27 0.41 60 0.25 63 48 Site 6, 6 m 533 1.1 16 10.8 0.23 0.51 60 0.28 64 49 Site 7, 0.5 m, Dup 1 638 1.0 19 8.1 0.23 0.40 53 0.24 54 43 Site 7, 0.5 m, Dup 1 659 0.7 21 7.9 0.20 0.42 54 0.21 54 47 Site 7, 0.5 m, Dup 1 648 0.9 20 8.0 0.21 0.41 54 0.22 54 45
[Trace metal concentrations in Port Curtis] | 53
Table B19. TSS‐bound metals: spike recovery analysis
Site Ag Al As Ba Be Cd Co Cr Cu Fe Hg Recovery (%)
Site 1, 0.5 m 91 87 106 96 113 106 105 106 110 86 107 Site 3, 0.5 m 90 91 104 96 102 104 103 101 104 88 103 Site 9, 3 m 93 ‐‐‐ 107 95 104 108 107 105 106 ‐‐‐ 106 Site 5, 5.5 m 90 ‐‐‐ 106 96 100 105 105 103 104 ‐‐‐ 102 Site 6, 0.5 m 93 ‐‐‐ 105 96 98 104 104 102 105 ‐‐‐ 103
Site Mn Mo Ni Pb Sb Se Sr Tl V Zn Recovery (%)
Site 1, 0.5 m 100 104 106 102 105 107 94 103 105 111 Site 3, 0.5 m 99 101 104 98 102 101 93 97 102 106 Site 9, 3 m 98 104 106 97 105 103 91 99 105 105 Site 5, 5.5 m 100 102 105 97 100 102 90 99 104 101 Site 6, 0.5 m 99 103 102 98 102 102 92 99 102 105
54 |Trace metal concentrations in Port Curtis
Appendix C Dissolved metal concentrations in waters between the Southern Narrows and Rodds Bay
10
8 .
g/L) g/L) 6 μ
4
Dissolved Al ( 2 Low reliability ANZECC/ARMCANZ trigger value
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
1.8 Low reliability ANZECC/ARMCANZ trigger value = 2.3-4.5 µg/L 1.5 . 1.2 g/L) g/L) μ 0.9
0.6
Dissolved ( As 0.3
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
10 ANZECC/ARMCANZ 95% trigger value = 5500 ng/L
8 . Mean harbour, 2003 & 2004 6
4
2 Dissolved Cd (ng/L) (ng/L) Cd Dissolved
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 55
200 ANZECC/ARMCANZ 95% trigger value = 1000 ng/L / 1 μg/L
160 .
120
80
40 Dissolved Co (ng/L) Dissolved Co (ng/L)
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
1500 ANZECC/ARMCANZ 95% trigger value
1200 .
900
600
Mean harbour, 2003 & 2004 300 Dissolved Cu (ng/L) (ng/L) Cu Dissolved
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
14
12 . 10 g/L) g/L) μ 8
6
4
Dissolved Fe ( 2
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
8 Low reliability ANZECC/ARMCANZ trigger value = 80 µg/L
6 . g/L) g/L) μ 4
2 Dissolved ( Mn
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
56 |Trace metal concentrations in Port Curtis
1000 ANZECC/ARMCANZ 95% trigger value = 70000 ng/L / 70 μg/L
800 .
600
400
Mean harbour, 2003 & 2004
Dissolved Ni (ng/L) Dissolved Ni(ng/L) 200
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
100 90 ANZECC/ARMCANZ 95% trigger value = 4400 ng/L / 4.4 μg/L 80
. 70 60 50 40 30 20 Dissolved Pb (ng/L) Dissolved Pb (ng/L) 10 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
2000 ANZECC/ARMCANZ 95% trigger value = 15000 ng/L / 15 μg/L 1800 1600
. 1400 1200 1000 800 Mean harbour, 2003 & 2004 600 400 Dissolved Zn (ng/L) Dissolved(ng/L) Zn 200 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 57
Appendix D Total metal concentrations in waters between the Southern Narrows and Rodds Bay
2500 ANZECC/ARMCANZ 95% trigger value = 0.5 µg/L
2000
. 1500
1000 Total Al (µg/L) 500
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
2.0
1.5 .
1.0
Total As (µg/L) Total As (µg/L) 0.5
ANZECC/ARMCANZ 95% trigger value = 2.3 µg/L 0.0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
1.0 ANZECC/ARMCANZ 95% trigger value = 1 µg/L
0.8 . 0.6
0.4 Total Co (µg/L) Co (µg/L) Total 0.2
0.0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
58 |Trace metal concentrations in Port Curtis
4 ANZECC/ARMCANZ 95% trigger value = 27.4 µg/L
3 .
2
Total Cr (µg/L) (µg/L) Cr Total 1
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
4
3 .
2 ANZECC/ARMCANZ 95% trigger value
Total Cu (µg/L) Total Cu(µg/L) 1
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
2000
1500 .
1000
Total Fe (µg/L) (µg/L) Fe Total 500
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
50 ANZECC/ARMCANZ 95% trigger value = 80 µg/L
40 . 30
20 Total Mn (µg/L) (µg/L) Total Mn 10
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 59
5 ANZECC/ARMCANZ 95% trigger value = 70 µg/L
4
. 3
2 Total Ni (µg/L) Total Ni (µg/L) 1
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
1.0 ANZECC/ARMCANZ 95% trigger value = 4.4 µg/L
0.8
. 0.6
0.4 Total Pb (µg/L) 0.2
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
5 ANZECC/ARMCANZ 95% trigger value = 15 µg/L
4
. 3
2 Total Zn (µg/L) Zn (µg/L) Total 1
0 0123456789101112131415161718192021 Sites (Narrows to Rodd's Bay)
60 |Trace metal concentrations in Port Curtis
Appendix E TSS‐bound metals between the Southern Narrows and Rodds Bay
80000
. 60000
40000 TSS-Al (µg/g)
20000
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Sites (Narrows to Rodd's Bay)
40 . 30
20 TSS-As (µg/g) (µg/g) TSS-As
10
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
80 . 60
40 TSS-Ba (µg/g) TSS-Ba (µg/g)
20
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 61
2.0 . 1.5
1.0 TSS-Be (µg/g) (µg/g) TSS-Be
0.5
0.0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021 Sites (Narrows to Rodd's Bay)
20 . 15
10 TSS-Co (µg/g)
5
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
80 . 60
40 TSS-Cr (µg/g)
20
0 0123456789101112131415161718192021 Sites (Narrows to Rodd's Bay)
62 |Trace metal concentrations in Port Curtis
50
. 40
30
TSS-Cu (µg/g) TSS-Cu (µg/g) 20
10
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
50000
. 40000
30000
TSS-Fe (µg/g) (µg/g) TSS-Fe 20000
10000
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Sites (Narrows to Rodd's Bay)
1200 . 900
600 TSS-Mn (µg/g) (µg/g) TSS-Mn
300
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
4 . 3
2 TSS-Mo (µg/g) (µg/g) TSS-Mo
1
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 63
40 . 30
20 TSS-Ni (µg/g) (µg/g) TSS-Ni
10
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
20 . 15
10 TSS-Pb (µg/g) (µg/g) TSS-Pb
5
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
1
. 0
0
TSS-Sb (µg/g) (µg/g) TSS-Sb 0
0
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
1
. 1
1
TSS-Se (µg/g) (µg/g) TSS-Se 0
0
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
64 |Trace metal concentrations in Port Curtis
300
. 240
180
TSS-Sr (µg/g) (µg/g) TSS-Sr 120
60
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
1
0 .
0
TSS-Tl (µg/g) 0
0
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
120
. 90
60 TSS-V (µg/g) (µg/g) TSS-V
30
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
120
. 90
60 TSS-Zn (µg/g)
30
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 65
Appendix F Particulate metal concentrations measured in the total and <63 µm benthic sediment fractions between the Southern Narrows and Rodds Bay
0.10 ANZECC/ARMCANZ ISQG-low value = 1 μg/g . ANZECC/ARMCANZ ISQG-high value = 3.7 μg/g 0.08
0.06
0.04
0.02 <63 µm Sediment-Ag (µg/g) (µg/g) Sediment-Ag µm <63 0.00 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
0.10 ANZECC/ARMCANZ ISQG-low value = 1 μg/g . ANZECC/ARMCANZ ISQG-high value = 3.7 μg/g 0.08
0.06
0.04
0.02 Total Sediment-Ag (µg/g) (µg/g) Sediment-Ag Total
0.00 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
50000 . 40000
30000
20000
10000 <63 µm Sediment-Al (µg/g) (µg/g) Sediment-Al µm <63 0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
50000 .
40000
30000
20000
Total Sediment-Al (µg/g) 10000
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
66 |Trace metal concentrations in Port Curtis
60 ANZECC/ARMCANZ ISQG-high value =70 μg/g . 50
40
30 ANZECC/ARMCANZ ISQC-low value 20
10 <63 µm Sediment-As (µg/g) (µg/g) Sediment-As µm <63 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
60 ANZECC/ARMCANZ ISQG-high value =70 μg/g . 50
40
30 ANZECC/ARMCANZ ISQC-low value 20
Total Sediment-As (µg/g) (µg/g) Sediment-As Total 10
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
100 . 80
60
40
20 <63 µm Sediment-Ba (µg/g) (µg/g) Sediment-Ba µm <63 0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
100 .
80
60
40
20 Total Sediment-Ba (µg/g) (µg/g) Sediment-Ba Total
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
2.0 . 1.6
1.2
0.8
0.4 <63 µm Sediment-Be (µg/g) Sediment-Be (µg/g) µm <63 0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 67
2.0 .
1.6
1.2
0.8
0.4 Total Sediment-Be (µg/g) (µg/g) Sediment-Be Total
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
2.0 ANZECC/ARMCANZ ISQG-high value =10 μg/g . 1.6 ANZECC/ARMCANZ ISQC-low value 1.2
0.8
0.4 <63 µm Sediment-Cd (µg/g) Sediment-Cd (µg/g) µm <63 0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
2.0 ANZECC/ARMCANZ ISQG-high value =10 μg/g .
1.6 ANZECC/ARMCANZ ISQC-low value 1.2
0.8
0.4 Total Sediment-Cd (µg/g) Total Sediment-Cd (µg/g)
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
40 .
30
20
10 <63 µm Sediment-Co (µg/g) (µg/g) Sediment-Co µm <63 0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
40 .
30
20
10 Total Sediment-Co (µg/g) (µg/g) Sediment-Co Total
0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
68 |Trace metal concentrations in Port Curtis
50 ANZECC/ARMCANZ ISQG-low value = 80 μg/g . ANZECC/ARMCANZ ISQG-high value =370 μg/g 40
30
20
10 <63 µm Sediment-Cr (µg/g) (µg/g) Sediment-Cr µm <63 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
50
. ANZECC/ARMCANZ ISQG-low value = 80 μg/g ANZECC/ARMCANZ ISQG-high value =370 μg/g 40
30
20
10 Total Sediment-Cr (µg/g)
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
50 ANZECC/ARMCANZ ISQG-low value = 65 μg/g . ANZECC/ARMCANZ ISQG-high value =270 μg/g 40
30
20
10 <63 µm Sediment-Cu (µg/g) Sediment-Cu (µg/g) µm <63 0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
50
. ANZECC/ARMCANZ ISQG-low value = 65 μg/g ANZECC/ARMCANZ ISQG-high value =270 μg/g 40
30
20
10 Total Sediment-Cu (µg/g) (µg/g) Total Sediment-Cu
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay)
80000 .
60000
40000
20000 <63 µm Sediment-Fe (mg/g) (mg/g) Sediment-Fe µm <63 0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 69
80000 .
60000
40000
20000 Total Sediment-Fe (mg/g) (mg/g) Sediment-Fe Total
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay) 20 .
15
10
5 <63 µm Sediment-Ga (µg/g) (µg/g) Sediment-Ga µm <63 0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay) 20 .
15
10
5 Total Sediment-Ga (µg/g)
0 0123456789101112131415161718192021
Sites (Narrows to Rodd's Bay) 2.0 . 1.6
1.2 ANZECC/ARMCANZ ISQG-high value
0.8
0.4 ANZECC/ARMCANZ ISQC-low value <63 µm Sediment-Hg (µg/g) Sediment-Hg (µg/g) µm <63 0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
2.0 ANZECC/ARMCANZ ISQG-high value =1 μg/g .
1.6
1.2
0.8
0.4 Total Sediment-Hg (µg/g) (µg/g) Sediment-Hg Total ANZECC/ARMCANZ ISQC-low value
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
70 |Trace metal concentrations in Port Curtis
2000 . 1600
1200
800
400 <63 µm Sediment-Mn (µg/g) (µg/g) Sediment-Mn µm <63 0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
2000 .
1600
1200
800
400 Total Sediment-Mn (µg/g) (µg/g) Sediment-Mn Total
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
2.0 . 1.6
1.2
0.8
0.4 <63 µm Sediment-Mo (µg/g) (µg/g) Sediment-Mo µm <63 0.0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
2.0 .
1.6
1.2
0.8
0.4 Total Sediment-Mo (µg/g) (µg/g) Sediment-Mo Total
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
30 ANZECC/ARMCANZ ISQG-high value = 52 μg/g . 25 ANZECC/ARMCANZ ISQC-low value 20
15
10
5 <63µm Sediment-Ni (µg/g) 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 71
30
. ANZECC/ARMCANZ ISQG-high value = 52 μg/g 25 ANZECC/ARMCANZ ISQC-low value 20
15
10
Total Sediment-Ni (µg/g) Total Sediment-Ni (µg/g) 5
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
30 ANZECC/ARMCANZ ISQG-low value = 50 μg/g . 25 ANZECC/ARMCANZ ISQG-high value =220 μg/g
20
15
10
5 <63 µm Sediment-Pb (µg/g) (µg/g) Sediment-Pb µm <63 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
30 ANZECC/ARMCANZ ISQG-low value = 50 μg/g . 25 ANZECC/ARMCANZ ISQG-high value =220 μg/g
20
15
10
Total Sediment-Pb (µg/g) (µg/g) Total Sediment-Pb 5
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
0.8 ANZECC/ARMCANZ ISQG-low value = 2 μg/g . ANZECC/ARMCANZ ISQG-high value =25 μg/g
0.6
0.4
0.2 <63 µm Sediment-Sb (µg/g) (µg/g) Sediment-Sb µm <63 0.0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
0.8 ANZECC/ARMCANZ ISQG-low value = 2 μg/g . ANZECC/ARMCANZ ISQG-high value =25 μg/g 0.6
0.4
0.2 Total Sediment-Sb (µg/g) (µg/g) Total Sediment-Sb
0.0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
72 |Trace metal concentrations in Port Curtis
1.0 . 0.8
0.6
0.4
0.2 <63 µm Sediment-Se (µg/g) Sediment-Se (µg/g) µm <63 0.0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
1.0 .
0.8
0.6
0.4
0.2 Total Sediment-Se (µg/g) (µg/g) Sediment-Se Total
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
300 . 250
200
150
100
50 <63 µm Sediment-Sr (µg/g) (µg/g) Sediment-Sr µm <63 0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
300 . 250
200
150
100
Total Sediment-Sr (µg/g) 50
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
0.4 .
0.3
0.2
0.1 <63 µm Sediment-Tl (µg/g) (µg/g) Sediment-Tl µm <63 0.0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
[Trace metal concentrations in Port Curtis] | 73
0.4 .
0.3
0.2
0.1 Total Sediment-Tl (µg/g) (µg/g) Sediment-Tl Total
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
150 . 125
100
75
50
25 <63 µm Sediment-V (µg/g) (µg/g) Sediment-V µm <63 0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
150 . 125
100
75
50
Total Sediment-V (µg/g) (µg/g) Sediment-V Total 25
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
100 ANZECC/ARMCANZ ISQG-low value = 200 μg/g
. ANZECC/ARMCANZ ISQG-high value =410 μg/g 80
60
40
20 <63 µm Sediment-Zn (µg/g) (µg/g) Sediment-Zn µm <63 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sites (Narrows to Rodd's Bay)
100 ANZECC/ARMCANZ ISQG-low value = 200 μg/g . ANZECC/ARMCANZ ISQG-high value =410 μg/g 80
60
40
20 Total Sediment-Zn (µg/g) (µg/g) Total Sediment-Zn
0 0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Sites (Narrows to Rodd's Bay)
74 |Trace metal concentrations in Port Curtis
[Trace metal concentrations in Port Curtis] | 75
CONTACT US FOR FURTHER INFORMATION t 1300 363 400 CSIRO LAND AND WATER +61 3 9545 2176 Dr Simon Apte e [email protected] t +61 2 9710 6838 w www.csiro.au e [email protected] w Simon Apte
YOUR CSIRO Australia is founding its future on science and innovation. Its national science agency, CSIRO, is a powerhouse of ideas, technologies and skills for building prosperity, growth, health and sustainability. It serves governments, industries, business and communities across the nation.
76 |Trace metal concentrations in Port Curtis
FINAL REPORT
INVESTIGATION OF CONTAMINANT LEVELS IN GREEN TURTLES FROM GLADSTONE
31 March 2012
Prepared by: Caroline Gaus1*, Sharon Grant1, Nat Ling Jin1, Kristina Goot1, Lan Chen1, Alex Villa1, Frank Neugebauer2, Lixia Qi1, Colin Limpus3
1National Research Centre for Environmental Toxicology (Entox), The University of Queensland, 39 Kessels Road, Brisbane, QLD 4108, Australia
2Eurofins GfA Lab Service GmBH, Neulaender Kamp 1, 21079 Hamburg, Germany
3Aquatic Threatened Species and Threatening Processes, Environment and Resource Sciences Division, Department of Environment and Resource Management, Block C1, 41 Boggo Rd, Dutton Park QLD 4102
*Correspondence to: Caroline Gaus, email: [email protected]
Investigation of contaminant levels in green turtles from Gladstone
ACKNOWLEDGEMENTS We thank Julia Playford and her team at the Department of Environment and Resource Management for support, and Dr Michael Warne for review comments. We thank Prof. Jack Ng and Prof. Beate Escher for reviewing this report, and their helpful discussions throughout this study.
2 Investigation of contaminant levels in green turtles from Gladstone EXECUTIVE SUMMARY The objective of the present study was to measure the concentration of contaminants in blood of live green turtles captured in the Boyne River estuary near Gladstone, and to evaluate whether the contaminant levels are elevated and may pose a risk to the health of the turtle population.
During early 2011, Port Curtis experienced approximately 5 times higher mortality rates of sea turtles compared to previous years, as well as increased mortality rates of other wildlife species. In July 2011, an evaluation of the health status of live and diseased local green turtles was conducted. In parallel with this investigation, blood was collected from 40 live green turtles to assess exposure to a range of organic and inorganic contaminants that may be associated with agricultural, urban and industrial activities and that are known to accumulate in marine wildlife and may present a hazard to these species. Three of these 40 green turtles had to be euthanised due to poor diagnoses for survival, providing liver and kidney samples in addition to blood. Additional liver and fat samples were also obtained from stranded specimens.
The measured levels of contaminants in the Boyne River estuary turtle samples were compared to the levels reported in the peer-reviewed scientific literature for other green turtles, sea turtles and, where limited information was available, other vertebrates from both polluted and relatively low impacted areas. These levels were further evaluated against reported contaminant concentrations in a range vertebrate species where either chronic health effects (after long term exposure to contaminants) or acute health effects (after short term exposure) have been observed. Based on these assessments, the contaminants that were found in the turtle samples were classified into three categories:
1. Contaminants were considered of “relatively low concern” if they were detected in the Boyne River turtles at relatively low concentrations that were comparable to those reported for most other sea turtles and vertebrates, including those considered healthy and originating from relatively low impacted areas. At these levels, no associated adverse health effects have been reported in the scientific literature for turtles or other vertebrate species.
Contaminants assigned to this category were: bioaccumulative pesticides, organotins, flame retardants (polybrominated diphenyl ethers (PBDEs)), perfluorinated compounds (perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA)), aluminium (Al), iron (Fe), manganese (Mn), and zinc (Zn).
2. Contaminants were considered “possibly of concern” if they were present at concentrations that were comparable to the upper ranges of those reported for other sea turtles and vertebrates. Where relevant information was available, the contaminant levels in a proportion of the Boyne River green turtles were found to be above the concentrations where chronic effects occur in other vertebrates; i.e. long term exposure at these levels may result in adverse health effects. In contrast, the levels in the turtles were lower than the concentrations expected to result in adverse health effects after short term, acute exposure to these compounds.
3 Investigation of contaminant levels in green turtles from Gladstone
Contaminants that fell within this category were: polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (PCBs), silver (Ag), copper (Cu), chromium (Cr), molybdenum (Mo), and lead (Pb).
3. Contaminants were considered “of concern” if their concentrations were clearly higher compared to most other green turtles and sea turtles, or within the upper levels reported from animals that were moribund and/or originated from areas considered relatively polluted. These contaminants were also present at higher levels compared to normal concentrations known for other vertebrates from low impacted or unpolluted areas. In particular, the measured concentrations in Boyne River turtles were found to be above or near the concentrations where acute adverse health effects have been observed across different vertebrate taxa. Although the sensitivity of sea turtles to these contaminants is mostly unknown, this suggests that adverse health effects are possible in the Boyne River estuary turtle population at the detected concentrations.
Contaminants that fell within this category were: arsenic (As), cadmium (Cd), cobalt (Co), mercury (Hg), nickel (Ni), selenium (Se), and vanadium (V).
It should be noted that information on the sensitivity of green turtles to contaminants are limited. For this study, as for other studies reported in the scientific literature, comparisons to other vertebrates were required in most instances. There is, therefore, an uncertainty involved when evaluating the effects that a particular concentration of contaminants may have on green turtles. Considering these results, it is recommended to monitor the health and contaminant levels in adult and juvenile green turtles from Gladstone as well as other, suitable control populations. Investigation of contaminants with strong tendencies to biomagnify in marine biota should be carried out across species of different trophic levels, and detailed speciation of metal/metalloids should be considered to provide a better understanding on the risks associated with the compounds of concern based on total metal/metalloid concentrations.
4 Investigation of contaminant levels in green turtles from Gladstone
TABLE OF CONTENTS 1.0 BACKGROUND ...... 12
1.1 Blood as exposure surrogate ...... 12 2.0 OBJECTIVES AND SCOPE ...... 14
3.0 METHODOLOGY ...... 16
3.1 Sampling ...... 16 3.2 Analyses ...... 18 3.2.1 Description of tiered analysis approach ...... 18 3.2.2 Trace element analysis ...... 19 3.2.3 Analysis for organotins ...... 20 3.2.4 Analysis for bioaccumulative pesticides ...... 20 3.2.5 Analysis for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) ...... 21 3.2.6 Analysis for polybrominated diphenyl ethers (PBDEs) ...... 22 3.2.7 Analysis for perfluorinated compounds (PFCs) ...... 22 3.2.8 Statistical analyses ...... 23 4.0 RESULTS...... 25
4.1 Turtle biometrics and health states ...... 25 4.2 Screening ...... 25 4.2.1 Tier 1 - Qualitative (non-target) screening ...... 25 4.2.2 Tier 2 – Quantitative (target) screening ...... 26 4.2.3 Tier 3 – Quantitative target analysis ...... 29 5.0 DISCUSSION ...... 34
5.1 Contaminant levels in relation to turtle biometrics, health and sampling location ...... 34 5.2 Contaminant exposure concentrations and risk evaluation ...... 35 5.2.1 Contaminants of relatively low concern ...... 36 5.2.2 Contaminants possibly of concern ...... 36 5.2.3 Contaminants of concern ...... 37 5.3 Review - contaminants of concern ...... 38 5.3.1 Arsenic (As) ...... 38 5.3.2 Cadmium (Cd) ...... 42 5.3.3 Cobalt (Co) ...... 47 5.3.4 Mercury (Hg) ...... 50 5.3.5 Nickel (Ni) ...... 55 5.3.6 Selenium (Se)...... 58 5.3.7 Silver (Ag) ...... 62 5.3.8 Vanadium (V) ...... 65 5.3.9 Zinc (Zn) ...... 68 5.3.10 Dioxins and PCBs ...... 71 6.0 CONCLUSIONS AND RECOMMENDATIONS ...... 76
7.0 REFERENCES ...... 77
8.0 APPENDICES...... 87
5 Investigation of contaminant levels in green turtles from Gladstone
8.1 Results for individual turtle samples ...... 87 8.2 Comparisons of contaminant concentrations in sea turtles ...... 94 8.2.1 Aluminium (Al) ...... 95 8.2.2 Arsenic (As) ...... 97 8.2.3 Cadmium (Cd) ...... 102 8.2.4 Chromium (Cr) ...... 110 8.2.5 Cobalt (Co) ...... 112 8.2.6 Copper (Cu) ...... 115 8.2.7 Iron (Fe) ...... 121 8.2.8 Lead (Pb) ...... 125 8.2.9 Manganese (Mn) ...... 130 8.2.10 Mercury (Hg) ...... 134 8.2.11 Molybdenum (Mo) ...... 139 8.2.12 Nickel (Ni) ...... 141 8.2.13 Selenium (Se)...... 145 8.2.14 Silver (Ag) ...... 149 8.2.15 Vanadium (V) ...... 151 8.2.16 Zinc (Zn) ...... 153 8.2.17 Dioxins ...... 159
6 Investigation of contaminant levels in green turtles from Gladstone LIST OF FIGURES Figure 1 Three-tiered approach adopted for the present study to prioritise contaminant analysis in live green turtles from Boyne River estuary, Gladstone...... 14 Figure 2 Total Ion Count (TIC) GC-MS chromatogram of a green turtle liver pool (n=9). The 10 most abundant peaks (numbered) were identified based on the mass spectra of each peak...... 26 Figure 3 Box and whisker plots for metal and metalloid concentrations (ppb ww) in blood from individual (n=40) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. Box plots show the mean (red cross) and median (red line), the 25th (bottom of box) and 75th (top of box) percentiles, and 1.5 times the inter quartile range (whiskers)...... 33 Figure 4 Probabilistic distributions of body burden (ng kg-1 bw (x-axis)) in juvenile green turtles from Gladstone; A) derived using mammalian TEFs and B) derived using avian TEFs. The blue portion of the graph depicts the fraction of the juvenile population at or above the LOAEL of A) 3 ng kg-1 bw for biochemical effects in mammals (29%) and B) 9 ng kg-1 bw for developmental toxicity in chickens (5.0%)...... 74
LIST OF TABLES Table 1 Sample information for green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland ...... 17 Table 2 List of target contaminant groups and individual analytes quantified under Tier 2 and Tier 3 analysis; note: organotin concentrations are reported on the basis of their organic forms as well as normalised to tin (Sn)...... 24 Table 3 Concentrations of perfluorinated compounds (PFOS/PFOA; ppb ww) in pooled green turtle (Chelonia mydas) blood (n=40) from Boyne River estuary near Gladstone, Queensland. Water content approximately 89%...... 27 Table 4 Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F; ppt lw), WHO-PCBs (ppt lw) and indicator PCBs (ppt lw) in pooled green turtle (Chelonia mydas) fat (n=9) from Boyne River estuary near Gladstone, Queensland. Lipid content 1.7%...... 27 Table 5 Concentrations of brominated flame retardants (PBDEs; ppb dw), organotins (ppb dw), perfluorinated compounds (PFOS/PFOA; ppb dw) and bioaccumulative pesticides (ppb dw) in pooled green turtle (Chelonia mydas) liver (n=9) from Boyne River estuary near Gladstone, Queensland. Water content approximately 78%...... 28 Table 6 Summary (descriptive statistics) of concentrations of polychlorinated dibenzo-p- dioxins and dibenzofurans (PCDD/F; ppt lw) and WHO-PCBs (ppt lw) in blood from individual (n=22) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 30
7 Investigation of contaminant levels in green turtles from Gladstone
Table 7 Summary (descriptive statistics) of concentrations of bioaccumulative pesticides (ppb ww) and organotins (ppb ww) in blood from individual (n=7) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 31 Table 8 Summary (descriptive statistics) of concentrations of metals and metalloids (ppb ww) in blood from individual (n=40) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 32 Table 9 Summary (descriptive statistics) of concentrations of metals and metalloids (ppm ww) in liver and kidney from individual (n=3) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 32 Table 10 Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs; ppt lw) in individual (n=22) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 88 Table 11 Concentrations of polychlorinated biphenyls (WHO-PCBs; ppt lw) in individual (n=22) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 89 Table 12 Concentrations of organotins (ppb ww) in individual (n=7) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 90 Table 13 Concentrations of bioaccumulative pesticides (ppb ww) in individual (n=7) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 91 Table 14 Concentrations of metals and metalloids (ppb ww) in individual (n=40) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 92 Table 15 Concentration of metals and metalloids (ppm ww) in liver and kidney of individual (n=3) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland...... 93
8 Investigation of contaminant levels in green turtles from Gladstone
ABBREVIATIONS AND ACRONYMS Ag Silver
Al Aluminium
As Arsenic
Bioaccumulation Uptake (from the environment or food) and net contaminant accumulation over time (age) within an organism at a rate greater than that at which the contaminant is lost
Biomagnification Increase of contaminant concentrations between successive trophic levels via uptake from food; progressive build-up of contaminants by successive trophic levels
Body condition A measure of health condition based on body mass in relation to CCL
Cd Cadmium
Co Cobalt
Cr Chromium
Cu Copper
DERM Queensland Department of Environment and Resource Management
Dioxin A group of 210 compounds, comprising polychlorinated dibenzo-p-dioxins and dibenzofurans dw Dry weight
Entox National Research Centre for Environmental Toxicology, The University of Queensland
Eurofins Eurofins GfA Laboratory Service, Hamburg, Germany
Fe Iron
Hg Mercury
Indicator PCBs Six PCBs are commonly measured as indicators for the group of non dioxin- like PCBs; non dioxin-like PCBs have a different toxic mechanism to dioxins and accordingly are not assigned TEFs
Inorganic metals Metals combined with elements such as chlorine, sulfur, or oxygen
LD50 Lethal dose at which 50% of the study population died
Lipophilicity Affinity for lipids and organic matter
LOQ Limit of quantification
Lower bound Contaminants below the LOQ are not accounted for (i.e. concentration are assumed to be zero)
9 Investigation of contaminant levels in green turtles from Gladstone lw Lipid weight
Metalloid An element having both properties of a metal and non-metal
Microgram (µg) 10-6 grams
Middle bound Contaminants below the LOQ are assumed to be present at half the LOQ concentration
Milligram (mg) 10-3 grams
Mn Manganese
Mo Molybdenum
Moribund In a state of dying or near death based on biological condition
NA Not available
Nanogram (ng) 10-9 grams
ND No data
Ni Nickel
Organic metals Metals combined with carbon
Pb Lead
PCBs Polychlorinated biphenyls
PCDD/Fs Polychlorinated dibenzo-p-dioxins and dibenzofurans, collectively also referred to as dioxins
Pesticides A general term for a range of chemicals used as herbicides, insecticides, fungicides or biocides
PFOS/PFOA The fluorosurfactants perfluorooctane sulfonate (PFOS); perfluorooctanoic acid (PFOA)
Physico-chemical The properties of a particular chemical which describe their behaviour, e.g. properties its stability, tendency to volatilise, affinity for organic carbon and lipids etc.
Picogram (pg) 10-12 grams ppb Parts per billion (= µg/kg, µg/L, ng/g, ng/mL) ppm Parts per million (= mg/kg, mg/L, µg/g, µg/mL) ppt Parts per trillion (= ng/kg, ng/L, pg/g, pg/mL)
QHFSS Queensland Health and Forensic Scientific Services
Se Selenium
TEF Toxic Equivalency Factor; a relative measure of toxic potency of individual dioxin and dioxin-like PCB congeners compared to the most toxic dioxin (2,3,7,8-TCDD). In this report, TEFs adopted by WHO in 2005 have been used.
10 Investigation of contaminant levels in green turtles from Gladstone
TEQ Toxic Equivalency based on toxic equivalency factors (TEFs) adopted by WHO in 2005; a measure of the overall toxic potency of a dioxin mixture
TEQdf Toxic Equivalency (TEQ) for PCDD/Fs
TEQpcb Toxic Equivalency (TEQ) for PCBs
Upper bound Contaminants below the LOQ are assumed to be present at the LOQ concentration
V Vanadium
WHO PCBs Dioxin-like PCBs, having the same toxic mechanism as dioxins. TEFs for dioxin-like PCBs have been adopted by the World Health Organisation (WHO) ww Wet weight (or fresh weight)
Zn Zinc
11 Investigation of contaminant levels in green turtles from Gladstone 1.0 BACKGROUND Since early 2011, Port Curtis has been experiencing higher than usual mortality rates of sea turtles, with 260 reported strandings between 1 January 2011 and 28 February 2012 in the Gladstone region from Rodds Bay Peninsula to Sandy Point north of Yeppoon, compared to 50-51 reported strandings per year during 2008-2010 (DERM, 2012). There has also been an increase in the number of other wildlife strandings, as well as outbreaks of diseases in fish in this region (DEEDI, 2011).
The mass turtle stranding event was attributed partly to the significant loss of seagrass beds, which form important foraging habitats for resident populations of green turtles (DERM, 2012). The summer of 2010-2011 witnessed unprecedented extensive flooding in the Gladstone Harbour region as well as across much of Queensland, resulting in increased freshwater and sediment outflow and subsequent reduced seagrass cover (Sankey et al., 2011). These events are compounded by the large-scale industrial development in the Gladstone Harbour region. As a major port city along the Queensland coast, Gladstone hosts a variety of industries, including mining and processing of minerals, and liquefied natural gas, a large fishing industry, as well as agricultural activities within the catchment. Since 20 May 2011, the city has been undergoing substantial development of its port resources, including dredging and land reclamation (Gladstone Ports Corporation, 2011).
In response to the wildlife strandings, a Scientific Advisory Committee was formed at the request of the Queensland Minister for the Environment, and recommended the investigation of the health status of green turtles within the Gladstone Harbour. This investigation commenced with an on-site survey and sample collection during 8-11 July 2011 by a team from Queensland Department of Environment and Resource Management (DERM) and the School of Veterinary Sciences, The University of Queensland. Clinical examination of 56 green turtles revealed that the juvenile turtle population from this region were generally in poor health, due most likely to chronic malnutrition (Eden et al., 2011). Diseases of the digestive, respiratory, and circulatory systems were found and, in most cases, may have developed secondary to chronic debilitation. Spirorchiid fluke infection was the most commonly identified infectious agent on complete necropsy of 10 green turtles, with other infectious diseases diagnosed as fibropapillomatosis and bacterial gastroenteritis.
In parallel with the health assessment, a comprehensive contaminant exposure assessment was conducted for blood of live captured green turtles. Of interest were a range of inorganic and organic contaminants that may have been brought downstream from the catchment with flood waters or have arisen from industrial activities.
1.1 BLOOD AS EXPOSURE SURROGATE Blood has been demonstrated to be an appropriate matrix for assessing exposure to a broad range of chemical groups, including both organic and inorganic compounds (Hermanussen et al., 2008; van de Merwe et al., 2010). Blood provides a logistically feasible, ethical and nonlethal option for exposure assessment of free ranging wildlife. Despite this, blood and tissue concentrations of contaminants are dependent on a number of factors that need to be considered when interpreting analytical results for exposure and risk assessment.
The contaminant’s physico-chemical properties and its speciated ion (molecular form) affect the toxicokinetics (uptake, distribution, metabolism and excretion) in organisms. Persistent lipophilic 12 Investigation of contaminant levels in green turtles from Gladstone contaminants are accumulated in body lipids, and their concentrations in blood, when normalised to a lipid basis, are typically comparable to those in other tissues (Hermanussen, 2009; van de Merwe et al., 2010). Thus, blood concentrations of persistent lipophilic contaminants can inform on tissue or body burdens, and long-term exposure regimens. Many metals and metalloids exist as different reduced and oxidised species, ranging from water-soluble ions to relatively lipophilic metalorganic compounds. While the more water soluble ionic species are mostly circulated through the body via the blood stream after absorption, they are often stored predominantly in the liver and kidney and can be rapidly eliminated through faeces or urine. Therefore, blood analysis often provides a snapshot of the most recent exposure to most metals and metalloids (in the order of days to months, depending on the element and speciation), while storage tissues can inform on longer term exposure regimens. Understanding of toxicokinetics of individual metals is thus particularly important for interpreting blood concentrations of metals (Grillitsch and Schiesari, 2010). At constant exposure, the concentrations of such contaminants in blood and organs are often correlated, with blood containing considerably lower levels, except during initial phases of high-level exposure (Grillitsch and Schiesari, 2010). However, changes in exposure will be reflected rapidly in blood, with the levels depending on time of exposure relative to time of sampling (Day et al., 2010).
An organism’s trophic level, age, and breeding status can considerably affect the distribution and levels of many contaminants in tissues and blood. Concentrations of chemicals that are only poorly metabolised typically (at constant exposure) increase with age (bioaccumulation) until a steady state is reached where their rate of uptake is equal to the rate of metabolism or transformation. Such chemicals may accumulate over time to levels that may be harmful, even at relatively low exposure regimens (van den Berg et al., 2006). Some of these compounds also have strong tendencies to biomagnify through the food chain, whereby the highest trophic levels contain the highest concentrations. However, low trophic benthic feeders, such as green turtles, may take in substantial amounts of such contaminants sorbed to seagrasses or sediments (Hermanussen, 2009).
Health and nutritional states are additional factors that may affect the toxicokinetics of contaminants in organisms (Eisler, 2007). Nutrient deficient states and declining health of organisms can disturb contaminant equilibria through mobilisation of lipid stores and associated chemicals, and may influence the metabolic capacity of liver and kidneys, thus affecting storage, detoxification and elimination pathways. This is particularly relevant for the present study, which focused on an area where a large proportion of green turtles were found to be near or at emaciated states.
13 Investigation of contaminant levels in green turtles from Gladstone 2.0 OBJECTIVES AND SCOPE The present study focused on assessing contaminants in live green turtles collected from the Boyne River estuary, Gladstone, using mainly blood as anexposure surrogate. The objectives were:
To quantify a range of contaminant groups that are known to bioaccumulate in marine wildlife and may present a hazard to green turtles in Gladstone To evaluate whether detected contaminant concentrations in green turtles from Gladstone are elevated and may present a risk to the turtle population.
Analysis was carried out using a tiered approach (Figure 1) whereby pooled samples were initially screened for the presence of relatively high levels of nonpolar organic chemicals, in order to identify contaminant groups that should be covered. In a second tier, pooled samples were analysed for a broad range of known and potentially hazardous bioaccumulative pollutants to direct further prioritisation. Based on information from these screenings, individual samples were analysed in the third tier for compounds that may be elevated and/or have relatively high toxic potency.
Tier 1: Pooled tissue Identify possible presence of Non-target screen contaminant groups at high levels
Initial information on type and Pooled tissue and Tier 2: level of contaminants present for further prioritisation and sample blood Target screen volume adjustment
Blood from Quantification of prioritised individuals Tier 3: contaminants, based on results of Tiers 1-2, and taking into account Tissue from Target analysis chemical hazard matched individuals
Figure 1 Three-tiered approach adopted for the present study to prioritise contaminant analysis in live green turtles from Boyne River estuary, Gladstone.
To evaluate whether contaminants detected in the green turtle samples are elevated, a literature review was carried out to compare concentrations with those reported for other green turtles, and where necessary due to a lack of data for green turtles, other sea turtles, marine biota or reptiles, birds and mammals in general.
To evaluate whether contaminants present at elevated levels may present a risk to green turtles, reptile specific toxicological studies were reviewed and, where insufficient information was available, contaminant concentrations in green turtles from Gladstone were compared to effect concentrations across a range of vertebrate taxa. Where possible, green turtle contaminant body burdens were estimated using probabilistic approaches and compared to body burdens that elicit physiological
14 Investigation of contaminant levels in green turtles from Gladstone effects in a dose-dependent manner, to estimate the proportion of green turtles that may be at risk of adverse effects. Where such approaches were not feasible, contaminant levels in green turtles were compared with available tissue based effect concentrations to identify whether adverse effects may be possible at the determined exposure levels.
15 Investigation of contaminant levels in green turtles from Gladstone 3.0 METHODOLOGY
3.1 SAMPLING Green turtles (Chelonia mydas) were collected from the Boyne River estuary near Gladstone (-23.9 °S, 151.3 °E) during 8-11 July 2011. This population is characterised by turtles in poor health and associated elevated incidence of mortality. The samples were collected using best practice Australian standard procedures developed by DERM, and were stored at The University of Queensland School of Veterinary Science and Entox.
For contaminant analysis, blood samples were collected from 40 live green turtles (Table 1). The animals were collected while basking on land (n=31) or captured using a rodeo technique (n=9) described in Limpus (1978). All specimens underwent assessment as described in Limpus et al. (1994) including measurements of size (curved carapace length, CCL) and body weight, as well as determination of age class (new recruit, juvenile, sub-adult or adult), gender and body condition, the latter informing on body mass for a given CCL (according to Limpus and Chalaupka (1997)).
For contaminant analysis, 13-24 mL blood, depending on the individual’s size and body condition and up to a maximum of 4% body weight, was collected from each turtle. Blood samples were taken from the dorso-cervical sinus using an 18 gauge 38 mm needle and 10-25 mL syringe. Whole blood was transferred to solvent-washed Schott bottles, with Teflon lined caps, containing 1.5 mL of heparinised saline (50 international units (IU)), and stored at -20°C until analysis.
Three of the animals were severely emaciated and moribund, with poor clinical diagnosis for survival; these were euthanized (by intravenous injection of sodium pentobarbitone (325 mg/mL)) by a registered veterinarian and necropsied at The University of Queensland’s School of Veterinary Science. Necropsies included gross pathology and histopathology examinations, and the results are reported in Eden et al (2011). Blood, liver, kidney and fat samples were collected from these three specimens (Table 1).
Additional stranded animals were collected by Queensland Parks and Wildlife Service staff and underwent necropsy at the School of Veterinary Science, The University of Queensland, as described above. Liver and fat tissues were collected from six additional specimens and pooled, together with liver and fat from euthanized specimens described above, for analyses (n=9). Tissues were wrapped in aluminium foil and stored frozen at -20°C until analysis.
16 Investigation of contaminant levels in green turtles from Gladstone
Table 1 Sample information for green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland
EX Sampling Location CCL Weight Lipid Barnicle Body Sex FP* ID Date Lat. Long. (cm) (kg) (%) count condition Juveniles that were euthanised and necropsied (blood, liver and kidney samples) 2 8/07/2011 -23.92641 151.355 Female 48 8.6 0.14 42 Very poor - 3 8/07/2011 -23.9267 151.3542 Male 47 8.7 0.22 26 Very poor - 22 9/07/2011 -23.92739 151.3549 Female 42 6.9 0.09 26 Very poor - Live captured juveniles (blood samples) 7 8/07/2011 -23.9283 151.3538 Male 39 5.4 0.06 87 Very poor - 8 8/07/2011 -23.9267 151.3544 Female 43 8.2 ND - Normal - 9 8/07/2011 -23.92835 151.3544 Male 44 8.0 0.20 29 Poor - 10 8/07/2011 -23.92621 151.355 Female 43 7.8 ND 68 Injured - 11 8/07/2011 -23.92789 151.3534 Male 45 9.4 ND 27 Normal - 13 9/07/2011 -23.92825 151.3548 Male 45 10 0.12 23 Normal - 14 8/07/2011 -23.92837 151.3542 Male 44 8.3 ND 38 Poor - 15 8/07/2011 -23.92729 151.3542 Male 46 9.5 ND 34 Poor - 20 9/07/2011 -23.92811 151.3552 Male 43 8.7 0.11 15 Poor - 21 9/07/2011 -23.94009 151.3531 Male 47 9.8 ND 7 Normal - 23 9/07/2011 -23.92581 151.3552 Male 42 7.9 ND 22 Normal - 24 9/07/2011 -23.92752 151.3544 Male 45 9.3 ND 59 Poor - 25 9/07/2011 -23.92802 151.354 Unknown 47 9.3 0.23 30 Very poor C3 26 9/07/2011 -23.92802 151.354 Male 49 10 ND 27 Poor - 30 10/07/2011 -23.92798 151.3535 Female 60 22 0.13 21 Poor B1 31 10/07/2011 -23.92792 151.3535 Female 47 8.6 ND - Poor - 32 10/07/2011 -23.92798 151.3535 Male 62 25 0.20 - Normal - 33 10/07/2011 -23.93218 151.3568 Female 45 10 ND 2 Normal - 34 10/07/2011 -23.93072 151.3571 Male 47 10 0.07 33 Poor - 35 10/07/2011 -23.93047 151.3572 Female 45 8.4 ND 2 Poor - 37 10/07/2011 -23.93132 151.3572 Male 48 12 ND 10 Normal B2 38 11/07/2011 -23.92681 151.3572 Female 52 15 0.15 - Normal - 39 10/07/2011 -23.94009 151.3531 Male 43 8.1 ND - Poor - 40 11/07/2011 -23.92823 151.3543 Female 45 8.6 ND 23 Poor - 41 11/07/2011 -23.93501 151.3566 Female 52 15 0.18 10 Normal - 42 11/07/2011 -23.9337 151.3562 Unknown 47 8.8 0.23 66 Very poor - 43 11/07/2011 -23.93316 151.3601 Male 44 9.7 0.11 - Normal - 44 11/07/2011 -23.93346 151.3564 Female 44 8.3 ND - Poor - 45 11/07/2011 -23.93188 151.3564 Female 44 9.2 0.17 35 Normal - 46 11/07/2011 -23.9317 151.3561 Unknown 45 8.8 0.17 1 Very poor - 47 11/07/2011 -23.93307 151.3564 Female 48 8.8 0.14 - Poor - 48 11/07/2011 -23.93108 151.3569 Male 53 15 0.11 - Normal - 49 11/07/2011 -23.93057 151.3567 Male 46 10 ND - Normal - 50 11/07/2011 -23.93158 151.3567 Female 43 8.0 0.12 22 Normal - 51 11/07/2011 -23.93078 151.3566 Female 46 9.8 ND - Normal A1 53 11/07/2011 -23.9338 151.3564 Female 48 13 0.090 1 Normal B3 Live captured adult (blood samples) 36 10/07/2011 -23.92798 151.3535 Unknown 100 86 0.15 14 Very poor - ND No data FP* Fibropapilloma codes according to DERM classifications
17 Investigation of contaminant levels in green turtles from Gladstone 3.2 ANALYSES
3.2.1 Description of tiered analysis approach
TIER 1 - QUALITATIVE (NON-TARGET) SCREENING This analysis was undertaken as a non-target-screening for the purpose of identifying the presence of possible contaminants at high levels, to inform subsequent Tiers 2 and 3 (Figure 1). Analysis was carried out on a high resolution gas chromatograph low resolution mass spectrometer at Eurofins GfA.
One gram of liver was pooled from stranded and euthanized specimens that underwent necropsy (n=9, including the three specimens EX2, 3, and 22 for which blood samples were also available; Table 1). Approximately 0.5 g homogenised sample was extracted with n-hexane using ultrasonication. The raw extract was then directly used for injection on an Agilent 6890/5973 GC-MS system using a non-polar DB5-type capillary column. An electron ionisation mode was used to scan a mass range of m/z 50-600. For evaluation, the 10 most abundant peaks were baseline subtracted and evaluated with the assistance of spectra libraries (Wiley 75K; NIST) by manual spectra interpretation and judgement for presence of artefacts or contaminants from the process.
TIER 2 - QUANTITATIVE (TARGET) SCREENING Tier 2 screening comprised target chemical analysis using pooled samples of blood, liver and fat to provide initial information on the type and levels of contaminants to be expected, and thus estimation of minimum sample volume required for each contaminant group, as well as further prioritisation for Tier 3 analysis (Figure 1).
For blood pools, 1 mL blood was sub-sampled and combined from each specimen (n=40). Liver and fat pools comprised of 1 g tissue, respectively, from each necropsied specimen (n=9). These pools underwent quantitative analyses for a set of contaminants listed in Table 2, except for metals and metalloids (which were analysed for each sample under Tier 3).
Pooled turtle fat was analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (WHO-PCBs) and a set of 7 indicator PCBs listed in Table 2. Pooled turtle liver was analysed for organotins, polybrominated flame retardants (PBDEs), bioaccumulative pesticides and perfluorinated compounds. Pooled turtle blood was analysed for perfluorinated compounds. These analyses were carried out at an accredited laboratory according to standardised protocols which are described briefly below.
TIER 3 - QUANTITATIVE TARGET ANALYSIS In the third tier, blood samples from individual turtles underwent quantitative target analyses for selected contaminant groups as prioritised based on the two screening Tiers (i.e. based on contaminant type and expected concentrations, taking into account toxic potency) (Figure 1). In addition to blood, liver and kidney from euthanized specimens (n=3) were analysed for individual compound groups to evaluate tissue distributions and facilitate comparisons to literature data.
18 Investigation of contaminant levels in green turtles from Gladstone
Individual blood samples were analysed for metals and metalloids (n=40), organotins (n=7), WHO- PCBs (n=22), PCDDs and PCDFs (n=22), and bioaccumulative pesticides (n=7). These analyses were carried out and evaluated on a batch-by-batch approach. Where Tier 1, 2 and 3 confirmed the presence of low levels, the limited volume for blood samples was prioritised for other analytes. Hence, a varying number of samples have been analysed for the different contaminant groups. Individual analytes for each of these groups are listed in Table 2, and a brief description on the analytical methods, and associated quality assurance and quality control procedures are provided below.
Analysis for organic compounds were performed at Eurofins GfA in Hamburg, Germany, which is accredited for the determination of PCDD/F, PCB, chlorinated pesticides, PBDE and polyfluorinated compounds (PFC) in biological material in accordance with DIN EN ISO/IEC 17025:2005. Analysis for metals and metalloids was undertaken at the National Research Centre for Environmental Toxicology (Entox) according to standardised protocols.
3.2.2 Trace element analysis Analysis for the trace elements Al, As, Cd, Cr, Co, Cu, Fe, Pb, Mn, Hg, Mo, Ni, Se, Ag, V, and Zn was undertaken using inductively coupled plasma mass spectrometry (ICP-MS).
Samples were prepared according to in-house standardised protocols. Briefly, a subsample of 0.5 mL of whole blood was diluted to 10 mL with high purity MilliQ water (Millipore, Australia), and then vortex mixed and centrifuged to remove precipitate. Liver and kidney samples were freeze-dried and homogenised using a mortar and pestle. As tissue samples were stored in aluminium foil, the outer tissue was removed; nevertheless, cross-contamination with aluminium cannot be excluded. Aliquots of approximately 0.10 g homogenised tissue was then transferred into Teflon vessels and mixed with 1 mL of concentrated nitric acid (HNO3; 70% AR grade, BioLab (Aust) Pty Ltd). Tissue samples were then digested in a water bath at 60-70 °C for 4 to 6 hours until the solution was clear. After cooling down to room temperature, digested solutions were diluted (x50) with MilliQ water and filtered through 0.45 m filters prior to analysis.
Blood and tissue solutions were then spiked with an internal standard solution containing the elements Ge, Rh, Sc, Y, In and Bi (Agilent) to a final concentration in the samples equivalent to 10 g/L. Analysis and quantification was performed using an Agilent 7500CS ICP-MS equipped with a quartz torch, and a quartz double-pass spray chamber fitted with a Micro Flow nebulizer. Quantification was performed using the relative response of each trace metal to internal standards against an external 5-point calibration curve.
For quality assurance and quality control, duplicates, reagent blanks, blank spikes, analytical spikes were run with each batch of samples. Certified reference materials were analysed with each batch of samples to ensure accuracy; these included DORM-3 fish protein standard reference material (National Research Council, Canada), an in-house certified reference material (human blood reference material provided by Queensland Health and Forensic Scientific Services) and Seronorm L-1 and L-2 whole blood trace elements (SERO, Norway). The limit of quantification (LOQ) for each element was defined as three times the standard deviation of blank replicates (n=10) expressed in g/L. The LOQs for each element in blood and tissue samples ranged from 0.11 (As) to 5.76 (Fe) and
19 Investigation of contaminant levels in green turtles from Gladstone
0.020 (Cr) to 22 (Fe) µg/L, respectively. Recovery was calculated using a triplicate analysis of certified reference material DORM 3 (for tissue samples) and were generally between 70% and 130%, which is considered acceptable for this analysis.
3.2.3 Analysis for organotins The organotin compounds monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), tetrabutyltin (TTBT), monooctyltin (MOT), dioctyltin (DOT), triphenyltin (TPhT), tricyclohexyltin (TCHT) were analysed using high resolution gas chromatography low resolution mass spectrometry (HRGC-LRMS).
Prior to extraction, all samples were spiked with internal standard substances (monoheptyltintrichloride, diheptyltindichloride, tripropyltinchloride, tetrapropyltin). The samples were homogenized, mixed and conditioned over night with methanol and trimethyl ammoniumhydroxid, then buffered with an acetic acid/acetate buffer and extracted and simultaneously derivatized with hexane and sodium tetraethylborate. The hexane phase was used for clean-up by column chromatography on alumina, deactivated with 10% water and eluted with hexane. The cleaned extract was evaporated and tetrapentyltin was added as injection standard for the determination of recovery rates.
Analytical measurement was performed on an Agilent 6890/5973 HRGC-LRMS system with a DB-XLB fused silica column. Quantification of the organotin compounds was carried out via the internal standard method and based on daily instrument calibration.
For quality control, method blanks were run with each sample batch to monitor for possible background contamination. Reference materials (pooled samples) are regularly monitored and the laboratory participates in respective interlaboratory comparisons (e.g. QUASIMEME).
3.2.4 Analysis for bioaccumulative pesticides Target analytes for pesticides were o,p'-DDT, p,p'-DDT, α-HCH, β-HCH, γ-HCH (lindane), δ-HCH; three main toxaphene compounds (Parlar #26, #50 and #62), α-chlordane, γ-chlordane, oxychlordane, heptachlor, cis-heptachlor epoxide, trans-heptachlor epoxide, aldrin, dieldrin, endrin, α-endosulfan, β-endosulfan, endosulfan sulfate, mirex, hexachlorobenzene (HCB) and pentachlorobenzene. The analysis was carried out by high resolution gas chromatography high resolution liquid mass spectrometry (HRGC-HRMS), and high resolution gas chromatography tandem mass spectrometry (HRGC-MS-MS).
Tissue samples were homogenized, mixed with sodium sulphate to create a free flowing mixture, after which ultrasonic extraction was carried out with a mixture of n-hexane/acetone. Blood samples were extracted by a specialised liquid-liquid extraction with n-hexane, followed by n-hexane/i- propanol. All samples were spiked with quantification standards (internal standards) before extraction using the following 13C-labeled compounds: β-HCH, γ-HCH, p,p'-DDT, p,p'-DDE, pentachlorobenzene, hexachlorobenzene, endosulfan sulfate, β-endosulfan, dieldrin.
Clean-up was performed by column chromatography applying a combination of columns with basic alumina and Florisil. Hexane was used for elution of the main fraction and toluene for a second fraction for endosulfan compounds which underwent an additional clean-up step using acetonitrile:hexane partitioning. The fractions were evaporated and 13C-PCB #105 was added as
20 Investigation of contaminant levels in green turtles from Gladstone injection standard for the analytes of the first fraction and 13C-PCB #28 for the analytes of the second fraction. Analyses for compounds of the first fraction was performed by HRGC/HRMS on a Thermo DFS at mass resolution R ≥ 8,000 on a DB5-type fused silica column (60m x 0.25 mm i.d. x 0.25 µm dF). Endosulfan compounds were determined on an Agilent 7000 triple quadropole HRGC-MS-MS. Quantification was carried out by isotope dilution and internal standard methods against daily calibration points, together with a multipoint calibration.
For quality control, method blanks were run with each sample batch to monitor for possible background contamination. Reference materials (pooled samples) are regularly monitored and the laboratory participates in respective interlaboratory comparisons (e.g. AMAP).
3.2.5 Analysis for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) Target analytes were the 17 2,3,7,8-substituted PCDD/Fs and the 12 dioxin-like PCBs (WHO-PCBs; PCB #77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189). Analyses were carried out using a high resolution gas chromatograph high resolution mass spectrometer (HRGC-HRMS).
Tissue samples were homogenised, mixed with sodium sulphate to create a free flowing mixture after which ultrasonic extraction was carried out with a mixture of n-hexane/acetone. Blood samples were extracted by a specialised liquid-liquid extraction with n-hexane followed by n-hexane/i- propanol. All samples were spiked with quantification standards (internal standards) prior to extraction using all PCDD/F and PCB analytes as 13C-labeled compounds (exception: 1,2,3,7,8,9- HexaCDD). The obtained raw extract was gently evaporated for fat determination and the yielded lipids were used for clean-up.
The clean-up consisted of a sulfuric acid treatment and a fractionation on active carbon for separation of PCDD/Fs and PCBs. This was followed by column chromatography with a combination of columns using silica modified with sulfuric acid, basic alumina (activity super I) and florisil. Elution was carried out with hexane, toluene and dichloromethane. The fractions were evaporated and a set of four 13C-PCDD/Fs and four 13C-PCBs were added as injection standards. Analytical measurement was performed by HRGC/HRMS on a Waters Autospec HRMS at mass resolution R ≥ 10,000 equipped with a DB5ms-type fused silica column (60m x 0.32mm i.d. x 0.25µm dF). Quantification was carried out by isotope dilution against daily calibration points together with a multipoint calibration.
For quality control, method blanks were run with each sample batch to monitor for possible background contamination. Reference materials (pooled samples) are regularly monitored and the laboratory participates in respective interlaboratory comparisons (e.g. Norway/ Norwegian Institute of Public Health).
Analytes were accepted for quantification if their retention times were within 2 seconds of the retention times of the relevant labelled internal standards and the ratios for the area of the two most abundant isotopes were within 20% of their calculated values. The limit of quantification for PCDD/F and PCB congeners was defined as a signal–to-noise ratio greater than 3 times the average baseline variation. Analytes were marked with ‘<’ when the sample concentration did not exceed 3 times the concentration found in the batch blank. Toxic equivalencies (TEQs) were calculated using mammalian 21 Investigation of contaminant levels in green turtles from Gladstone toxic equivalency factors (TEFs) adopted by the World Health Organisation (van den Berg et al., 2006), unless otherwise stated, and are reported using middle bound concentrations (i.e. half the concentration of the limit of quantification (LOQ) or values marked with a “<”), unless otherwise stated.
3.2.6 Analysis for polybrominated diphenyl ethers (PBDEs) Target analytes for PBDEs were the congeners #17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, 154, 156, 183, 184, 191, 196, 197, 206, 207, 209. The analyses were carried out using high resolution gas chromatography tandem mass spectrometry (HRGC-MS-MS).
Tissue samples were homogenised, mixed with sodium sulphate to create a free flowing mixture after which ultrasonic extraction was carried with a mixture of n-hexane/acetone. Blood samples were extracted by a specialised liquid-liquid extraction with n-hexane followed by n-hexane/i- propanol. All samples were spiked with isotope-labelled quantification standards prior to extraction 13 using the six C12-PBDEs #28, 47, 99, 153, 154, 183 and 209. The obtained raw extract was gently evaporated and the yielded lipids were used for clean-up. The clean-up consisted of a sulfuric acid treatment followed by column chromatography and fractionation on alumina, preconditioned with hexane and toluene, and eluted with dichloromethane. The eluate was evaporated and 13C-HexaBDE #138 was added as injection standard. Analytical measurement was performed by HRGC/MS-MS on an Agilent 7000 with a Restek RTX1614 column (15m x 0.25 mm i.d. x 0.1 µm dF). Quantification was carried out by isotope dilution against daily calibration points together with a multipoint calibration.
For quality control, method blanks were run with each sample batch to monitor for possible background contamination. Reference materials (pooled samples) are regularly monitored and the laboratory participates in respective interlaboratory comparisons (e.g. Norwegian Institute of Public Health and QUASIMEME).
3.2.7 Analysis for perfluorinated compounds (PFCs) Target analytes for PFCs were perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). The analyses were carried out using high performance liquid chromatography tandem mass spectrometry (HPLC-MS-MS).
The whole blood sample was homogenized and extracted using acetonitrile with ultrasonic extraction. The tissue sample was homogenized, mixed with sodium sulphate and extracted with acetonitrile. All samples were spiked with quantification standards (internal standards) before extraction using 13C-labeled C8-PFOA and C4-PFOS.
Clean-up was performed by acetonitrile-hexane distribution and interference adsorption on activated carbon (Envicarb). After removal from the carbon the extract was evaporated, dissolved in 13 methanol and C4-PFOA was added as injection standard for monitoring of the quantification standard recoveries. Analytical measurement was performed on an Agilent Triple Quad 6460 LC-MS- MS system equipped with a 100 x 2mm Phenomenex Synergi 4u Fusion RP80A column. Mobile phase was methanol (0.05% acetic acid) and reagent water (2 mmol ammonium acetate), run with a gradient programme. Quantification was carried out by isotope dilution against multiple daily calibration points together with a multipoint calibration.
22 Investigation of contaminant levels in green turtles from Gladstone
For quality control, method blanks were run with each sample batch to monitor for possible background contamination. Reference materials (pooled samples) are regularly monitored and the laboratory participates in respective interlaboratory comparisons (e.g. University of Erlangen).
3.2.8 Statistical analyses All statistical analyses were performed using XLSTAT Version 2012.2.01. Descriptive statistics (mean, maximum, minimum, standard error, percentiles and median) were determined for analytes and analyte groups, and are provided as box and whisker plots for metals and metalloids. A box plot combines multiple information that can be obtained from a group of data points. Box plots used in this report show the mean (red cross) and median (red line). The box represents the 25th (bottom) and 75th (top) percentiles and whiskers represent 1.5 times the inter quartile range (i.e. the difference between the 75th and 25th percentiles). All individual data points are also provided on these plots.
Nonparametric one-way analysis of variance was performed using the Kruskal Wallis test to evaluate statistically significant (p<0.05) differences of contaminant concentrations between turtles with very poor, poor and normal body conditions.
Correlations between % lipid, turtle weight, turtle size (CCL) and contaminant concentrations were tested using Pearson correlation coefficient with significance determined at p<0.05.
23 Investigation of contaminant levels in green turtles from Gladstone
Table 2 List of target contaminant groups and individual analytes quantified under Tier 2 and Tier 3 analysis; note: organotin concentrations are reported on the basis of their organic forms as well as normalised to tin (Sn).
Metals and Metalloids WHO-PCBs PBDEs Aluminium Al Non-ortho 2,2',4-TriBDE BDE 17 Arsenic As 3,3',4,4'-TCB PCB 77 2,4,4'-TriBDE BDE 28 Cadmium Cd 3,4,4',5-TCB PCB 81 Total TriBDE Chromium Cr 3,3',4,4',5-PeCB PCB 126 2,2',4,4'-TBDE BDE 47 Cobalt Co 3,3',4,4',5,5'-HxCB PCB 169 2,2',4,5'-TBDE BDE 49 Copper Cu Mono-ortho 2,3',4,4'-TBDE BDE 66 Iron Fe 2,3,3',4,4'-PeCB PCB 105 2,3',4',6-TBDE BDE 71 Lead Pb 2,3,4,4',5-PeCB PCB 114 3,3',4,4'-TBDE BDE 77 Manganese Mn 2,3',4,4',5-PeCB PCB 118 Total TBDE Mercury Hg 2',3,4,4',5-PeCB PCB 123 2,2',3,4,4'-PeBDE BDE 85 Molybdenum Mo 2,3,3',4,4',5-HxCB PCB 156 2,2',4,4',5-PeBDE BDE 99 Nickel Ni 2,3,3',4,4',5'-HxCB PCB 157 2,2',4,4',6-PeBDE BDE 100 Selenium Se 2,3',4,4',5,5'-HxCB PCB 167 2,3',4,4',6-PeBDE BDE 119 Silver Ag 2,3,3',4,4',5,5'-HpCB PCB 189 3,3',4,4',5-PeBDE BDE 126 Vanadium V TEQ Total PeBDE Zinc Zn 2,2',3,4,4',5'-HxBDE BDE 138 Indicator PCBs 2,2',4,4',5,5'-HxBDE BDE 153 PCDDs 2,4,4'-TriCB PCB 28 2,2',4,4',5,6'-HxBDE BDE 154 2,3,7,8-TCDD D4 2,2',5,5'-TCB PCB 52 2,3,3',4,4',5-HxBDE BDE 156 Total TCDDs 2,2',4,5,5'-PeCB PCB 101 Total HxBDE 1,2,3,7,8-PeCDD D5 2,3',4,4',5-PeCB PCB 118 2,2',3',4,4',5,6'-HpBDE BDE 183 Total PeCDDs 2,2',3,4,4',5'-HxCB PCB 138 2,2',3,4,4',6,6'-HpBDE BDE 184 1,2,3,4,7,8-HxCDD D6-1 2,2',4,4',5,5'-HxCB PCB 153 2,3,3',4,4',5',6-HpBDE BDE 191 1,2,3,6,7,8-HxCDD D6-2 2,2',3,4,4',5,5'-HxCB PCB 180 Total HpBDE 1,2,3,7,8,9-HxCDD D6-3 2,2',3,4,4',5,5',6-OctaBDE BDE 196 Total HxCDDs Bioaccumulative Pesticides 2,2',3,3',4,4',6,6'-OctaBDE BDE 197 1,2,3,4,6,7,8-HpCDD D7 Aldrin Total OctaBDE Total HpCDDs α-chlordane 2,2',3,3',4,4',5,5',6-NonaBDE BDE 206 OCDD D8 γ-chlordane 2,2',3,3'4,4',5,6,6'-NonaBDE BDE 207 Total PCDDs and TEQ o,p-DDT Total NonaBDE p,p'-DDT DecaBDE BDE 209 PCDFs Dieldrin 2,3,7,8-TCDF F4 α-endosulfan Organotins Total TCDFs β-endosulfan Monobutyltin MBT 1,2,3,7,8-PeCDF F5-1 Endosulfan sulphate Monobutyltin-Sn MBT-Sn 2,3,4,7,8-PeCDF F5-2 Endrin Dibutyltin DBT Total PeCDFs α-HCH Dibutyltin-Sn DBT-Sn 1,2,3,4,7,8-HxCDF F6-1 β-HCH Tributyltin TBT 1,2,3,6,7,8-HxCDF F6-2 γ-HCH Tributyltin-Sn TBT-Sn 1,2,3,7,8,9-HxCDF F6-3 Heptachlor Tetrabutyltin TTBT 2,3,4,6,7,8-HxCDF F6-4 cis -heptachlor epoxide Tetrabutyltin-Sn TTBT-Sn Total HxCDFs trans -heptachlor epoxide Monooctyltin MOT 1,2,3,4,6,7,8-HpCDF F7-1 Hexachlorobenzene Monooctyltin-Sn MOT-Sn 1,2,3,4,7,8,9-HpCDF F7-2 Mirex Dioctyltin DOT Total HpCDFs Octachlorostyrene Dioctyltin-Sn DOT-Sn OCDF F8 Oxychlordane Triphenyltin TPhT Total PCDFs and TEQ Pentachlorobenzene Triphenyltin-Sn TPhT-Sn Toxaphene 26 Parlar 26 Tricyclohexyltin TCHT PFCs Toxaphene 50 Parlar 50 Tricyclohexyltin-Sn TCHT-Sn Perfluorooctane sulfonate PFOS Toxaphene 62 Parlar 62 Perfluorooctanoic acid PFOA
24 Investigation of contaminant levels in green turtles from Gladstone 4.0 RESULTS
4.1 TURTLE BIOMETRICS AND HEALTH STATES Among the forty green turtles sampled for this study, 39 were in their juvenile, neretic life stage (average CCL 46; range 39-62 cm); the remaining specimen was an adult of unknown gender (CCL 100 cm) (Table 1). A large proportion of the animals (55%; n=22) were evaluated to have poor (35%; n=14) or very poor (20%; n=8) body conditions, with the latter showing signs of emaciation; three of these specimens were considered to have no chance of survival and were euthanized by a registered veterinarian (Table 1). The remaining 18 animals (45%) appeared to have normal body conditions. Accordingly, body weight was significantly (p<0.05) lower in green turtles with very poor (average 8.1; range 5.4-9.3 kg) and poor (average 9.8; range 8.0-22 kg), compared to normal (average 11; range 7.8-25 kg) body conditions; curved carapace length (CCL) did not differ significantly between these three groups. Despite this, no significant differences were observed for blood lipid content between animals with normal (0.14 ±0.038; range 0.087-0.20%; n=9), poor (0.13 ±0.047; range 0.070- 0.20%; n=5) or very poor (0.16 ±0.064; range 0.062-0.23%; n=8) body conditions. This suggests that the blood lipids consisted mainly of fats not used for storage (e.g. lipoproteins, cholesterol).
4.2 SCREENING
4.2.1 Tier 1 - Qualitative (non-target) screening Figure 2 shows all signals obtained in the total ion count for the liver pool. No signals were identified that could be traced to halogenated compounds or other common environmental pollutants. Using the mass spectra, the most abundant peak was identified as the barbiturate pentobarbital (1), which originates from the use of pentobarbitone to euthanize specimens included in the liver pool. The phthalate, diisobutyl phthalate (2), was identified but possibly originates from the use of materials to collect the samples (e.g. syringe) or materials in contact with the sample (e.g. heparinised saline). The remaining peaks are associated with lipids and sterols naturally occurring in biological samples: several fatty acid derivatives (3-6), a derivative of the hydrocarbon squalene (7), and derivatives of the steroid cholestadien (8-10). Peaks 11a-e could not be identified but are likely to represent sterols or similar compounds.
25 Investigation of contaminant levels in green turtles from Gladstone
Figure 2 Total Ion Count (TIC) GC-MS chromatogram of a green turtle liver pool (n=9). The 10 most abundant peaks (numbered) were identified based on the mass spectra of each peak.
4.2.2 Tier 2 – Quantitative (target) screening Detailed results from Tier 2 analysis of pooled blood (n=40 individuals), liver (n=9 individuals) and fat (n=9 individuals) are presented in Table 3, Table 4 and Table 5. The lipid content in pooled carapace fat was determined to be 1.7% and the water content 89%; the water content of the liver pool was not determined, but averaged 78% (range 76-80%) in liver of three of the specimens included in this pool.
The concentrations for the majority of contaminant groups analysed in these pooled samples were below the limit of quantification (LOQ).
In pooled blood, middle bound total PFOS and PFOA levels were 100 ppb ww; upper bound concentrations were 200 ppb ww (Table 3).
Middle bound concentrations for toxic equivalency (TEQ) of PCDD/Fs and PCBs in pooled fat were 6.1 ppt lw and 4.9 ppt lw, respectively (Table 4). Respective upper bound estimates were 12 and 22 ppt lw. The middle and upper bound concentrations for sum indicator PCBs in pooled fat were 13,000 and 25,000 ppt lw, respectively (Table 4).
The middle to upper bound concentration ranges for sum tri- to deca-brominated flame retardants (PBDEs) and sum organotins in pooled liver were 2.4 to 3.0 ppb dw (approx. 0.53 to 0.66 ppb ww) and 29 to 58 ppb dw (approx. 6.4 to 13 ppb ww), respectively, while perfluorinated compounds were present at 0.65 to 0.70 ppb dw (approx. 0.14 to 0.15 ppb ww) (Table 5).
26 Investigation of contaminant levels in green turtles from Gladstone
Table 3 Concentrations of perfluorinated compounds (PFOS/PFOA; ppb ww) in pooled green turtle (Chelonia mydas) blood (n=40) from Boyne River estuary near Gladstone, Queensland. Water content approximately 89%.
PFCs Perfluorooctane sulfonate <100 Perfluorooctanoic acid <100
SPFOS/PFOA (Lower) Table 4 Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F; ppt lw), WHO-PCBs (ppt lw) and indicator PCBs (ppt lw) in pooled green turtle (Chelonia mydas) fat (n=9) from Boyne River estuary near Gladstone, Queensland. Lipid content 1.7%. PCDD/Fs WHO-PCBs 2,3,7,8-TCDD <3.6 Non-ortho 1,2,3,7,8-PeCDD <2.4 PCB 77 <170 1,2,3,4,7,8-HxCDD <5.3 PCB 81 <34 1,2,3,6,7,8-HxCDD <5.3 PCB 126 <46 1,2,3,7,8,9-HxCDD <5.3 PCB 169 <170 1,2,3,4,6,7,8-HpCDD <40 Mono-ortho OCDD <130 PCB 105 <360 PCB 114 <80 2,3,7,8-TCDF <5.3 PCB 118 <1300 1,2,3,7,8-PeCDF <4.7 PCB 123 <110 2,3,4,7,8-PeCDF <4.7 PCB 156 <440 1,2,3,4,7,8-HxCDF <4.7 PCB 157 <77 1,2,3,6,7,8-HxCDF <4.7 PCB 167 <170 1,2,3,7,8,9-HxCDF <5.9 PCB 189 <110 2,3,4,6,7,8-HxCDF <4.7 1,2,3,4,6,7,8-HpCDF <7.7 TEQ05 WHO-PCBs (Lower) 1,2,3,4,7,8,9-HpCDF <7.1 TEQ05 WHO-PCBs (Middle) 4.9 OCDF <37 TEQ05 WHO-PCBs (Upper) 9.8 < Below the limit of quantification (LOQ) TEQ05 PCDD/Fs (Lower) TEQ05 PCDD/Fs (Middle) 6.1 Indicator PCBs TEQ05 PCDD/Fs (Upper) 12 PCB 28 <5000 TEQ05 PCDD/Fs + WHO-PCBs (Lower) TEQ05 PCDD/Fs + WHO-PCBs (Middle) 11 PCB 101 <3700 TEQ05 PCDD/Fs + WHO-PCBs (Upper) 22 PCB 118 <1300 < Below the limit of quantification (LOQ) PCB 138 <4400 PCB 153 <4700 PCB 180 <3400 SIndicator PCBs (Lower) 27 Investigation of contaminant levels in green turtles from Gladstone Table 5 Concentrations of brominated flame retardants (PBDEs; ppb dw), organotins (ppb dw), perfluorinated compounds (PFOS/PFOA; ppb dw) and bioaccumulative pesticides (ppb dw) in pooled green turtle (Chelonia mydas) liver (n=9) from Boyne River estuary near Gladstone, Queensland. Water content approximately 78%. PBDEs Organotins 2,2',4-TriBDE <0.020 Monobutyltin <5.0 2,4,4'-TriBDE <0.016 Monobutyltin-Sn <3.4 Total TriBDE 0.036 Dibutyltin <5.0 2,2',4,4'-TBDE <0.025 Dibutyltin-Sn <2.6 2,2',4,5'-TBDE <0.031 Tributyltin <5.0 2,3',4,4'-TBDE <0.036 Tributyltin-Sn <2.1 2,3',4',6-TBDE <0.031 Tetrabutyltin <5.0 3,3',4,4'-TBDE <0.025 Tetrabutyltin-Sn <1.7 Total TBDE 0.15 Monooctyltin <5.0 2,2',3,4,4'-PeBDE <0.039 Monooctyltin-Sn <2.6 2,2',4,4',5-PeBDE <0.028 Dioctyltin <5.0 2,2',4,4',6-PeBDE <0.025 Dioctyltin-Sn <1.7 2,3',4,4',6-PeBDE <0.030 Triphenyltin <5.0 3,3',4,4',5-PeBDE <0.025 Triphenyltin-Sn <1.7 Total PeBDE 0.15 Tricyclohexyltin <5.2 2,2',3,4,4',5'-HxBDE <0.044 Tricyclohexyltin-Sn <1.7 2,2',4,4',5,5'-HxBDE <0.040 2,2',4,4',5,6'-HxBDE <0.040 SOrganotins (Lower) 28 Investigation of contaminant levels in green turtles from Gladstone 4.2.3 Tier 3 – Quantitative target analysis Table 6, Table 7 and Table 8 provide a summary of the mean, minimum, maximum and median concentrations, as well as other descriptive statistics, for PCDD/Fs, PCBs, bioaccumulative pesticides, organotins and metals and metalloids analysed in blood of individual green turtles from Boyne River estuary. Table 9 provides mean, minimum and maximum concentrations for metal and metalloid concentrations obtained in liver and kidney samples. The mean lipid content in blood was determined to be 0.15% (n=22, range 0.062-0.23%). In liver, the mean water content was 78% (range 76-80%) and in kidney 88% (range 85-92%). Combined blood TEQ levels for PCDD/Fs and PCBs (TEQdf+pcb) in Gladstone green turtles ranged from 7.1-130 ppt lw on a mammalian TEF basis (middle bound). Using avian TEFs, the levels were 13-120 ppt lw. The highest blood TEQdf+pcb levels were found in the adult turtle blood (130 ppt lw, n=1). For the juvenile samples (n=21), the mean middle bound TEQdf+pcb levels were 19 (range 7-39) and 33 (range 13-62) ppt lw using mammalian and avian TEFs, respectively. For four blood samples, concentrations of some individual PCDD/F and PCB congeners could not be quantified due to analytical interferences in the chromatograms, partially due to low sample volumes. Reported TEQs would potentially be appreciably understated if these congeners were not included in the TEQ calculation. Consequently, predicted values for these congeners were determined and are reported in brackets in Table 6, and in Table 10 and Table 11 in Appendix 8.1. A consistent relative contribution for each PCDD/F and PCB congener (i.e. congener profile) across all (complete) blood samples for juvenile green turtles was observed, and this common profile was used to predict the missing congener values. Analytes of bioaccumulative pesticides and organotins were mostly below the limit of quantification, or were present at relatively low concentrations in blood of green turtles. Results for all analytes in these groups and for each individual turtle are provided in Table 7, and in Table 12 and Table 13 in Appendix 8.1. Total metal and metalloid concentrations were highly variable in blood of green turtles, often ranging over 2 (maximum 3) orders of magnitudes for individual elements (Table 8; Figure 3). For three turtles, blood, liver and kidney concentrations were determined for each individual (Ex 2, 3 and 22; Table 9). Concentrations of most metals and metalloids were, as expected, lower in blood compared to the matched liver or kidney samples, but concentrations of arsenic (As), iron (Fe) copper (Cu), selenium (Se) and lead (Pb) in blood were similar (within the same order of magnitude) or higher compared to those present in matched kidney (and for As also liver) samples. The concentrations for all analytes in this group are summarised in Table 8 and Table 9 and are listed for each individual sample in Table 14 and 15 in Appendix 8.1. 29 Investigation of contaminant levels in green turtles from Gladstone Table 6 Summary (descriptive statistics) of concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F; ppt lw) and WHO-PCBs (ppt lw) in blood from individual (n=22) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. 25th 75th Standard Compound Mean Minimum Maximum Median percentile percentile error Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs; ppt lw) † TEQ05 SPCDD/Fs 16 2.7 120 5.8 13 16 5.0 PCDDs 2,3,7,8-TCDD <3.9 <0.69 <12 <1.3 <2.8 <5.5 <0.70 1,2,3,7,8-PeCDD 9.0 <0.89 82 2.7 5.0 8.6 3.5 1,2,3,4,7,8-HxCDD 11 <0.22 90 1.8 3.8 12 4.0 1,2,3,6,7,8-HxCDD 12 2.8 100 4.2 5.9 14 4.3 1,2,3,7,8,9-HxCDD 11 2.7 76 4.1 5.9 13 3.3 1,2,3,4,6,7,8-HpCDD 54 18 180 32 40 65 8.2 OCDD 200 58 (<470) 110 150 260 25 PCDFs 2,3,7,8-TCDF 11 <1.2 43 3.7 6.4 18 2.2 1,2,3,7,8-PeCDF 2.5 <0.44 6.7 1.0 2.1 3.4 0.41 2,3,4,7,8-PeCDF 3.0 <0.34 7.7 1.2 1.8 5.6 0.55 1,2,3,4,7,8-HxCDF 3.0 <0.32 14 0.93 1.7 3.5 0.71 1,2,3,6,7,8-HxCDF 2.7 <0.31 14 0.84 1.7 3.1 0.64 1,2,3,7,8,9-HxCDF 3.6 <0.42 26 1.3 2.6 3.5 1.1 2,3,4,6,7,8-HxCDF 3.2 0.61 19 0.92 1.8 3.2 0.84 1,2,3,4,6,7,8-HpCDF 11 2.5 26 5.1 9.0 16 1.4 1,2,3,4,7,8,9-HpCDF 5.3 <1.0 33 2.1 3.4 5.9 1.4 OCDF 49 19 98 32 43 62 4.8 Polychlorinated biphenyls (PCBs; ppt lw) † TEQ05 SWHO-PCBs 8.2 3.7 18 5.1 7.8 9.5 0.77 Non-Ortho PCB 77 <150 <75 <290 <100 <140 <190 <11 PCB 81 <55 <25 <110 <42 <54 <65 <4.2 PCB 126 <120 <50 <290 <69 <110 <140 <12 PCB 169 <150 <75 <300 <100 <150 <190 <12 Mono-ortho PCB 105 810 <300 3300 430 640 850 140 PCB 114 <220 <100 <620 <140 <200 <260 <24 PCB 118 3500 <1,500 11000 2100 3000 4200 460 PCB 123 220 <100 440 140 210 280 21 PCB 156 780 <300 2600 410 640 860 120 PCB 157 410 <150 1600 210 330 420 76 PCB 167 620 <250 1800 300 470 590 99 PCB 189 230 <100 520 140 210 280 24 † Middle bound TEQ reported: TEQ values are calculated using WHO 2005 TEFs; non-quantified congeners are included at half the value of their LOQ < Below the limit of quantification (LOQ); (<) Predicted value (see text) 30 Investigation of contaminant levels in green turtles from Gladstone Table 7 Summary (descriptive statistics) of concentrations of bioaccumulative pesticides (ppb ww) and organotins (ppb ww) in blood from individual (n=7) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. 25th 75th Standard Compound Mean Minimum Maximum Median percentile percentile error Bioaccumulative pesticides (ppb ww) Aldrin NA <0.10 <0.10 NA NA NA NA α-chlordane NA <0.020 <0.020 NA NA NA NA γ-chlordane NA <0.020 <0.020 NA NA NA NA o,p-DDT <0.022 <0.02 <0.027 <0.020 <0.020 <0.023 <0.0011 p,p'-DDT <0.024 <0.02 <0.032 <0.022 <0.023 <0.027 <0.0017 Dieldrin <0.064 <0.057 <0.079 <0.059 <0.062 <0.066 <0.0029 α-endosulfan <0.14 <0.10 <0.18 <0.12 <0.13 <0.16 <0.012 β-endosulfan NA <0.20 <0.20 NA NA NA NA Endosulfan sulphate NA <0.20 <0.20 NA NA NA NA Endrin <0.11 <0.099 <0.14 <0.10 <0.11 <0.11 <0.0051 α-HCH 0.037 <0.02 0.14 0.020 0.020 0.020 0.017 β-HCH <0.022 <0.02 <0.027 <0.020 <0.021 <0.024 <0.0010 γ-HCH <0.021 <0.02 <0.023 <0.020 <0.020 <0.020 <0.00040 Heptachlor NA <0.10 <0.10 NA NA NA NA cis -heptachlor <0.047 <0.035 <0.061 <0.041 <0.043 <0.052 <0.0034 epoxide trans -heptachlor NA <0.10 <0.10 NA NA NA NA epoxide Hexachlorobenzene 0.032 <0.023 0.045 0.027 0.030 0.036 0.0031 Mirex <0.026 <0.02 <0.034 <0.023 <0.024 <0.029 <0.0019 Octachlorostyrene NA <0.020 <0.020 NA NA NA NA Oxychlordane <0.072 <0.052 <0.095 <0.062 <0.068 <0.081 <0.0061 Pentachlorobenzene <0.023 <0.020 <0.034 <0.020 <0.020 <0.025 <0.0023 Toxaphene 26 <0.11 <0.085 <0.15 <0.10 <0.11 <0.13 <0.0084 Toxaphene 50 <0.24 <0.18 <0.31 <0.21 <0.22 <0.27 <0.017 Toxaphene 62 <0.48 <0.35 <0.62 <0.42 <0.44 <0.54 <0.035 Organotins (ppb ww) Monobutyltin <8.5 <6.8 <9.4 <8.6 <8.6 <8.7 <0.30 Monobutyltin-Sn <5.7 <4.6 <6.3 <5.8 <5.8 <5.9 <0.20 Dibutyltin <12 <6.8 <20 <8.6 <10 <14 <1.9 Dibutyltin-Sn <6.0 <3.5 <10 <4.4 <5.1 <7.1 <0.98 Tributyltin <16 <8.6 <27 <13 <13 <19 <2.4 Tributyltin-Sn <6.6 <3.5 <11 <5.2 <5.5 <7.9 <0.97 Tetrabutyltin <20 <15 <27 <19 <20 <21 <1.4 Tetrabutyltin-Sn <6.9 <5.0 <9.3 <6.5 <6.8 <7.3 <0.49 Monooctyltin <9.7 <6.8 <16 <7.8 <8.6 <10 <1.2 Monooctyltin-Sn <5.0 <3.5 <8.3 <4.0 <4.4 <5.3 <0.62 Dioctyltin <13 <8.6 <27 <9.3 <10 <15 <2.6 Dioctyltin-Sn <4.6 <2.9 <9.1 <3.2 <3.5 <5.2 <0.91 Triphenyltin <8.7 <6.8 <10 <8.6 <8.6 <9.1 <0.38 Triphenyltin-Sn <2.9 <2.3 <3.4 <2.9 <2.9 <3.1 <0.13 Tricyclohexyltin <34 <30 <41 <30 <31 <39 <2.0 Tricyclohexyltin-Sn <11 <9.6 <13 <9.7 <9.8 <13 <0.64 < Below the limit of quantification (LOQ) NA Not applicable 31 Investigation of contaminant levels in green turtles from Gladstone Table 8 Summary (descriptive statistics) of concentrations of metals and metalloids (ppb ww) in blood from individual (n=40) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. 25th 75th Standard Compound Mean Minimum Maximum Median percentile percentile error Metals and Metalloids (ppb ww) Aluminium ND ND ND ND ND ND ND Arsenic 2300 40 20000 410 1200 2600 550 Cadmium 40 8.1 110 16 36 61 4.3 Chromium 16 1.3 340 2.3 3.3 3.8 9.3 Cobalt 150 28 440 73 120 200 15 Copper 780 450 1900 610 710 840 43 Iron 66000 33000 96000 54000 67000 79000 2400 Lead 18 0.20 76 7.2 15 21 2.5 Manganese 35 16 92 24 32 39 2.4 Mercury 9.3 <0.22 38 1.2 3.3 13 1.8 Molybdenum 11 4.6 83 6.5 8.5 11 1.9 Nickel 5.2 0.67 17 3.1 4.6 6.9 0.53 Selenium 1900 84 8600 410 1000 2700 330 Silver 0.66 0.011 7.1 0.084 0.22 0.74 0.20 Vanadium 12 3.5 38 6.7 8.2 14 1.4 Zinc 8400 3800 12000 6800 8400 9600 310 ND not determined < Below the limit of quantification (LOQ) Table 9 Summary (descriptive statistics) of concentrations of metals and metalloids (ppm ww) in liver and kidney from individual (n=3) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. Compound Mean Minimum Maximum Mean Minimum Maximum Liver Kidney Metals and Metalloids (ppm ww) Aluminium 2.8 2.4 3.5 0.39 0.28 0.48 Arsenic 2.0 2.0 2.0 1.2 0.88 1.5 Cadmium 17 13 24 48 17 90 Chromium 0.18 0.092 0.29 0.32 0.17 0.62 Cobalt 1.4 0.93 2.3 2.1 0.99 3.2 Copper 84 67 100 4.4 1.8 9.4 Iron 1900 1100 2800 15 11 21 Lead 0.16 0.12 0.20 0.096 0.047 0.15 Manganese 2.5 2.3 2.6 0.66 0.48 0.87 Mercury 1.3 0.86 1.6 0.42 0.15 0.72 Molybdenum 0.54 0.39 0.83 0.16 0.062 0.30 Nickel 0.20 0.17 0.23 9.1 0.42 26 Selenium 5.4 4.0 7.2 1.3 0.62 2.4 Silver ND ND ND ND ND ND Vanadium 0.45 0.23 0.79 0.30 0.23 0.34 Zinc 45 41 51 33 20 40 ND No data 32 Investigation of contaminant levels in green turtles from Gladstone Arsenic Cadmium Chromium Cobalt 20,000 120 350 500 100 300 16,000 400 250 80 12,000 200 300 60 150 8,000 200 40 100 Concentration (ppb ww) (ppb Concentration 4,000 100 20 50 0 0 0 0 Copper Iron Lead Manganese 2,000 100,000 80 100 70 90 1,600 80,000 80 60 70 50 1,200 60,000 60 40 50 800 40,000 30 40 30 Concentration (ppb ww) (ppb Concentration 20 400 20,000 20 10 10 0 0 0 0 Mercury Molybdenum Nickel Selenium 40 90 18 10,000 35 80 16 8,000 30 70 14 60 12 25 6,000 50 10 20 40 8 15 4,000 30 6 Concentration (ppb ww) (ppb Concentration 10 20 4 2,000 5 10 2 0 0 0 0 Silver Vanadium Zinc 8 40 12,000 7 35 10,000 6 30 8,000 5 25 4 20 6,000 3 15 4,000 Concentration (ppb ww) (ppb Concentration 2 10 2,000 1 5 0 0 0 Figure 3 Box and whisker plots for metal and metalloid concentrations (ppb ww) in blood from individual (n=40) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. Box plots show the mean (red cross) and median (red line), the 25th (bottom of box) and 75th (top of box) percentiles, and 1.5 times the inter quartile range (whiskers). 33 Investigation of contaminant levels in green turtles from Gladstone 5.0 DISCUSSION 5.1 CONTAMINANT LEVELS IN RELATION TO TURTLE BIOMETRICS, HEALTH AND SAMPLING LOCATION Among the forty individual green turtles included in the present study, 39 were juveniles, thus minimising variation of bioaccumulative contaminant levels due to organism age or breeding status. Across the bioaccumulative contaminant groups analysed, only dioxin concentrations were clearly higher in the adult specimen compared to juveniles (see discussion below). Other contaminant groups that were detected and known to bioaccumulate with age (PCBs, mercury, arsenic, cadmium, lead, selenium, silver), were often lower, or similar in the adult specimen compared to most juveniles. This may be due to a) different long-term feeding habitats of the adult, or b) recent increases in the exposure regimen for metals/metalloids. A large proportion (55%) of the animals sampled presented with poor (35%) or very poor (20%) body conditions, and associated deficient nutritional and general poor health states. Despite this, no clear and consistent differences were observed in organic contaminant levels between animals with different body conditions. Although mobilisation of lipids and associated lipophilic contaminants are expected in these specimens, blood lipid content did not differ among animals of different body conditions and, although generally low compared to other sea turtles, percent lipid in blood was comparable to live captured green turtles in Moreton Bay (average 0.18; range 0.080-0.55%; n=35) (Hermanussen, 2009). Concurrent with this, no significant difference was observed between the levels of lipophilic contaminants (which were mostly present at relatively low levels) in blood of Gladstone green turtles with different body conditions. Among metal and metalloids, Cr, Fe, Mn, Ni, and Zn levels in blood were significantly (p<0.05) lower in green turtles that were classified with very poor compared to those with normal body conditions. Similar trends have previously been reported for loggerhead turtles, and were hypothesised to relate to a lack of feeding, and thus lower metal exposure, for some time prior to sampling (Day et al., 2010). These metals (Cr, Fe, Mn, Ni, Zn) have among the fastest clearance rates from blood with half- lives in the order of 2-48 hours ((Farheen et al., 2002) for Fe; (ATSDR, 2008b) for Cr; (ATSDR, 2005a) for Ni; and (ATSDR, 2005b) for Zn). Since the green turtles presenting with very poor body conditions are likely to have stopped or reduced feeding for prolonged periods, it is feasible to assume associated reduced metal uptake and rapid decrease in blood concentrations of metals with such short half-lives. Metals that generally have longer half-lives and relatively slow blood clearance rates in vertebrates (Hg, Cd, and V) were present at similar concentrations in turtles across all three body conditions. These results may thus reflect the varying toxicokinetics of individual element species and forms in combination with the animals’ exposure levels and cessation of exposure relative to the time of sampling. Juvenile green turtles recruit to neretic feeding grounds at around 40-50 cm CCL (Limpus and Limpus, 2003). Satellite tracking studies indicate that green turtles display high site fidelity to foraging grounds, undertaking short term movements of 2-24 km (Limpus, 2008). Upon reaching maturity, adults migrate to their breeding sites, but return to the same feeding area home range (Limpus et al 34 Investigation of contaminant levels in green turtles from Gladstone 1992). Considering these studies, the contaminant levels in juvenile green turtles of this study are likely associated with exposure in the local area from which they were sampled. 5.2 CONTAMINANT EXPOSURE CONCENTRATIONS AND RISK EVALUATION Contaminant exposure and associated risks of adverse effects are ideally assessed by integrating spatial and temporal data on the exposure with detailed understanding on the mechanisms and dose-dependent effect measures. Realistically, exposure is often unknown, and effect doses, which vary among species, are only investigated for few, mostly laboratory test animals. Regardless of the complexities and existing gaps, however, evaluations can be carried out using exposure surrogates (e.g. analysis of blood) in combination with information on toxicokinetics (uptake, metabolism, elimination) and effects, which, to some degree, can be extrapolated across species. Such evaluations inherently carry uncertainties, but provide a reasonable preliminary basis to assess whether the estimated exposure may be of concern (Hermanussen, 2009; Grillitsch and Schiesari, 2010). While reptiles are generally underrepresented in toxicological studies (Grillitsch and Schiesari, 2010) several publications are available to provide a comparative basis on tissue based exposure concentrations of many contaminant groups in sea turtles, including green turtles (reviewed in (Eisler, 2010; Grillitsch and Schiesari, 2010)). These studies indicate that, similar to vertebrates, tissue levels in sea turtles parallel the degree of environmental contamination (Day et al., 2005; Hermanussen, 2009; Grillitsch and Schiesari, 2010). Particularly for metals and metalloids, however, it is difficult to establish what constitutes non-elevated, normal background levels in sea turtles due to a) the spatial variability of naturally occurring elements, b) a general bias in the literature on stranded and/or moribund sea turtles or live captured specimens from areas near agricultural, urban and industrial sources, and c) relatively few comparable blood based concentrations in combination with the rapid clearance rates of most metals and metalloids in blood. Available studies also indicate that key uptake pathways, systemic transport, distribution and elimination routes of many contaminants are similar in reptiles compared to those known for other vertebrates (Hermanussen, 2009; Grillitsch and Schiesari, 2010), and that adverse effects are possible in sea turtles at elevated exposure levels experienced by wild specimens (Day et al., 2007; Grillitsch and Schiesari, 2010). In the absence of reptile specific data for most contaminants, extrapolation from across vertebrate taxa (fish, birds, mammals) is thus a commonly used approach (Grillitsch and Schiesari, 2010). For the present study, exposure was assessed using predominantly blood, and where available, matched tissue concentrations in comparison to those reported for other green turtles (Appendix 8.2 and Section 5.3). Where insufficient data was available, data from other sea turtles, and organisms were used to evaluate whether contaminant tissue levels may be elevated, taking into account the potential for contaminant biomagnification through the food chain. To determine whether exposure may represent a risk to the study population, blood and tissue levels or, where possible, estimated body burdens were compared to blood, tissue or body burden based effect concentrations reported for reptiles, and across other vertebrate taxa (see Section 5.3). Note that comparisons of the measured blood or tissue concentrations to oral doses (e.g. lowest-observed adverse effect levels) was not possible, as very limited species/reptile-specific data is available in the literature, and blood 35 Investigation of contaminant levels in green turtles from Gladstone or tissue concentrations are not comparable to dose effect concentrations across taxa; thus, comparisons focus on tissue based effect levels. Based on these comparisons, contaminants were classified into the following three categories: 5.2.1 Contaminants of relatively low concern Overall, the samples analysed for the present study contained relatively low levels of bioaccumulative pesticides, organotins, flame retardants (PBDEs), and perfluorinated compounds (PFOS/PFOA). The concentrations of these contaminant groups in fat, liver and/or blood samples were mostly near or below the limit of quantification (LOQ) (Table 3, Table 5, Table 7, Table 12, Table 13). Comparisons to the literature indicate that these concentrations are similar to background levels reported in other green turtles and sea turtles (Hermanussen et al., 2008; Swarthout et al., 2010; Malarvannan et al., 2011), or other marine megafauna, and considerably lower than the levels that are considered elevated or of concern in such wildlife (Kannan et al., 2000; Keller et al., 2004a; Ross et al., 2007; Orós et al., 2009; van de Merwe et al., 2009). Where detected, the concentrations of these contaminants in tissue or blood therefore most likely represent background levels, and the risk of adverse effects associated with each of these compounds in the study population is considered relatively low; no further review was therefore conducted Concentrations of aluminium (Al), iron (Fe), manganese (Mn) and zinc (Zn) were present in blood and tissues (except for Al in blood, which could not be quantified) that were comparable to those reported for many other sea turtles, including from apparently healthy specimens and locations considered to be relatively unimpacted by local urban, agricultural or industrial point sources (Appendix 8.2). The concentrations of these elements also generally fall within normal ranges observed in other marine megafauna, and are thus considered likely to represent normal background levels of little hazard to the study population; no further review was thus conducted. In this context, it has to be noted that the presence of low levels of complex chemical mixtures may result in chronic biochemical and/or physiological changes that can adversely affect organisms, even if individual contaminants are below their respective threshold levels. However, current scientific understanding is insufficient to quantitatively assess such mixture effects in most biota, particularly megafauna such as sea turtles. 5.2.2 Contaminants possibly of concern Concentrations of silver (Ag), copper (Cu), chromium (Cr), molybdenum (Mo) and lead (Pb) in blood and for Cu also in liver and kidney were higher than those reported for most other sea turtles and other vertebrates, but comparable to the upper range reported from moribund green turtles and specimens from relatively polluted areas (Appendix 8.2). Compared to other vertebrates, these levels appear to be elevated. Toxicological information for other organisms, where available, indicates tissue-based concentrations for acute effects are considerably higher, but information on chronic effects was lacking. Thus, there was insufficient information to assess whether these elements pose a risk of effects to the turtle population at the exposure levels in Gladstone. Dioxin and PCB toxic equivalencies (TEQ) in blood of juvenile green turtles from Gladstone were comparable to the lower ranges reported for other green turtles (Appendix 8.2) and similarly low trophic marine mammals (dugongs). However, the adult specimen contained elevated TEQ levels 36 Investigation of contaminant levels in green turtles from Gladstone (mainly due to elevated dioxins, rather than PCBs), comparable to the upper ranges reported for turtles and dugongs, and other, higher trophic marine wildlife. This may indicate chronic exposure to elevated levels of dioxins, rather than elevated recent exposure, but more adult specimens would be required to evaluate this. Risk assessment based on estimated body burdens suggests that TEQ levels in 6.6% of the juvenile green turtles are above adverse effect levels (LOAELs) where biochemical effects occur in mammals; these may or may not be harmful to the animals. Using upper bound TEQs (i.e. a worst case scenario), the estimated body burden of up to 5.0% of the juvenile green turtles are above the LOAELs for chronic developmental toxicity in avian species. While only one adult specimen was obtained, it is noteworthy that the estimated body burden in this specimen exceeds the LOAEL for immunological and developmental effects in both mammals and birds. The risk assessment and results are discussed in more detail below (Section 5.3.10). 5.2.3 Contaminants of concern For several metals/metalloids (arsenic (As), cadmium (Cd), cobalt (Co), mercury (Hg), nickel (Ni), selenium (Se), and vanadium (V)), blood and/or tissue concentrations were clearly higher in green turtles from Gladstone compared to those reported for most other green turtles (and for non- biomagnifying compounds other sea turtles or vertebrates), or within the upper levels reported for specimens that were moribund and/or originated from areas considered relatively polluted (Appendix 8.2). In addition, these elements were present at higher levels compared to normal background concentrations known for other vertebrates, including marine megafauna. In many cases, elevated levels were present in blood, rather than in matched liver or kidney samples. Based on the relatively rapid blood clearance rates of many of these elements, this suggests that exposure may have occurred relatively recent prior to sampling (days to months, depending on the element and level of exposure), rather than via chronic accumulation. Concentrations of Hg, Cd and Se were above or within the levels where adverse effects have been suggested to occur in reptiles. The concentrations of the remaining metals/metalloids (As, Co, Ni, and V) were above, near or within tissue-based concentrations where acute effects have been observed in other vertebrates (birds and mammals). Although the sensitivity of sea turtles to these elements is unknown, this suggests that acute adverse effects from exposure of green turtles in Gladstone are possible, and chronic effects may be expected if exposure persists. These elements are discussed individually in Section 5.3. These sections include a brief background on sources, fate and toxicokinetics, a detailed comparison of blood and tissue levels among green turtles, sea turtles and other organisms, and a review of studies on toxicology and effects, including a summary of available information on tissue based effect concentrations. 37 Investigation of contaminant levels in green turtles from Gladstone 5.3 REVIEW - CONTAMINANTS OF CONCERN 5.3.1 Arsenic (As) SOURCES Arsenic is a metalloid that occurs naturally in trace quantities in rock, soil, water and air. Arsenic exists as four, but commonly only as three valency states (0 (elemental), +III (arsenite), +V (arsenate)), and as numerous species in inorganic (combined with oxygen, chlorine, sulfur) and organic (combined with carbon and hydrogen) form, which vary in their properties (e.g. water solubility) and toxicities. Mining, smelting of non-ferrous metals, and burning of fossil fuels are the key industrial processes that contribute to arsenic contamination of air, water and soil (Gomez- Caminero et al., 2001). Depending on the level of industrialisation, significant quantities may also be released by wastewater runoff derived from e.g. atmospheric depositions, residues from pesticide usage, phosphate detergents and industrial effluent, particularly from the metal-processing industry (Gomez-Caminero et al., 2001). Arsenic has been widely used in wood treatment as copper chromate arsenate (CCA) and arsenic-containing pesticides were historically used primarily in cotton and orchards (Gomez-Caminero et al., 2001; ATSDR, 2007). Typically, key arsenic input pathways to marine environments are river runoff and atmospheric deposition (Sanders, 1980; Gomez-Caminero et al., 2001). TOXICOKINETICS Organisms are exposed to many different forms of inorganic and organic arsenic species in food, water, air, soil and sediments. Approximately 25% of arsenic in human food is inorganic, but levels in fish or shellfish are low (<1%). Due to the different properties of arsenic species, including their varying bioavailability and considerable interspecies differences in metabolism, the toxicokinetics of arsenic is highly complex (Gomez-Caminero et al., 2001). Arsenic is rapidly cleared from blood (within hours to days, depending on the organism, arsenic forms and dose) (Gomez-Caminero et al., 2001; ATSDR, 2007). Blood and urine thus serve as useful markers for very recent acute or stable, chronic, high-level exposure. Keratin rich tissues (e.g. scutes of the shell in turtles) can, in contrast, be used as indicators of past arsenic exposure (Gomez- Caminero et al., 2001). In general, organisms can be exposed to arsenic via inhalation, ingestion of contaminated food or water, and dermal exposure. As(III) and As(V) are also known to readily cross the placenta in laboratory animals and humans (Gomez-Caminero et al., 2001). Oral bioavailability in laboratory animals varies widely (5-85%), depending on the dose, matrix, arsenic form and animal species. Dermal absorption of organoarsenic chemicals are in the order of 3-40%. Soluble arsenates (arsenobetaine, monomethyl arsenic (MMA) and dimethyl arsenic (DMA)) and arsenates are rapidly and extensively (near complete) absorbed from the gastrointestinal tract in laboratory animals and most forms are excreted primarily via urine (Gomez-Caminero et al., 2001; ATSDR, 2007). In general, organoarsenicals are less extensively metabolized than inorganic arsenic, but more rapidly eliminated in both laboratory animals and humans. After exposure, arsenic is transported in blood and distributed to liver, kidney, spleen and lung. Several weeks after exposure, arsenic is 38 Investigation of contaminant levels in green turtles from Gladstone translocated to ectodermal tissues (hair, nails) because of the high concentration of sulfur-containing proteins in these matrices (Eisler, 1988). Aquatic organisms, particularly marine plants, can accumulate organic arsenic species, but biomagnification has not been observed in the aquatic food chain (Eisler, 1988; Gomez-Caminero et al., 2001; ATSDR, 2007). EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Arsenic concentrations in blood of green turtles from Gladstone were highly variable, ranging from 40 ppb to 20,000 ppb ww (mean: 2,300 ppb ww). To date, only few reports exist on arsenic in blood of sea turtles and similarly high levels (94-20,000 ppb ww; mean 4,400 ppb; SE ±1400; n=16) have been reported in green turtles from Moreton Bay or other areas in southeast Queensland (van de Merwe et al., 2010). However, the latter study was focused on severely debilitated turtles which died at the SeaWorld rehabilitation program and may have originated from relatively contaminated zones (van de Merwe et al., 2010). In contrast, arsenic levels in blood from green turtles from San Diego Bay (average 160 ± 26 ppb ww; n=30) are an order of magnitude lower, despite its highly urbanised sources and routine dredging activities (Komoroske et al., 2011). Similarly, urine (an appropriate marker for recent exposure) of green turtles from Japan contained arsenic levels of 900 ppb ww (n=2) (Agusa et al., 2011), which is comparable to blood of clinically healthy loggerhead turtles from the Mediterranean (average 770; range 230-2,600 ppb ww; n=5) (Jerez et al., 2010). Much lower background blood As concentrations have been reported in four Amazon river turtle species (averages 1.3, 3.5, 3.8, 4.9 ppb ww; n=60) (Burger et al., 2009) which are similar to those considered normal for non-exposed humans, (<1 ppb) (ATSDR, 2007). It is widely known that marine organisms, especially plants, shellfish and fish but also some higher trophic marine mammals and seabirds (Kubota et al., 2003a) naturally accumulate higher quantities of particular arsenic compounds, and thus contain higher total arsenic levels compared to terrestrial biota. Typically, the predominant arsenic species accumulated in marine organisms, including marine mammals, are water soluble organic forms, particularly arsenosugars and arsenobetaine, respectively (Gomez-Caminero et al., 2001; Kunito et al., 2008), which have much lower toxic potency compared to inorganic and other organic forms. Based on arsenic speciation studies it has, however, been suggested that in addition to arsenobetaine, both green turtles and dugongs (who share common food sources and habitats) may accumulate higher proportions of lipid soluble and/or As(III) compounds such as MMA(III) and DMA(III). Arsenobetaine was for example found to be a minor constituent in dugongs (n=4/4), who contained MMA at a relatively high portion (~40%) of total arsenic (Kubota et al., 2003a). As(III) was detected in green turtles (Styblo et al., 2000; Kubota et al., 2003b; Kubota et al., 2003a), including in liver and urine (Agusa et al., 2011), and relatively high proportions of MMA(III) (1.9%; n=3/5), DMA(III) (5.2%; n=5/5), dimethylarsinic acid (6.6%; n=5/5) and tetramethylarsonium ion (1%; n=4/5) were quantified in addition to arsenobetaine in green turtle liver (Kubota et al., 2003b; Kubota et al., 2003a). Considering such unusual accumulation patterns, adverse effects on turtle biological system are considered possible at elevated arsenic levels (Kubota et al., 2002). In addition to blood, arsenic was analysed in liver and kidney from three euthanized green turtles (EX2, EX3 and EX 22; see Table 1) from Gladstone. Concentrations in these tissues were 2.0, 2.0 and 2.0 ppm ww and 1.2, 1.5 and 0.88 ppm ww, respectively. These concentrations are comparable to 39 Investigation of contaminant levels in green turtles from Gladstone average levels reported from stranded or moribund green turtle liver and kidney from southeast Queensland (3.2 and 2.7 ppm ww, respectively; (van de Merwe et al., 2010)). Similar levels have also been reported in green turtle liver and kidney from Torres Strait (1.5 and 0.42 ppm ww, respectively; (Gladstone, 1996)), Turkey (2.1 and 1.7 ppm ww; (Kaska et al., 2004)), Japan (0.38-1.2 and 1.6-2.1 ppm ww, respectively; (Agusa et al., 2008)) and China (1.0 and 0.85 ppm ww, respectively; (Lam et al., 2004)). A recent study reported relatively low (0.67 ±0.019 ppm ww; n=20) arsenic levels in eggs of flatback turtles collected on Curtis Island off Gladstone in 2006, which are considered to reflect the exposure of the laying adults (Ikonomopoulou et al., 2011), however the transfer efficiency of arsenic to eggs is unknown. Notably, the blood arsenic concentrations in the three euthanised specimens from Gladstone were below the average (1100, 570, and 650 ppb ww, respectively), and assuming a similar relationship between blood, liver and kidney concentrations as reported in green turtles from southeast Queensland (van de Merwe et al., 2010), liver concentrations in some live turtles from Gladstone may be several fold higher (up to 9.7 ppm ww in liver were observed in turtles with blood arsenic levels of 20,000 ppb; (van de Merwe et al., 2010)). For context, background arsenic levels in tissue of most other living animals are usually <1 ppm ww, including humans (Eisler, 1988; Gomez-Caminero et al., 2001). Low levels have also been reported for alligator and crocodile eggs (0.05-0.2 and 0.2 ppm ww, respectively; (Eisler, 1988), and most marine mammals contain generally <1 ppm in liver and muscle (Muir et al., 1988; Varanasi et al., 1994; Neff, 1997; Gomez-Caminero et al., 2001; Stavros et al., 2011; Poulsen and Escher, 2012). However, pinnipeds can contain arsenic up to 1.7 ppm ww (Eisler, 1988). Among the highest arsenic concentration recorded in marine mammals was 2.8 ppm ww in lipid of a cetacean from Norway (Eisler, 1988). TOXICITY AND EFFECTS Different organ systems can be affected by arsenic, including skin, respiratory, cardiovascular, immune, genitourinary, reproductive, gastrointestinal and nervous systems (Gomez-Caminero et al., 2001). Symptoms of toxication can include gastrointestinal disorders, hepatic and renal failure, disturbances of cardiovascular and nervous system functions, and eventually death. Chronic exposure to arsenic is linked to increased risks of cancer in the skin, lungs, bladder and kidney, as well as other skin changes such as hyperkeratosis and pigmentation changes. There is some evidence for arsenic to cause hypertension and cardiovascular disease, diabetes, reproductive effects, cerebrovascular disease, long-term neurological effects, and cancer at sites other than lung, bladder, kidney and skin (Gomez-Caminero et al., 2001). Both inorganic and organic forms of arsenic can cause adverse effects in organisms, however, the degree of toxicity varies with speciation and oxidation state (valency). Generally, water soluble inorganic arsenic species are more toxic than organic forms, and within these two classes, the trivalent (III) arsenites tend to be more toxic than the pentavalent (V) arsenates (ATSDR, 2007). For example, the lethal dose (LD50) values (oral administration to mice) range from approximately 8 ppm (As(III), 21 ppm As(V)), 580 ppm (tetramethylarsonium chloride), 1800 ppm (MMA and DMA), to >10,000 ppm (arsenobetaine) (Gomez-Caminero et al., 2001; ATSDR, 2007). However, it was also reported that dimethylarsinic acid has cytotoxicity (Ochi et al., 1999; Kubota et al., 2003b) and genotoxicity (Mass and Wang, 1997; Yamanaka et al., 1997; Kubota et al., 2003b). Furthermore, 40 Investigation of contaminant levels in green turtles from Gladstone toxicity of methylarsonous acid and di-methylarsinous acid, metabolites of methylarsonic acid and dimethylarsinic acid, respectively, is comparable or higher than that of arsenite (Styblo et al., 2000; Kubota et al., 2003b). In addition, different biota exhibit a range of sensitivities to different arsenic species, which is modified by numerous biological and environmental factors, particularly in the aquatic environment (Eisler, 1988). In marine fish, the water based LC50 (96-hours) range from 13-29 ppm for As(III). In birds, dietary LD50 were reported at 48 ppm As(III) and >2000 ppm MMA (Costigan et al., 2001). In marine mammals, water doses of 0.37-3.7 ppm arsenic (as AsCl3) resulted in immunotoxic effects in lymphoma B cell lines from harbour seals (decreased lymphoproliferation, phagocytic activity and efficiency) (Frouin et al., 2010). No blood based effect levels are available for wildlife, but acutely toxic and fatal human cases have been reported to occur at blood As levels of ~ 1,000 ppb (ATSDR, 2007). Reported tissue based effect concentrations vary widely among animal species, however, most organisms show acute effects at tissue levels in the low to mid ppm ww range. For example, lethal arsenic toxicoses in cattle, horses and deer was reported at liver concentrations of 4-22 ppm (Gomez-Caminero et al., 2001). In birds, residues in the 2 to 10 ppm ww range in liver or kidney are considered elevated; residues >10 ppm are indicative of arsenic poisoning (Eisler, 1988). Adverse effects of arsenic on aquatic organisms have been reported at concentrations of 1.3 to 5 ppm ww in tissues (Eisler, 1988). However, as discussed above, many marine organisms can contain several fold higher organic arsenic levels that seem to present little hazard to the organism or its consumers (Gomez-Caminero et al., 2001). SUMMARY Considering the arsenic levels reported for other sea turtles, and other marine species, As levels in green turtle blood from Gladstone are unusually elevated, but comparable to those reported for moribund green turtles. In contrast, liver and kidney As levels are within the typical ranges reported from green turtles and other marine wildlife. This suggests recent high-level exposure may have occurred. Considering the limited information on arsenic accumulation in sea turtles in general, and the lack of information on arsenic species present in Gladstone green turtles, it is not possible to conclude whether the levels observed present a hazard to these wildlife. However, available speciation studies indicate that sea turtles can contain inorganic and other highly toxic arsenic species. Considering this, in combination with blood arsenic levels (up to 20 ppm ww) in the range of those where effects can be elicited in other organisms based on blood or tissue levels, adverse effects due to arsenic exposure may be possible in Gladstone green turtles. Speciation of arsenic, which is essential in understanding the toxicity, is thus recommended to improve evaluation of risks to green turtles in Gladstone. 41 Investigation of contaminant levels in green turtles from Gladstone 5.3.2 Cadmium (Cd) SOURCES Cadmium is a rare heavy metal and typically present in small amounts in zinc ores. It commonly exists only in one oxidation state (+2) and does not undergo oxidation-reduction reactions. It is typically obtained as an industrial by-product of the production of zinc, copper and lead. Cd is used in electroplating, pigment production, the manufacture of plastic stabilisers and batteries (ATSDR, 2008a). Major anthropogenic sources of Cd include smelter fumes and dusts, non-ferrous metal mining and refining, incineration and disposal of Cd containing waste and fossil fuels, fertilisers, and municipal as well as sludge discharges (Eisler, 1985a). Cd contamination can be especially severe in the vicinity of smelters and urban industrialised areas, both from historical or current operations (Eisler, 1985a; ATSDR, 2008a). The fate of Cd in the environment and its availability to organisms depends on numerous factors, including its chemical speciation, adsorption and desorption rates from soil/sediments, the concentration of complexing ligands, pH, and the redox potential of the surroundings (Eisler, 1985a). Elemental Cd is mostly insoluble in water and deposits and absorbs to sediments, but its chloride and sulphate salts are freely soluble (and can also travel long distances in air a particles or vapours) (Eisler, 1985a; ATSDR, 2008a). Changes in physico-chemical conditions, particularly pH and redox potential may increase chemical mobility, and therefore bioavailability of sediment-bound Cd (Eisler, 1985a). It is also possible that Cd contaminated sediments are a source for root uptake by aquatic plants, and Cd in plants growing in contaminated soils can contain very high levels that may be detrimental not only to the plants but also to their consumers (Eisler, 1985a). TOXICOKINETICS The major pathway for exposure to Cd are food consumption, particularly plants grown in contaminated grounds, and soil/sediment ingestion, although inhalation of significant Cd levels can occur near cadmium emitting industries (ATSDR, 2008a). Dermal exposure to Cd is considered negligible (<1%) in humans and laboratory animals, but may increase over prolonged exposure (ATSDR, 2008a). Aquatic plants can accumulate Cd from sediments, and very high levels can be present in contaminated areas, presenting a key source of exposure for herbivorous animals and the food chain (ATSDR, 2008a). Various seagrass species have, however, been shown to contain relatively low Cd concentrations (Denton et al., 1980; Talavera-Saenz et al., 2007). After oral exposure, only <10% of Cd in the digestive tract enters the body in humans and laboratory animals, although, absorption can be higher under iron and other nutrition deficient states (ATSDR, 2008a). The biological half times of Cd are relatively long (in the order of years to decades) in humans (ATSDR, 2008a); birds showed similarly long biological half-lives of 99 days (Eisler, 1985a). Cd tends to accumulate preferentially in kidneys and liver of mammals, and only small amounts are eliminated via urine and faeces (ATSDR, 2008a). Cd has also been observed to accumulate readily in sea turtle liver and kidneys, with the latter typically containing significantly higher levels (e.g. (Sakai et al., 2000b; Anan et al., 2001; Kaska et al., 2004; Storelli et al., 2005; Andreani et al., 2008; Barbieri, 2009; Agusa et al., 2011)). Cd accumulation in these tissues is mainly due to the binding of metal ions by metallothionein, a low molecular weight metal binding protein implicated in the detoxification of 42 Investigation of contaminant levels in green turtles from Gladstone toxic heavy metals and homeostasis of essential elements in humans and animals (ATSDR, 2008a), including sea turtles (Andreani et al., 2008). As metallothionein is synthesised in the liver and then transported in the bloodstream to the kidney in mammals, higher Cd concentrations in the kidney compared to the liver are considered indicative of long-term exposure, while both tissues contain similar levels after short-term exposure (except at very high levels) (Andreani et al., 2008; ATSDR, 2008a; Barbieri, 2009). Related to this, kidney Cd levels also tend to rise slower than in the liver immediately after exposure; Cd half-lives for kidneys and liver have been estimated at 4-19 and 6-38 years, respectively (ATSDR, 2008a). Cd tends to bioaccumulate with age in organisms, particularly in carnivores and marine vertebrates (Eisler, 1985a). In sea turtles, including green turtles, significantly higher Cd levels have been reported for older/larger specimens (Godley et al., 1999; Storelli et al., 2005; Barbieri, 2009), although opposite trends are also reported (Gordon et al., 1998; Sakai et al., 2000a; Komoroske et al., 2011; Labrada-Martagón et al., 2011). It remains unknown whether this is due to the exposure history, the ontogenetic shift and associated lower Cd intake in the herbivorous life stages (Sakai et al., 2000a; Labrada-Martagón et al., 2011), or an associated change in physiology/metallothionein production capacity (Caurant et al., 1999). Apart from turtles, studies on other animals also indicate that younger organisms may absorb more Cd (and have higher sensitivity to Cd) than adults (ATSDR, 2008a). Biomagnification of Cd through the food chain is not considered significant (ATSDR, 2008a), and contradictory studies in different species of sea turtles do not provide evidence of biomagnification through the food chain. Higher Cd concentrations in green turtles compared to loggerheads were reported by (Andreani et al., 2008), while the opposite was observed in (Kaska et al., 2004). While Cd can be transferred to offspring via mother milk, studies on turtles indicate that excretion via eggs may not be important, with only <0.5% of Cd burden being eliminated by the mother (Sakai et al., 1995). Blood is an appropriate marker for Cd exposure and may reflect both recent and cumulative exposures over time; the half-life of Cd in blood of laboratory mammals (mice) is estimated at 291 days (ATSDR, 2008a). Urine, which reflects kidney concentrations at chronic intakes, is also used to inform on both recent and past exposure, while kidney Cd levels are generally considered the most important indicator for toxicology (ATSDR, 2008a). EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Cd concentrations in blood of green turtles from Moreton Bay ranged from 40 to 110 (average 40) ppb ww. Similar blood Cd levels were reported from moribund green turtles in southeast Queensland (11-122; average 35 ppb ww; n=16), but also from green turtles caught live at two sites in Mexico (10-50; average 30 and 8.0-120, average 60 ppb ww; n=30 and 60, respectively (Labrada-Martagón et al., 2011)). The latter is considered generally a relatively pristine area, although agricultural and urban discharges occur, and Cd, as well as a number of other metals (Zn, Cu and Pb) in sediments were reported above those in many industrial regions, possibly due to upwelling and/or historical mining activities (Talavera-Saenz et al., 2007; Labrada-Martagón et al., 2011). In contrast, blood Cd levels in green turtles from the highly urbanised and generally contaminated San Diego bay were several fold lower (13 ±4.2 ppb ww; n=19), and were below the limit of quantification in flatback 43 Investigation of contaminant levels in green turtles from Gladstone turtles off the coast of Gladstone (<0.1 ppb ww; n=20) (Ikonomopoulou et al., 2011). Average Cd levels in blood of Florida manatees were 1.0 (range 1.0-3.0) ppb ww (in (Eisler, 2010)). Mean blood Cd in humans are typically around 0.47 ppb ww with slightly higher levels in older age groups, and females (ATSDR, 2008a). In liver and kidney of green turtles from Gladstone, Cd concentrations (average 17, 13-24 and average 47, 17-90 ppm ww, respectively) are also comparable with elevated levels reported from elsewhere. For example, green turtle liver and kidney from Moreton Bay contained what the authors considered among the highest Cd levels recorded for marine vertebrates (average 38, 2.5-57 and average 38, 1.7-76 ppm ww, respectively) (Gordon et al., 1998). Moribund green turtles from southeast Queensland contained similarly high levels (average 14, 4.3-32 and 46, 13-100 ppm ww, respectively) (van de Merwe et al., 2010). In the Torres Strait, Cd levels in liver and kidney of green turtles (average 11, 6.0-17 and average 26, 12-42 ppm ww) were also comparably high (Gladstone, 1996). Similar Cd levels in kidneys (average 28, 4-56 ppm ww) of green turtles were also reported from Japan, and were considered extremely high, although liver contained lower Cd concentrations (average 5.6, 1.1-12 ppm ww) compared to Gladstone turtles (Anan et al., 2001). Similar Cd kidney concentrations were reported from moribund green turtles with severe fibropapilloma (average 42, 16-70 ppm ww) compared to a captive (22 ppm ww) and stranded specimens (average 7.6, 4.7-10 ppm ww) (Aguirre et al., 1994). Liver Cd levels in these same specimens averaged 16 (5-26), 3.1 and 2.7 (0.39-5.4), respectively (Aguirre et al., 1994). Apart from these studies, Cd levels in green turtles are typically one or two magnitudes lower. These include for example average kidney samples of adults and juveniles from Brazil (0.26 and 0.12 ppm ww, respectively; (Barbieri, 2009)), Costa Rica (4.7 ppm ww; (Andreani et al., 2008)), Cyprus (1.0 ppm ww; (Godley et al., 1999)), Turkey (1.9 ppm ww; (Kaska et al., 2004)), Hong Kong (0.30 ppm ww; (Lam et al., 2004)) and Mexico (1.6 ppm ww; (Talavera-Saenz et al., 2007)); liver tissue analysed in these latter studies contained similarly low or lower Cd concentrations. In seabirds, Cd levels in liver and kidney are typically <15 ppm ww and often much lower, but high concentrations >50 ppm ww have been reported from various areas and species (Eisler, 2010). Similarly, studies on marine mammals from Australia, indicate Cd concentrations typically range from It has been suggested that the sometimes very high (up to 80 ppm ww) Cd levels in green turtles may be a result of high accumulation in seagrass (Talavera-Saenz et al., 2007) and/or incidental ingestion of sediment (Gladstone, 1996), although seagrass and sediment Cd concentrations have been found to be relatively low in areas (Denton et al., 1980; Talavera-Saenz et al., 2007) (Gladstone, 1996). Similar to green turtles, loggerhead and other higher trophic sea turtles appear to be able to accumulate comparably high Cd levels which may be taken up via benthic food sources (e.g. crustaceans, muscles) (Caurant et al., 1999). The elevated levels sometimes observed in sea turtles may also be consequence turtle specific metabolic capacities (Caurant et al., 1999). Despite the unknown reasons for the high accumulation efficiencies, there is strong evidence that higher concentrations of Cd in individuals of a given species collected at different locations is almost always 44 Investigation of contaminant levels in green turtles from Gladstone associated with proximity to industrial and urbanised areas or to point source discharges of Cd containing waters (Eisler, 1985a). TOXICITY AND EFFECTS There is no evidence that Cd performs a beneficial role in biological systems, but it is known to be one of the most toxic elements and exerts toxic effects including nephrotoxicity, carcinogenicity, mutagenicity and reproductive toxicity (Eisler, 1985a). Cd has been implicated in severe deleterious effects on wildlife, as well as deaths in humans (Eisler, 1985a). Long term exposure can lead to accumulation of Cd in the kidneys and a range of effects (e.g. decreased growth, respiratory disruption, altered enzyme levels, and abnormal muscular contractions (Eisler, 1985a)) and eventually causing kidney damage and result in debilitating bone disease (Itai-Itai disease), particularly in individuals with poor nutrition (ATSDR, 2008a). The various clinical symptoms from chronic exposure are thought to result from the degeneration and atrophy of the proximal tubules or, in the worse cases, interstitial fibrosis of the kidney (ATSDR, 2008a). In reptiles, ovo-exposure to toxic elements including Cd and As has been shown to affect hatchling growth, foraging efficiency, mortality, thyroid function or later reproductions (Hopkins et al., 1999; Brasfield et al., 2004; Marco et al., 2004; Guirlet et al., 2008). A correlation between reduced vitellogenic capacity and increased hepatic Cd concentrations was also reported for freshwater turtles (Storelli et al., 2005). The sensitivity of mammalian kidneys to Cd is related to Cd distribution in the body and the production of metallothionein (a metal binding protein) in the kidney. Similarly, metallothionein has been suggested to be involved in the regulation of Cd in sea turtles (Anan et al., 2001). Binding of Cd to metallothionein decreases the toxicity of Cd (ATSDR, 2008a). When total Cd content in the renal cortex reaches between 50-300 ppm ww, however, the amount of Cd not bound to metallothionein becomes sufficiently high to cause tubural damage (ATSDR, 2008a). Sublethal effects in most marine animals occur at Cd levels of 0.5-10 ppb in water (Eisler, 1985a). Cd concentrations exceeding 10 ppm ww in liver or kidney of vertebrates, or 2 ppm ww whole body are considered evidence of probably contamination, while elevated levels of 13-15 ppm ww in tissue may represent a significant hazard to animals of higher trophic levels, and residues of 200 ppm ww or 5 ppm ww whole body, are probably life-threatening to most organisms (Eisler, 1985a). A recent study on freshwater turtles showed that relatively low Cd levels (7 ppm) in yolk could impact on gonadal development and may impact the animals by disrupting reproductive process and lowering fertility (Guirlet et al., 2008; Kitana and Callard, 2008). Blood Cd levels (average 13 ±4.2 ppb ww) were also correlated with several health markers in green turtles however interpretation was confounded by covariance with turtle size (Komoroske et al., 2011). Cd levels of 8.3 and 3.3 ppm ww in liver of loggerhead turtles were considered high enough to potentially affect the health of these organisms (Storelli et al., 2005). In occupationally exposed humans, chronic blood Cd levels of 5.6 and 10 ppb were associated with a 10% prevalence of abnormal biomarkers of tubular damage (β2-microglobulin) and renal dysfunction, respectively, and 33% had signs of glomerular damage at blood Cd levels of 5.6-<8.4 ppb (ATSDR, 2008a). Kidney Cd burdens >50 ppm cortex are associated with renal damage in humans, 45 Investigation of contaminant levels in green turtles from Gladstone and blood Cd levels of >1.5 ppb are significantly correlated with reduced sperm count in humans, and showed weak correlations with defective sperm (ATSDR, 2008a). SUMMARY Cd levels in green turtle blood, liver and kidney from Gladstone are comparable to the upper concentrations reported from green and other sea turtles from elsewhere, and are relatively high compared to average concentrations typically found in marine mammals and seabirds. Lowest levels reported in green and higher trophic sea turtle species are 1-2 orders of magnitude below these concentrations; however, several other studies have reported high levels of Cd in different species of sea turtles. While various hypotheses have been proposed to explain such elevated Cd levels in turtles, to date these observations cannot be explained, and it remains unknown whether the associated individuals or populations are adversely affected. In accord with other studies, the elevated Cd levels observed in Gladstone green turtles are near or above tissue based concentrations where significant adverse effects are observed in other animals, and higher compared to levels where sublethal and biochemical effects were implicated, also for sea turtles. While the sensitivity of turtles to Cd is unknown, these studies suggest that adverse effects are possible at the observed Cd exposure levels, although sea turtle specific information is sparse. 46 Investigation of contaminant levels in green turtles from Gladstone 5.3.3 Cobalt (Co) SOURCES Cobalt is a naturally occurring element present at relatively low concentrations in the environment. It commonly occurs in three valence states (0, +2 and +3) (ATSDR, 2004). It is an essential element required in trace amounts to maintain health in animals and humans. In the environment, it is usually combined with other elements (e.g. oxygen, sulfur, and arsenic). Co is used in the form of alloys in a range of industrial, medical and agricultural applications. It may be released from a number of anthropogenic activities, including coal-fired power plants and incinerators, vehicle exhaust, industrial activities related to mining and processing of cobalt-containing ores, smelting facilities and the production and use of cobalt alloys and chemicals (ATSDR, 2004). The fate of Co in the environment depends on many factors, such as the release route, the chemistry of the water and sediment. In general, Co compounds are non-volatile and most have a high affinity for particles (ATSDR, 2004). Such forms are thus strongly associated with soils and sediments, but ionic forms can also remain in the water column and the amount of Co that is mobile increases under more acidic conditions (ATSDR, 2004). Plants can accumulate the cobalt from their surroundings and animals can accumulate Co in their body, but biomagnification through the food chain has not been observed (ATSDR, 2004). TOXICOKINETICS Generally, exposure to Co may occur via air or food and water, but Co can also readily enter an organism via abraded parts of the skin, and has been shown to cross the placenta in animal studies (ATSDR, 2004). Based on its fate in the environment, the predominant exposure route for turtles would be expected to be contaminated sediments and seagrass, however, exposure via water may also occur. The proportion of Co that enters the body from the gastrointestinal tract varies considerably (18-97% in humans, 13-34% in rats, 1-2% in cows), based on the animal species, type and dose of Co, and the nutritional status of the subjects, with higher absorption under iron deficient nutritional states (ATSDR, 2004). Dermal exposure through abraded skin has been observed to be ~80% in guinea pigs, but is low (<1%) through intact skin (ATSDR, 2004). After exposure, Co distributes via the blood to all tissues, predominantly the liver, kidney and bones (ATSDR, 2004). Absorbed Co is eliminated from the body within days to weeks in humans and laboratory animals, with the main route of excretion via urine (ATSDR, 2004). Blood is thus an appropriate and commonly used marker for relatively recent (in the order of days to weeks) exposure to Co (ATSDR, 2004). EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Blood Co levels in Gladstone green turtles ranged from 28-440 (average 150) ppb ww. Average concentrations (36 ±6.7 ppb ww) were considerably lower in moribund green turtles from southeast Queensland (van de Merwe et al., 2010). In adult nesting flatback turtles off the coast of Gladstone (Curtis Island), blood Co levels were below the LOQ (<0.1 ppb ww) (Ikonomopoulou et al., 2011). No other information could be identified for Co blood concentrations in turtles. Normal Co blood levels in humans range from 0.05-2.7 ppb (Catalani et al., 2011), while Co levels as high as 57-187 ppb ww 47 Investigation of contaminant levels in green turtles from Gladstone have been observed in occupationally exposed cohorts (ATSDR, 2004), and a medical human case study reported extremely high Co levels of 549 ppb ww (Catalani et al., 2011). In liver and kidney of Gladstone turtles, average Co levels detected were 1.4 (range 0.93-2.3) and 2.1 (range 0.99-3.2) ppm ww, respectively. These concentrations are higher compared to those reported from most other green turtles, particularly in liver. In liver of green turtles from Japan for example, average Co levels were <0.030 (n=2; (Sakai et al., 2000a)), 0.077 (n=25; (Anan et al., 2001)), and 0.067 ppm ww (n=1; (Sakai et al., 2000b)). Approximately one order of magnitude lower levels were also reported in liver of green turtles from Hong Kong (0.13; n=2; (Lam et al., 2004)) and southeast Queensland (0.61; n=16; (van de Merwe et al., 2010)). Average kidney Co levels were also lower in green turtles from Japan (0.3 (Sakai et al., 2000a), 0.51 (Anan et al., 2001), 0.81 (Sakai et al., 2000b)), however the maximum Co levels in these studies reached the average concentration of green turtles from Gladstone. Similar Co kidney concentrations compared to Gladstone were reported in green turtles from Hong Kong (1.4 ppm ww; n=2) (Lam et al., 2004) and southeast Queensland (1.5 ppm ww; n=x) (van de Merwe et al., 2010); both studies show similarly elevated levels of other metals and metalloids. Co in livers of various seabird species are typically very low ranging from 0.0011 to 0.024 ppm ww (ATSDR, 2004). Similarly, in livers of cetaceans from Hong Kong, Co levels ranged from 0.0015-0.016 ppm ww (n=33) (Lam, 2009) and Co levels in marine mammals are usually less than 0.13 ppm ww (Eisler, 2010). Similarly low levels have been reported for human liver (0.017 ppm ww) from Japan (ATSDR, 2004). TOXICITY AND EFFECTS Co is part of the vitamin B12, and is (at trace levels) essential to the growth and development of various organisms. On the other hand, Co may also elicit harmful effects in organisms if exposure is sufficiently high. These include developmental and behavioural effects, and effects on the blood, liver, kidneys and heart. After dermal exposure, the most commonly observed effect is dermatitis, possibly caused by an allergic reaction (ATSDR, 2004). After inhalation, a range of effects on the respiratory system are also observed (e.g. decreased pulmonary function, asthma, lung disease, dyspnea), as well effects on thyroid and allergic dermatitis (ATSDR, 2004). Co has also been classified as possibly carcinogenic by IARC (ATSDR, 2004). Adequate chronic studies on the oral toxicity of Co in humans and animals are currently not available (ATSDR, 2004). A human case study reported very high cobalt levels (549 ppb ww; whole blood) in a subject that presented with cranial nerve impairment and mild distal sensory-motor disturbances, followed by blindness, deafness and severe limbs motor weakness. The blood Co dropped to ~100 ppb within 10 days and remained elevated (33.9 ppb ww) above background (0.05-2.7 ppb ww) 14 months after exposure (ATSDR, 2004). The doses for oral LD50 in rats range from 42 ppm body weight as cobalt chloride to 317 ppm body weight as cobalt carbonate (ATSDR, 2004). Box turtles that were subcutaneously injected with 5 ppm body weight 5 times per week died within 14 to 147 days (Altland and Thompson, 1958). 48 Investigation of contaminant levels in green turtles from Gladstone SUMMARY Based on the available studies on turtles and other organisms, blood Co levels appear to be relatively high in Gladstone green turtles, however, comparative data are sparse. Co concentrations determined in tissue samples also support that elevated exposure may have occurred, but while both liver and kidney concentrations are higher compared those reported for most other sea turtles, they are within the upper ranges of previously reported levels. Based on the general toxicokinetics of Co in other organisms, this suggests exposure to elevated Co may have occurred relatively recent (days, weeks to months) prior to sample collection. There is no information on the toxic effects of Co in reptiles and it is unknown whether the observed levels may be associated with effects. However, the blood Co levels are in the range of those where acute effects have been described in humans. 49 Investigation of contaminant levels in green turtles from Gladstone 5.3.4 Mercury (Hg) SOURCES Mercury occurs naturally in the environment and exists in several (elemental, inorganic, and organic) forms. There are numerous anthropogenic sources of Hg to the environment, including fossil fuel combustion, mining, smelting, steel mills, chloralkali plants, solid waste incineration, as well as via fertilisers, fungicides and municipal waste, cement production, uncontrolled industrial releases and from industrial wastewater (ATSDR, 1999). After release to air, the fate of mercury depends on its speciation. For example, gaseous elemental Hg can undergo global-scale transport, or particulate and reactive gaseous Hg is primarily deposited within the vicinity of the source. Hg can also be released directly to the marine environment (e.g. via wastewater) or indirectly, via contaminated soil. In aquatic systems, mercury is mostly bound to particles where it is relatively stable. Inorganic Hg is microbially transformed to methylmercury (MeHg), a potent neurotoxin with strong tendency to biomagnify in the aquatic food chain (ATSDR, 1999; Kampalath et al., 2006). TOXICOKINETICS The toxicokinetics of Hg species in organisms are complex and depend on the Hg form. Aquatic organisms are exposed to mercury mainly via food (and ingested sediments), but exposure via the water, air and skin may also occur, with bioavailability depending on the Hg form (ATSDR, 1999). In addition, Hg can transfer to offspring readily in humans (ATSDR, 1999), however, it has been suggested that maternal transfer is not a major elimination pathway for turtles, with only <5% of the maternal Hg burden transferred per clutch (Sakai et al., 1995; Godley et al., 1999). Generally, ingested MeHg is absorbed (almost completely) into the bloodstream within hours, which is the primary transport mechanism of mercury through the body. In blood, the cellular component (e.g. red blood cells) has the highest affinity for Hg, and can contain 10-200 times higher concentrations compared to plasma (Day et al., 2007). However, blood Hg concentrations decline within weeks after exposure ceases, as the dose is distributed to organs and tissues (ATSDR, 1999). This is followed by a slower elimination phase, which may last several months (Day et al., 2007). Organic Hg compounds are mainly excreted via the faeces in humans and animals, and predominantly in the inorganic form (ATSDR, 1999). Blood is therefore a biomarker for measuring relatively recent (within days to weeks) exposure to Hg, but is affected by short-term changes in Hg levels (Day et al., 2005). Particularly the onset of debilitated conditions in animals, including turtles, and the cessation of feeding may create artificially low Hg levels in blood that are no longer representative of the burden during the beginning of their health decline (Day et al., 2010). Despite this, blood Hg levels are often correlated to those in less dynamic tissues suggesting a proportion of blood Hg may also reflect longer term exposure (Day et al., 2005). Exposure assessment of mercury via blood has the added advantage that the majority of Hg present is in its most toxic methylated form (MeHg) thus reducing the need for complex speciation (Day et al., 2005; Day et al., 2007). In contrast to blood, keratinised tissues are commonly used biomarkers of long-term exposure to Hg due to its strong binding of keratin proteins, and relative persistence in these (Day et al., 2005). Liver and kidney typically contain larger proportions of inorganic Hg forms, due to Hg demethylation in 50 Investigation of contaminant levels in green turtles from Gladstone these organs (Day et al., 2005; Day et al., 2007). This is valid for green turtles, where liver MeHg was shown to contribute approximately 9-19% of total mercury (Kampalath et al., 2006). Hg has been shown repeatedly to bioaccumulate in a variety of organisms (ATSDR, 1999). Seemingly contradictory to this, studies indicate that green turtles contain higher Hg levels in their juvenile, rather than adult life stages (Gordon et al., 1998; Kampalath et al., 2006; Komoroske et al., 2011). This has been suggested to be related to their ontogenetic shift in diet from a higher to low trophic level and an associated growth dilution of Hg body burdens (McKenzie et al., 1999; Kampalath et al., 2006; Komoroske et al., 2011). As the opposite trend is observed for other metals (e.g. lead) alternative hypotheses for negative correlations between Hg levels and green turtle size may be a change in physiological biotransformation and elimination, or up-regulation of metallothionein in adult specimens (Komoroske et al., 2011). Despite this, juvenile green turtles typically contain considerably (order of magnitude) lower Hg levels compared to loggerheads when collected from the same area (e.g. (Godley et al., 1999; Anan et al., 2001; Kampalath et al., 2006)). This is consistent with the strong tendency of Hg to biomagnify through the food chain. EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Hg concentrations in blood of live green turtles from Gladstone ranged from <0.22 to 38 ppb ww (average 9.3 ppb ww). Approximately 4 and 9 times lower concentrations were reported in blood of moribund green turtles from southeast Queensland (0.25-7.1; average 2.5 ppb ww; n=16; (van de Merwe et al., 2010)), and a highly urbanised estuary in San Diego (1.0 ppb ±0.16; n=30; (Komoroske et al., 2011)), respectively. While Hg exposure in turtles has been investigated in a number of other studies, including in blood, these studies focus mostly on higher trophic species. Notwithstanding the expected higher Hg levels in higher trophic species (Kampalath et al., 2006) (even in blood, as discussed above), Hg was below the limit of quantification (<0.01 ppb ww) in blood of nesting flatback turtles collected on Curtis Island, off Gladstone in 2006 (Ikonomopoulou et al., 2011). Relatively low levels were also reported in blood of nesting females of carnivorous olive ridley turtles in Mexico (0.6 ppb dw or approx. 0.15 ppb ww using the reported conversion; n=25; (Páez-Osuna et al., 2011)). In contrast to the above mentioned literature, which possibly reflect low background exposure, higher concentrations of Hg were reported in blood of live (higher trophic) loggerhead turtles from the USA (6-77 ppb ww; average 29; n=60; (Day et al., 2007) and 5-188 ppb ww (Day et al., 2005)). Similar levels were detected in live loggerhead turtles from the same area collected 3 years earlier (average 29 ppb; n=34; (Day et al., 2005), with one severely and chronically emaciated animal containing 188 ppb ww (Day et al., 2005). Mercury levels in these individuals were correlated with the distance to the nearest major industrial river mouth. Blood from stranded loggerhead turtles, collected in conjunction with the latter study, contained an average of 99 ppb ww and the highest concentrations (306 ppm ww) was present in an individual that was severely and chronically emaciated and exhibited extreme muscle atrophy as well as an empty gastrointestinal tract (Day et al., 2005). These studies suggest a link between the observed blood Hg levels and negative impacts on loggerhead turtle immune function (Day et al., 2007), as further discussed below. For context, whole blood Hg levels of <5-20 ppb are considered normal in humans (ATSDR, 1999). 51 Investigation of contaminant levels in green turtles from Gladstone Similar to blood, Hg liver (1.3; 0.86-1.6 ppm ww) and kidney (0.42; 0.39-0.72 ppm ww) levels in the three euthanized green turtles from Gladstone were several fold to several magnitudes higher compared to those reported for other green turtles from Australia, and elsewhere. Stranded green turtles from Moreton Bay contained an average of 0.021 ( The body of literature on Hg concentrations in tissues of other aquatic organisms is extensive, mainly from higher trophic marine mammals (~0.3-300 ppm ww in liver) and seabirds (~0.1-100 ppm in liver) (Sakai et al., 2000a), however, marine birds and mammals appear to have either lower proportions of organic Hg, or lower susceptibility to Hg (reviewed in (NJDEP, 2001). Compared to these levels, Hg levels in green turtles are low, likely due to their low trophic level status, but it has been suggested that sea turtles may be substantially more sensitive to Hg toxicity (Day et al., 2007). Alligators from the Everglades contained approximately 10 ppm ww in kidney, which exceeded the chronic risk threshold (Yanochko et al., 1997; Duvall and Barron, 2000; NJDEP, 2001). TOXICITY AND EFFECTS Toxic effects of various mercuric forms include neurotoxicity, impaired growth and development, reproductive effects, liver and kidney damage and immunotoxicity (ATSDR, 1999; Day et al., 2007). Such effects have been shown to occur in mammals, birds and fish, and in contrast to many other metals and metalloids, are also increasingly being investigated in turtles (Day et al., 2007). The nervous system is highly sensitive to mercury (ATSDR, 1999). It has also been shown that Hg elicits immunosuppressive effects for most lymphocyte functions, which is often accompanied by an increase in the susceptibility to infectious agents (e.g. herpes virus; (Ellermann-Eriksen et al., 1994) or tumour cells (Moszczyński, 1997; Day et al., 2007)). In aquatic organisms, MeHg is the most toxic and physiologically important portion of the Hg burden. 52 Investigation of contaminant levels in green turtles from Gladstone Blood Hg levels in green turtles (average 1 ppb ww) were correlated with several clinical health markers from San Diego estuary (Komoroske et al., 2011), and similar results were reported in Kemp’s ridley sea turtles (Day et al., 2007) as well as loggerhead turtles (average 29 ppb ww) from southeast USA (Day et al., 2007), however, confounding factors could not be ruled out in these field studies. Nevertheless, these findings, together with ex-vivo results showing negative correlations with lymphocyte numbers and B-cell proliferative responses (in a population with average blood mercury of 29 ppb ww) and in-vitro immunosuppressive responses (e.g. suppression of B-cell proliferation with a no-observed-effect-level (NOEL) of 50 ppb ww in blood), indicate that adverse effects on sea turtle immune function are possible from elevated exposure to mercury (Day et al., 2007). These studies also suggest that effects in sea turtles occur at substantially lower concentrations compared to other vertebrates, including rats and humans; and thus, the sea turtle immune system may be highly sensitive to Hg toxicity (Day et al., 2007). Tissue based concentrations of 0.5-6 ppm in various bird eggs are associated with decreased egg weight, malformations, lowered hatchability, and /or altered behaviour in various species (reviewed in (NJDEP, 2001)), while acutely poisoned birds usually have whole body mercury levels >20 ppb ww (UNEP, 2002). In contrast, lethal or harmful effects in marine and terrestrial mammals are reported at Hg concentrations >25 to 60 ppm ww in kidneys and liver (UNEP, 2002), while sublethal adverse effects in harp seals were observed at tissue residue concentrations of 47-83 ppm ww (reviewed in (NJDEP, 2001)). In this respect it is however interesting to note that significantly higher levels of liver Hg (20 ppm ww) levels were reported in harbour porpoises that died from infectious diseases compared to uninfected animals (2.3 ppm ww) (reviewed in (Poulsen and Escher, 2012)). For protection of human consumers, maximum allowed or recommended levels of Hg in fish by various countries (including Australia) and WHO/FAO range from 0.5 ppm (fish, crustaceans, molluscs) ww to 1 ppm ww (high trophic fish). SUMMARY Overall, these comparisons suggest that green turtles from Gladstone were exposed to elevated levels of mercury that resulted in blood and tissue levels mostly exceed those reported from green turtles in Australia or elsewhere. As both blood and tissues are consistent in these results, the data indicate mercury levels may be chronically elevated, although short term high-level exposure may also have occurred. While the levels in low trophic, including juvenile, green turtles are expected to be considerably lower compared to higher trophic species, levels detected in Gladstone specimens are comparable to those reported from higher trophic loggerhead turtles foraging near known point sources or in relatively polluted areas. Sensitivity to mercury toxicity is species specific, making it difficult to predict toxic thresholds for green turtles from the limited available data. Nevertheless, previous studies suggests that sea turtles may be particularly sensitive to mercury exposure, and specimens from Gladstone, particularly those with higher mercury blood levels are within the range of those associated with abnormal haematological markers of health in other green and loggerhead turtles. These upper concentrations are also within the order of NOEL for immunosuppressive responses determined ex-vivo for loggerhead turtles. Compared to other relatively sensitive species (e.g. birds), tissue mercury levels in green turtles from Gladstone are also within the determined 53 Investigation of contaminant levels in green turtles from Gladstone effect concentrations. These results suggest Hg levels in Gladstone green turtles are sufficiently high to pose a potential risk of adverse effects in the study population. 54 Investigation of contaminant levels in green turtles from Gladstone 5.3.5 Nickel (Ni) SOURCES Nickel is a natural element that occurs at very low levels in the environment, and is essential for the normal growth of many organisms (Eisler, 1998a; ATSDR, 2005a). It occurs as five stable isotopes, most commonly in 0 and +2 oxidation states, and interacts with numerous inorganic and organic compounds. The dominant species in water is Ni2+ in the form of octahedral hexahydrate ion 2+ (Ni(H2O)6) ) as soluble salts (Ni chloride hexahydrate, and Ni sulphate hexahydrate) and adsorbed to organic matter (Ni nitrate, Ni hydroxide and Ni carbonate). The fate of Ni in marine and other aquatic systems is strongly affected by its speciated form, as well as the pH, redox potential, ionic strength, type and concentration of ligands (Eisler, 1998a). Anthropogenic sources of nickel include ore and mineral mining, smelting, refining, fossil fuel and waste combustion, processing of iron, steel, nonferrous metals, and timber products, electroplating, sludge disposal or application, effluents, and other industries that use, process or manufacture chemicals, gum and wood or carbon black (Eisler, 1998a) TOXICOKINETICS Organisms are typically exposed to Ni via ingestion of food or sediments/soils, inhalation or dermal absorption (Eisler, 1998a). The absorption of Ni is governed by the quantity of exposure and the forms of Ni. Absorption from the gastrointestinal tract is in the order of 1-10% in humans and laboratory animals, but higher absorption rates have been found when Ni is taken up via water, in the absence of food (ATSDR, 2005a). Unabsorbed Ni is rapidly excreted in the faeces, while absorbed Ni is primarily eliminated via urine (Eisler, 1998a; ATSDR, 2005a). Absorption via the skin has been observed with an efficiency of 55-77% within 24 hours (Eisler, 1998a; ATSDR, 2005a). Ni retention is relatively low in mammals with a rapid half-life of only several days (Eisler, 1998a). After absorption, Ni enters the bloodstream where it is present as free hydrated Ni2+ ions, small and protein complexes, and as Ni bound to blood cells in mammals. The partitioning among these compartments varies according to the metal-binding properties of serum albumin, which is highly variable among species (Eisler, 1998a). Via the bloodstream, Ni is distributed to all organs, but is typically found at highest levels in the kidneys, although significant levels can also be deposited in liver, heart, lungs and fat (Eisler, 1998a; ATSDR, 2004). Nickel does not bioaccumulate to a great extent in animals (ATSDR, 2005a), but accumulation may occur in some species, and Ni has been observed to increase in various organs with age of terrestrial and marine mammals (Eisler, 1998b). In mammals, Ni can cross the placental barrier, although this transfer route may be limited, and trophic position in the food chain, sex and reproductive state typically do not significantly influence the Ni body burdens (Eisler, 1998a). Ni levels in blood, as well as serum, plasma and urine provide the most appropriate indices of Ni exposure; blood rapidly reflects current exposure, peaking within hours after oral exposure but Ni is rapidly cleared with mean serum half-time of 30-60 hours (Eisler, 1998a; ATSDR, 2005a); thus blood only reflects the most recent exposure before sampling (within hours to days). 55 Investigation of contaminant levels in green turtles from Gladstone EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Ni concentrations in blood of green turtles from Gladstone averaged 5.2 ppb ww (range 0.67-17 ppb ww). Concentrations of Ni in blood were below the LOQ (<0.1 ppb ww) in adult flatback turtles collected in 2006 from Port Curtis (Ikonomopoulou et al., 2011), but surprisingly high levels were reported in blood of live captured and apparently healthy, higher trophic Olive Ridley turtles from Mexico (average 76 ±35 ppb ww). Normal serum levels for most mammalian animals are in the range of 2.0-5.3 ppb ww (Eisler, 1998a), while reference Ni levels in human serum are 0.20 ppb ww (ATSDR, 2005a), although values of 3-7 ppb ww have been reported in whole blood (Eisler, 1998a), and occupationally exposed humans plasma levels can reach >11 ppb ww, but decrease rapidly (Eisler, 1998a). Kidney of green turtles from Gladstone contained average Ni levels of 9.0 ppm ww (range 0.42-26 ppm ww). These concentrations are 1-2 orders of magnitude higher compared to kidney Ni concentrations reported from other green turtles (Aguirre et al., 1994; Sakai et al., 2000a; Sakai et al., 2000b; Lam et al., 2004{Barbieri, 2009 #103; Barbieri, 2009), including Mexico (Talavera-Saenz et al., 2007), and several fold higher compared to the maximum reported levels (average 1.2; range 0.51-1.7 ppm ww; n=14) from green turtles in the Mediterranean off Turkey (Kaska et al., 2004). Kidney Ni levels in green turtles from Gladstone are similar to levels considered high in loggerhead turtles from the Mediterranean off Spain (Torrent et al 2004) while the levels reported for other loggerhead turtles from Japan (Sakai et al., 1995; Sakai et al., 2000b) and the Mediterranean off Spain (Kaska et al., 2004) are considerably lower. In contrast to kidney, liver Ni levels in green turtles from Gladstone (average 0.20; range 0.17-0.23 ppm ww) are an order of magnitude lower compared to those reported in liver of green turtles from Turkey (Kaska et al., 2004) and Mexico (range Mammalian wildlife from uncontaminated habitats usually contain less than 0.1 to about 0.5 ppm dw (or approx. 0.025-0.125 ppm ww) in tissues, while these levels can reach up to 10 ppm dw (or approx. 2.5 ppm ww) in Ni contaminated areas (Eisler, 1998a). Similar levels are reported from birds (0.1-2.5 ppm ww in liver from contaminated areas) (Eisler, 1998a) and lower levels are found in unexposed humans (0.062 ppm dw (or approx. 0.0155 ppm ww) in kidney and 0.005 ppm dw (or approx. 0.0125 ppm ww) in liver) (ATSDR, 2005a). TOXICITY AND EFFECTS Ni is reportedly an essential micronutrient for maintaining health in plants, invertebrates, birds and mammals, including humans (Eisler, 1998a), although the functional important of Ni has not been clearly demonstrated (ATSDR, 2005a). Ni deficiency is primarily manifested in the liver with effects including abnormal liver morphology, oxidative and lipid metabolism, delayed gestation periods and fewer offspring, decreased growth, anaemia, and dermatitis, (Eisler, 1998a; ATSDR, 2005a). The toxicity of Ni is strongly dependent on its chemical and physical forms. Soluble Ni forms are more toxic (e.g. rat single oral dose LD50 = 39 and 136 ppm body weight for Ni sulphate and Ni acetate, 56 Investigation of contaminant levels in green turtles from Gladstone respectively) than less soluble forms (e.g. rat single oral dose LD50 >3,930 ppm body weight for Ni oxide) (ATSDR, 2005a). Generally, hazards to human health are lower when ingested, but can be severe when inhaled with dust, and for some aquatic crustaceans and fish, Ni is more potent at higher pH (Eisler, 1998a). In addition, mixtures of metals (As, Cd, Cu, Cr, Hg, Pb, Zn) containing Ni salts have been shown to be more toxic than predicted on the basis of individual components (Eisler, 1998a). The toxic and carcinogenic effects of Ni compounds are associated with Ni mediated oxidative damage to DNA and proteins and the inhibition of cellular antioxidant defences (Eisler, 1998a). At the cellular levels, Ni interferes with enzymatic functions of calcium, iron, magnesium, and zinc (Eisler, 1998a). Toxic effects of Ni to humans and laboratory animals are documented for respiratory, cardiovascular, gastrointestinal, haematological, musculoskeletal, hepatic, renal, dermal, ocular, immunological, developmental, neurological, and reproductive systems (Eisler, 1998a). The WHO classifies nickel compounds as Group 1 carcinogens and metallic nickel as Group 2B (possible human carcinogens) (Eisler, 1998b). The carcinogenicity of Ni compounds, however, varies significantly with the chemical form, route and duration of exposure and species (Eisler, 1998a). Ni carbonyl is a potent animal teratogen (Eisler, 1998a). In birds, adverse effects are expected in most species at kidney and liver concentrations of >10 ppm dw (approx. 2.5 ppm ww) and >3 ppm dw (approx. 0.75 ppm ww), respectively (Eisler, 1998a). Liver and kidney of birds fed very high Ni containing diets contained <1.0 ppm ww in survivors, but up to 22.7 ppm ww in liver and 74.4 ppm ww in kidney in those that died (Eisler, 1998a). Reduced growth rate in chickens fed with high Ni containing diets produced elevated kidney levels of 4.2 ppm ww versus 0.13 ppm ww in controls (Eisler, 1998a). In humans, serum Ni levels >4.6 ppb ww and plasma Ni levels >11.9 ppb ww are considered elevated while less than 2.6 ppb are considered normal (Eisler, 1998a). Workers accidentally exposed to high Ni levels contained serum concentrations of up to 286 ppb ww one day after exposure in individuals with symptoms, and 50 ppb in those without symptoms (Eisler, 1998a). However, Ni tissue levels do not always accurately predict potential health effects from exposure (ATSDR, 2005a). Rats exposed to high Ni doses, and showing depressed growth, low hematocrit and haemoglobin, and low tissue cytochrome oxidase had elevated Ni concentrations in kidney (40.7 ppm dw, or approx. 10 ppm ww) and liver (4.0 ppm dw, or approx. 1 ppm ww) (Eisler, 1998a). SUMMARY The Ni concentrations in blood of green turtles from Gladstone are lower compared to levels reported for other, albeit higher trophic sea turtle species. Considering the rapid clearance rates of Ni from blood in other organisms blood Ni levels provide information on exposure during the last hours to days prior to sampling, while kidneys and liver represent Ni exposure days to weeks, or longer prior to sampling, respectively. Liver Ni levels appear slightly elevated, but are within the levels observed for green turtles from several other areas. In contrast, kidney Ni concentrations are 1-2 orders of magnitude higher compared to those reported for other green turtles. While there are no toxicological data for sea turtles, the levels observed in kidney are within the tissue based concentrations where adverse effects have been reported for birds and rats. 57 Investigation of contaminant levels in green turtles from Gladstone 5.3.6 Selenium (Se) SOURCES Se is widely but unevenly distributed in the environment and particularly abundant in sulphide minerals of various metals, including iron, lead and copper (Eisler, 1985b). It exists as six stable isotopes, three allotropic forms and five valence states (-2 (selenide), 0 (elemental Se), +2 (selenium), +4 (selenite) and +6 (selenate), which are commonly combined with other substances. Key anthropogenic sources are combustion of coal, various industries, municipal wastes, as well as mining and smelting operations (ATSDR, 2003). Se is primarily obtained as a byproduct of copper refining, was used as a pesticide to control plant pests, and is today extensively used in the manufacture and production of e.g. glass, rubber, metal alloys, and petroleum. However, aside from highly localised contamination, the major source of Se is weathering of natural rock (ATSDR, 2003). Se tends to be present in large amounts where soils have been derived from cretaceous rocks (Eisler, 1985b). The fate of Se is highly complex and depends largely on its form and the conditions of the environment. In the absence of oxygen and in acidic soils, only low amounts of Se enter plants (ATSDR, 2003). Elemental Se and selenides are insoluble and largely unavailable to the biosphere, hydrogen selenide is highly toxic and unstable, while soluble selenates occur in alkaline soils, which are slowly reduced to selenites and may be taken up by plants. Selenites are less soluble and easily reduced to elemental Se; they are often the dominant chemical species in seawater (Eisler, 1985b) TOXICOKINETICS Se is taken up as essential nutrient with food, both as organic (mainly selenomethionine and selenocysteine) and inorganic (mainly selenate and selenite) forms, but higher than normal levels of Se can also be taken up via soil/sediment, associated plants or water at naturally high Se sites or anthropogenically contaminated areas (ATSDR, 2003). Dermal exposure to selenomethionine has been observed, but there is limited information for other forms (ATSDR, 2003). Se is readily absorbed in the gastrointestinal tract of humans and laboratory animals, often to >80% (ATSDR, 2003). After absorption, Se is distributed by the circulatory system to all body organs, the concentrations being often highest in liver and kidney of mammals (ATSDR, 2003), as well as sea turtles (Anan et al., 2001; Storelli et al., 2005). However, accumulation depends on the chemical form and exposure levels, and build up of Se can also occur in blood, lungs, heart, testes, and hair (ATSDR, 2003), as well as carapace in sea turtles (Komoroske et al., 2011). Se has a relatively short biological life (in the order of hours or days to weeks) in various organisms (Eisler, 1985b), and elimination occurs primarily in the urine, but also the faeces, depending on exposure time and level (ATSDR, 2003). However, Se metabolism is significantly modified by interaction with various heavy metals, other chemicals, and numerous physico-chemical factors, and it is thus difficult to meaningfully interpret Se residues in various tissues (Eisler, 1985b). Se exposure can be measured in blood and urine to provide information on recent exposure to high levels. The time of exposure reflected by Se blood levels depends on renewal of red blood cells, which is approximately 120 days in humans (ATSDR, 2003). In sea turtles, Se concentrations in different tissues are often correlated, for example, blood Se levels were significantly correlated with 58 Investigation of contaminant levels in green turtles from Gladstone those in liver, kidney and muscle (van de Merwe et al., 2010) as well as with those in eggs (Guirlet et al., 2008). Se concentrations in mammals are often also correlated with those of other metals, particularly Hg, As and Cd. Similar results have been observed for sea turtles (Komoroske et al., 2011), including in green turtles of this study (p<0.05 for As, Cd, Co, Hg, Mo). This may be the result of Se playing a role in various metal detoxification processes, as has been observed in other species. While Se is typically eliminated rapidly from the body, it can accumulate with age to elevated levels under long or high exposure regimes (ATSDR, 2003), particularly in higher trophic, long-lived, marine vertebrate species (Eisler, 1985b). However, chronically ill and older people have been shown to have lower organ concentrations of selenium than healthy individuals, although it is not clear if this is a cause or consequence of aging or illness (ATSDR, 2003). In green turtles, Se has been observed to be significantly negatively correlated with size (Komoroske et al., 2011), but positive correlations have been reported for hawksbill turtles (Anan et al., 2001). There is evidence that Se biomagnifies in the food chain and maternal transfer has been demonstrated for Se in humans and various animals (ATSDR, 2003) including turtles (Guirlet et al., 2008). EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Blood Se levels in Gladstone green turtles averaged 1900 (range 84-8600) ppb ww. These concentrations are high compared to those considered normal in other animals or humans, but similar levels (average 2400; range 68-9100 ppb ww) have been reported from moribund green turtles in southeast Queensland (van de Merwe et al., 2010), as well as apparently healthy green turtles from two areas in Mexico (average 1600 and 1800; range 30-5700 and 150-4700 ppb ww, respectively) (Labrada-Martagón et al., 2011). Lower Se concentrations were reported in green turtles from San Diego bay in the USA (average 780 ±250 ppb ww) (Komoroske et al., 2011). In blood of herbivorous and omnivorous Amazon river turtles, average Se levels ranged from 164 to 538 ppb ww (Burger et al., 2009). Despite their higher trophic levels, typical Se blood levels in humans range from 59 (New Zealand) to 210 (USA) ppb ww (ATSDR, 2003), and blood Se levels of >40-50 ppb are recommended for cattle and sheep to avoid Se deficiency (Eisler, 2007). In liver and kidney from three necropsied green turtles from Gladstone, Se concentrations averaged 5.4 (range 4.0-7.2) and 1.3 (range 0.62-2.4) ppm ww, respectively. Respective blood Se levels in these animals were below the average in two of these specimens (850 ppb ww) and above the average in the third individual (3,300 ppb ww). Similar to blood, Se levels in kidney and liver are comparable to the upper ranges observed in other green turtles. For example, similar or higher Se concentrations have been reported in kidney and liver of moribund green turtles from southeast Queensland (average 1.7, range 0.29-5.1 and average 4.0, range 0.52-10 ppm ww, respectively) (van de Merwe et al., 2010), stranded specimens from Japan (average 1.0, range 0.41-2.1 and average 1.6, range 0.62- 3.1 ppm ww, respectively) (Anan et al., 2001) and stranded specimens from the Mediterranean (average 0.94, range 0.31-1.4 and average 2.3, range 0.22-4.2 ppm ww, respectively) (Kaska et al., 2004), as well as Hong Kong (average 0.71 and 5.6 ppm ww, respectively) (Lam et al., 2004). The remaining reported average Se levels in kidney and liver of green turtles are, however, 2-3 (kidney) and 3-24 (liver) fold lower. These include samples collected from Australia (e.g. Moreton Bay (Gordon 59 Investigation of contaminant levels in green turtles from Gladstone et al., 1998) and Torres Strait (Gladstone, 1996)), Hawaii (Aguirre et al., 1994), and Oman (Al-Rawahy et al., 2007). Corresponding with the potential for Se to biomagnify through the food chain, higher Se levels have been reported from higher trophic hawksbill turtles from Japan (average of 5.5 and 15 ppm ww in liver and kidney, respectively) (Anan et al., 2001), however, hawksbill turtles from Moreton Bay in Australia contained Se levels comparable to green turtles from Gladstone (maximum 2.5 and 3.7 ppm ww, respectively) (Gordon et al., 1998). Similarly, Se levels in kidney and liver of carnivorous loggerhead turtles from Moreton Bay and the Mediterranean were similar or lower compared to green turtles from Gladstone (e.g. average kidney Se levels: 1.5 and 0.93, average liver Se levels: 2.2 and 2.8, respectively). Mean concentrations of Se in kidneys of coastal birds from highly industrialised areas in Texas, usually vary between 1.7 and 5.6 ppm ww; these concentrations are considered sufficient to possibly impair reproduction in shorebirds (Eisler, 1985b), but levels higher than 2 ppm ww have often been recorded in liver and kidney from higher trophic marine and coastal vertebrates, including birds and mammals (Eisler, 1985b), and Se appears to readily accumulate to elevated levels in reptiles (Grillitsch and Schiesari, 2010). TOXICITY AND EFFECTS Se is an essential micronutrient for humans and many animals, but can be harmful at levels not much higher than those considered beneficial (Eisler, 1985b). It constitutes an integral part of important proteins involved in antioxidant defense mechanisms (e.g. glutathione peroxidases), the thyroid hormone metabolism and redox control of intracellular reactions (ATSDR, 2003). Similar to vertebrates, it has been suggested that Se similarly plays a pivotal role at the beginning of embryonic development in reptiles, whereby Se might affect the activation, synthesis and release of thyroid hormones (Guirlet et al., 2008). Se deficiency may in part underlie susceptibility to cancer, arthritis, hypertension, heart disease, and possibly other diseases, including high embryonic mortality, anemia, poor growth and reproduction, hepatic necrosis, hair loss and sterility (Eisler, 1985b; ATSDR, 2003). On the other hand, exposure to Se above its beneficial levels can affect growth and reproduction in various organisms (Eisler, 1985b), and may cause cancer (ATSDR, 2003). Acute poisoning can result in nausea, vomiting and diarrhea in humans (ATSDR, 2003), and a range of symptoms have been observed in livestock (e.g. abnormal movements, laboured breathing, bloating, lethargy and death), with post-mortems indicating many pathological changes in the heart, lungs, rumen, liver, kidney and other organs (Eisler, 1985b). Chronic selenosis may be induced by dietary Se levels 10-20 times the norm (ATSDR, 2003); signs include skin lesions, lymph channel inflammation, loss of hair and nails, anaemia, enlarged organs, fatigue, and dizziness (Eisler, 1985b). Chronic doses around 5 times higher the norm may cause cardiovascular, gastrointestinal, haematological, hepatic, dermal, immunological, neurological and reproductive effects (Eisler, 1985b). A wide variety of interactions of Se have been demonstrated with essential and nonessential elements, vitamins, and xenobiotics, including reduction of toxicity of many metals such as Hg, Cd, Pb, Ag and to some extent, Cu. The degree to which Se is toxic, however, can be influenced by these interactions, but they are complex and still poorly understood (ATSDR, 2003). 60 Investigation of contaminant levels in green turtles from Gladstone Chicken embryos are among the most sensitive to Se, and deformed embryos are observed at concentrations of 6-9 ppm in feeds (Eisler, 1985b). A field study on wild birds (n=347) showed high incidences (40 and 20%, respectively) of dead embryos and chicks with severe external anomalies in animals from ponds with very high Se levels in water (300 ppb). The liver of these birds contained 19- 130 ppm dw (approx. 4-29 ppm ww). It was concluded that Se was the probable cause of poor reproduction and developmental abnormalities in these animals, due to interference with their reproductive processes (Eisler, 1985b). For snakes, it was estimated that individuals with >1700 ppb ww Se in blood would exceed liver toxicity thresholds recommended for other oviparous vertebrates and be at risk of reduced reproductive success (Hopkins et al 2005). In green turtles, Se in blood (average 780 ppb ww) was found to be correlated with several health markers, however, interpretation was confounded by covariance with turtle size (Komoroske et al., 2011). In humans, Se blood levels of 55-200 ppb were correlated with grasping power, blood pressure, serum cholesterol, triglycerides, and lipoproteins in humans (ATSDR, 2003). The NOEL for chronic selenosis in humans is based on a blood Se level of 1054 ppb ww (ATSDR, 2003). In cows, an association of cystic ovaries with blood selenium concentrations >108 ppb was reported (ATSDR, 2003) and other adverse effects in mammals, including body weight loss, were associated with concentrations in erythrocyte >2300 ppb ww and plasma >2800 ppb ww (Eisler, 2007). SUMMARY Selenium appears to be readily accumulated to elevated levels in many reptile species, including sea turtles. Blood and tissue Se concentrations in green turtles from Gladstone are, however, among the upper ranges reported from other green turtles and thus appear to be elevated. In addition, the Se levels in green turtles from Gladstone (as well as green turtles from elsewhere) are above those considered harmful in many vertebrates, including reptiles, although reptile specific data are limited. 61 Investigation of contaminant levels in green turtles from Gladstone 5.3.7 Silver (Ag) SOURCES Silver is a naturally but relatively rare occurring element. It exists in several oxidation states, most commonly as elemental Ag (0) and monovalent ion (+1). Silver is extracted mainly from argentite ore (by cyanide, zinc reduction, or electrolytic processes), and is often recovered as byproduct from smelting of nickel ores, lead-zinc and porphyry copper ores, platinum and gold deposits (Eisler, 1996). Secondary sources include scrap generated in the manufacture of silver containing products and electrical products, old film and photoprocessing wastes or batteries. Elevated silver concentrations in biota can occur in the vicinity of sewage outfalls, mine waste sites, smelting operations, manufacture and disposal of photographic and electrical supplies and coal combustion (Eisler, 1996; Howe and Dobson, 2002). Major anthropogenic releases to the aquatic environment include mining tails, soil erosion, urban runoff, sewage treatment plants and electroplating industries (Eisler, 1996). The fate of Ag in soils, sediments and water is controlled mainly via sorption processes, and sediments may be a significant source of Ag to the water column. Ag can be highly persistent in sediments under high pH and salinity conditions (Howe and Dobson, 2002). In water, Ag exists mainly as metallo-organic complexes or adsorbed to organic materials, including marine algae, which have been shown to have high bioconcentration factors (commonly up to 66,000) (Eisler, 1996). With increasing salinity in brackish and marine waters, sorption to particles decreases and concentrations - of chloro complexes (e.g. silver chloride (AgCl), silver chloride ion (AgCl2 )) increases, which retain some silver in the dissolved form. Thus, relatively small inputs can substantially increase dissolved Ag loads in these environments (Eisler, 1996). TOXICOKINETICS Organisms can be exposed to Ag via inhalation and ingestion, but Ag can also move across mucous membranes and broken skin (Eisler, 1996). After exposure, Ag is mainly transported in the protein fraction of blood plasma as silver albuminate or silver chloride (Eisler, 1996). Accumulation, retention and elimination of Ag differ widely among species. In general, the majority of Ag is excreted rapidly (in the order of hours to days/weeks) in faeces with <1% of intake absorbed and retained in tissues, primarily the liver, via precipitation of insoluble silver salts. But Ag may also accumulate in the spleen, muscles, kidney, skin and brain (Eisler, 1996). Tissue concentrations of Ag are related to the dose, chemical form and route of exposure. Intestinal absorption in rodents, canids and primates range from 10-50% (ATSDR, 1990). Blood is an appropriate marker for recent Ag exposure (over days to weeks) prior to sampling (ATSDR, 1990). Silver has been shown to bioaccumulate in mammalian tissues (Eisler, 1996), but food chain biomagnification in aquatic systems is not considered likely at background concentrations (Eisler, 1996). EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Ag concentrations in blood of green turtles from Gladstone ranged from 0.011 to 7.1 ppb ww (average 0.66 ppb ww), although the majority of blood samples contained Ag levels <2.0 ppb ww. The only identified published data on Ag in blood of green turtles reported approximately two times 62 Investigation of contaminant levels in green turtles from Gladstone higher average Ag levels (1.6 ppb ww (±0.53 SE; n=30)) from a highly urbanised and generally contaminated estuary in San Diego (Komoroske et al., 2011). In Kemp’s ridley sea turtles, however, average blood Ag levels were reported at 0.94 (range 0.042-2.7) ppb ww (Kenyon et al., 2001). In humans, blood Ag levels in unexposed humans are very low (<0.1-0.2 ppb (Armitage et al., 1996)). In highly and chronically exposed humans (chemical manufacturing workers) average blood Ag levels were 11 ppb ww (ATSDR, 1990) and 0.1-23 ppb ww (Armitage et al., 1996). Relatively high concentrations of Ag were observed in liver of green turtles from Japan (0.99 ppm ww; 0.21-2.9 ppm ww); kidney contained considerably lower levels (0.0057 ppm ww; 0.00059-0.023 ppm ww) (Anan et al., 2001). Similar levels were reported from liver and kidney of green turtles from South China (0.78 ±0.65 SE and 0.0070 ±0.0030 SE ppm ww, respectively) (Lam et al., 2004). In the present study, Ag could not be analysed in tissues of green turtles due to matrix interferences. Normal background levels in liver of most organisms are generally several orders of magnitude lower compared to those reported for green turtles from Japan and China (e.g. 0.0044-0.14 ppm ww in various birds, 0.006 ppm ww in humans, 0.16-0.21 in seals and polar bear ppm ww) (Eisler, 1996). Maximum concentrations, collected from contaminated areas, range from approximately 0.33 ppm ww in liver of marine mammals, 0.44 ppm ww in trout liver, 9.7 ppm ww in bird liver (Eisler, 1996; Howe and Dobson, 2002). TOXICITY AND EFFECTS Silver has no known biological function in the body of mammals, and is (as Ag+) one of the toxicologically most potent metals to aquatic organisms (Eisler, 1996). The acute toxicity to aquatic species varies depending on the chemical form and correlates with the availability of free ionic silver Ag+, which is the most toxic species (Eisler, 1996). Soluble silver salts are in general more toxic than insoluble salts, and in water, the soluble ion Ag+ is the form of most concern. More recently toxicity of silver nanoparticles has become an issue of concern because nano silver is widely a applied antibacterial in consumer products. The toxic species of nano silver is also the Ag+, which is set free intracellularly from the ingested nanoparticles. Long-term, chronic exposure to silver and its compounds by birds and mammals have been associated with induction of sarcomas, cardiac enlargement, vascular hypertension, hepatic necrosis, anemia, lowered immunological activity, altered membrane permeability, kidney pathology, enzyme inhibition, and growth retardation (Eisler, 1996). In aquatic environments ionic or free Ag have been shown to interfere with calcium metabolism in frogs (resulting in deterioration of muscle fibres) and with sodium and chloride uptake in gills of fish (Eisler, 1996). There is limited data on the toxic threshold of Ag in avian or mammalian wildlife, and no information for reptiles. Adverse effects of Ag on poultry occur at 1.8 ppm ww (whole egg), 10 ppm ww in copper-deficient diets and 200 ppm ww in copper adequate diets (Eisler, 1996). Death in sensitive mammalian species occurs at 14-20 ppm body weight (intraperitoneal injection). SUMMARY The average blood Ag levels in Gladstone green turtles are similar or lower compared to other green turtles (from relatively contaminated areas) and sea turtles. However, some individuals from Gladstone contained higher levels of Ag. Considering data from other organisms, the blood Ag 63 Investigation of contaminant levels in green turtles from Gladstone concentrations in some green turtles from Gladstone may be above background, however, normal background levels in sea turtles are unknown. No blood based Ag effect concentrations were identified in the literature and only few tissue based effect levels are available. However, Ag could not be quantified in tissues of the present study. Considering the limited comparable data for blood in marine turtles, and lack of blood based effect levels, it is not possible to assess whether exposure to Ag presents a hazard to the study population, but some individuals may contain levels that are elevated. 64 Investigation of contaminant levels in green turtles from Gladstone 5.3.8 Vanadium (V) SOURCES Vanadium is a naturally occurring element present in soil, water and air (ATSDR, 2009). It most commonly exists in the oxidation states of +3, +4 and +5 and various inorganic forms, e.g., vanadium pentoxide (V2O5), sodium metavanadate (NaVO3), sodium orthovanadate (Na3VO4), vanadyl sulphate (VOSO4), and ammonium vanadates (NH4VO3). V is found mostly in fossil fuel such as coal, oil shale, tar sands and crude oil and in numerous minerals such as bauxite and magnetite. Releases of V to the environment are primarily associated with oil refineries and power plants via combustion of petroleum crude oils and coal, and may also occur from mining, clay and metallurgical industries, municipal sewage and fertilisers (ATSDR, 2009). Upon entering the marine environment the main fraction of V is deposited and adsorbed to sediments and only a small fraction (0.001%) is estimated to persist in soluble form (Byerrum et al., 1974). TOXICOKINETICS Key pathways for marine organism exposure to vanadium are ingestion of soil/sediments and food. After oral exposure, only a small fraction of vanadium is absorbed through the gastrointestinal tract of animals (up to 17% in laboratory animals; approx. 3-20% in humans) (Costigan et al., 2001). Dermal adsorption is thought to be minimal due to the low lipid/water solubility of vanadium. Vanadium is distributed in blood and primarily to bone tissue with lesser amounts to kidney and liver (Costigan et al., 2001). Blood, as well as organ concentrations have been found to decline rapidly to trace levels within days upon cessation of exposure in mammals (ATSDR, 2009), via urine as the primary elimination route (Costigan et al., 2001). Reported elimination half-lives in various tissues and organisms are in the order of 1-14 days (ATSDR, 2009) (Costigan et al., 2001) (Miramand et al., 1992). There is no evidence of long-term accumulation in humans or marine organisms and food chains (Costigan et al., 2001). Bioconcentration factors for primary consumers in the marine food chain have been reported to range from 40 to 150 (Miramand et al., 1992; Costigan et al., 2001). Considering the toxicokinetics of vanadium in organisms, blood and urine are the most reliable indicators on the level of exposure in mammals and fish (Costigan et al., 2001). Based on the relatively rapid clearance of V from blood (in the order of days), V blood levels inform on recent exposure regimens. EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Vanadium concentrations in blood of green turtles from Gladstone ranged from 3.5 to 38 ppb ww with an average concentration of 12 ppb ww (SD 9.1). No published data is available on vanadium in blood of any sea turtle species, however, average levels are approximately 4 times lower in blood from live captured green turtles in Moreton Bay (average 2.8; 0.29-8.5 ppb) (unpublished data from 2011; n=9). Compared to levels in human blood (average background: <0.05 ppb ww; (Byrne and Kosta, 1978; Sabbioni et al., 1996; Nixon et al., 2002), these concentrations would be considered elevated, and are in the order of those observed for occupationally exposed cohorts (average 33 ppb ww) (Lin et al., 2004). However, marine organisms, including plants, invertebrates and seafood generally contain higher levels of vanadium than their terrestrial counterparts (Costigan et al., 2001), although reports on concentrations in blood from marine species are limited and background levels 65 Investigation of contaminant levels in green turtles from Gladstone for turtles are unknown. The maximum levels present in green turtles from Gladstone compare to the maximum V levels reported in blood from ospreys from relatively polluted Chesapeake Bay and Delaware Bay (range To facilitate further comparisons, liver and kidney (in addition to blood) were analysed from three euthanized green turtles from Gladstone. Vanadium levels in these tissues (0.23-0.79 ppm ww in liver and 0.23-0.34 ppm ww in kidney) are comparable to those in stranded or moribund green turtle liver and kidney from Hawaii and Japan, while approximately one order of magnitude lower V levels were reported in liver and kidney of stranded green turtles from Hong Kong and hawksbill turtles from Japan. These levels are several orders of magnitude higher than typical levels in meat, poultry and fish (around 0.1 ppt; range 0-11.9 ppt)(ATSDR, 2009) as well as those typically found in most marine organisms (generally in the order of ppb (Michibata, 2012), <0.01 ppm ww in marine mammals (Mackey et al., 1996) or fish (2.9-74 ppb ww; (Sepe et al., 2003; ATSDR, 2009). Liver tissue concentrations in turtles are, however, comparable to chronically elevated liver concentrations in common dolphins affected by high vanadium release via the Erika oil spill off the coast of France in 2000 (average 0.11; range 0.01-0.32 ppm ww, (Ridoux et al., 2004)), and approach the highest V concentrations recorded in some marine mammals (up to 1.6 ppm ww in liver of harbour seal (Saeki et al., 1999; Eisler, 2010). TOXICITY AND EFFECTS Although there is some evidence to suggest that vanadium is an essential nutrient, a functional role has not been established. It acts as phosphate analogue and as such interferes with various ATPases, phosphatises and phosphate-transfer enzymes; additionally, it has been shown to have insulin- mimicking properties and the ability to induce cell proliferation, and IARC classifies vanadium pentoxide as possibly carcinogenic (Group 2B) (IARC, 2009). Primary targets of toxicity following oral vanadium exposure include the gastrointestinal tract, haematological system and developing organism. Depending on the dose, effects in humans and laboratory animals exposed to vanadium can include decreased number of red blood cells, increased blood pressure, diarrhoea, neurological effects (e.g. decreased fetal growth, skeletal malformations) and lung cancer (through vanadium pentoxide). Clinical signs of toxicity include lethargic behaviour, paralysis, lacrimation and diarrhoea, and histological examination revealed necrosis of liver cells and cloudy swelling of renal tubules (Yao and Zhang, 1986; Costigan et al., 2001). In birds, liver V levels approaching 0.5 ppm ww have been suggested to alter lipid metabolism in laying females (White et al., 1980; Eisler, 2010). Similarly, V concentrations of around 0.4 ppm ww (whole body) have been reported to elicit effects in fish (reduced growth in juvenile rainbow trout) (Hilton and Bettger, 1988). In mammalian species, Lethal Doses (LD50) for sodium metavanadate range from 10-137 (rats) to 23-31 (mice) ppm/day (oral; 14 days) (Llobet and Domingo, 1984; Sun, 1987; Costigan et al., 2001; ATSDR, 2009). Minimal risk levels (MRLs) have been established for oral exposure to vanadium (e.g. intermedium duration (15-364 days) exposure oral MRL: 0.01 ppm/day). SUMMARY Considering V levels reported for sea turtles, and other wildlife and organisms, the concentrations detected in green turtles from Gladstone appear to be relatively high in blood, although information 66 Investigation of contaminant levels in green turtles from Gladstone on baseline levels in sea turtles are lacking. Tissue levels of green turtles from Gladstone are within or near the upper ranges reported from other green turtles and other marine wildlife. The levels present in blood from green turtles in Gladstone may indicate relatively recent exposure to elevated levels in food/sediment and/or water, but species specific toxicokinetics (e.g. absorption, long half- lives, bioaccumulation) are unknown. While limited information exists on tissue based effect concentrations across any species, and none is available for reptiles, the V tissue levels in green turtles from Gladstone are similar to those shown to elicit adverse effects in other wildlife (birds, fish). 67 Investigation of contaminant levels in green turtles from Gladstone 5.3.9 Zinc (Zn) SOURCES Zinc is among the most common elements and is naturally present in air, soil, water and food. It occurs as two common oxidation states (Zn(0) and Zn(+2)). A large proportion of zinc also enters the environment as a result of mining, purification of zinc, lead, and cadmium ores, steel production, coal burning, and burning of wastes (ATSDR, 2005b). Waste streams from metal manufacturing and zinc chemical industries, domestic waste-water and run-off from soil can discharge zinc into waterways. Sludge and fertilisers can also contribute to increased zinc levels in soil (ATSDR, 2005b). Zinc can combine with other elements, such as chlorine, oxygen, and sulfur to form organic or inorganic zinc compounds. In the aquatic environment, zinc occurs primarily in the +2 oxidation state, as the hydrated form of the divalent cation. Sorption is the dominant reaction, resulting in enrichment of zinc in suspended and bed sediments. However, a small proportion may remain either dissolved in the water or suspended with sediments. The levels of dissolved zinc in water can increase with the acidity of the water (ATSDR, 2005b). TOXICOKINETICS The major zinc exposure pathways for organisms are ingestion of food and contaminated soils/sediments, although exposure via water is a key pathway for fish and other organisms may be exposed via drinking water; inhalation exposure may also occur in contaminated areas (ATSDR, 2005b). Dermal exposure can occur, but absorption studies are limited (ATSDR, 2005b). Absorption of zinc from the gastrointestinal tract is homostatically regulated and ranges from 20 to 30% under normal physiological conditions (ATSDR, 2005b). A number of factors can influence the absorption, including the chemical form of zinc, the presence of inhibitors (e.g. calcium, phosphorus, dietary fiber) and enhancers (amino acids, picolinic acid) in the diet. After absorption, zinc increases most rapidly in blood (peaking within hours) and bone after exposure. In an initial phase after absorption, zinc is concentrated in the liver, and subsequently distributed throughout the body with major storage sites being the liver, pancreas, bone, kidney and muscle (ATSDR, 2005b). Highest concentrations are typically present in muscle, bone, gastrointestinal tract, kidney, brain, and skin. Elimination is predominantly via the urine and feces. Zinc concentrations in humans increase in several organs with age, including the liver and kidney, although levels in the kidneys peak at approximately 40-50 years of age and then decline. Zinc does not concentrate in fish tissues with exposure to elevated concentrations (ATSDR, 2005b) and has not been observed to biomagnify in reptiles (Grillitsch and Schiesari, 2010). Blood is a commonly used marker for recent zinc exposure (ATSDR, 2005b). In mammals, approximately two-thirds of zinc in plasma is loosely bound to albumin, which represents the metabolically active pool of zinc (ATSDR, 2005b). However, since zinc levels can be affected by dietary deficiency and cell stress, these result may not be directly related to current zinc exposure (ATSDR, 2005b; Eisler, 2010). 68 Investigation of contaminant levels in green turtles from Gladstone EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Zn blood levels in turtles from Gladstone averaged 8,400 ppb ww (range 3,800-12,000 ppb ww). Similar, or higher levels have been observed in blood of green turtles from Mexico (average 14,000; range 490-20,000 ppb ww) (Labrada-Martagón et al., 2011), moribund specimens from southeast Queensland (average 7,900; range 3,500-12,000 ppb ww) (van de Merwe et al., 2010) and leatherback turtles from French Guiana (average 11,000 ppb ww) (Guirlet et al., 2008). Similarly high Zn levels were also reported in blood of Kep’s ridley sea turtles from the Gulf of Mexico (average 7,500; range 3,280-18,900 ppb ww) (Grillitsch and Schiesari, 2010). In contrast, Zn levels in blood of flatback turtles from Curtis Island were considerably lower (average 150; range 98-210 ppb ww) (Ikonomopoulou et al., 2011). Substantially lower mean Zn concentrations are typically reported in whole blood of humans from regions with low pollution (6.0-7.0 ppb ww), while up to 4,000 ppb ww were have been detected in whole blood of children in highly industrialised urban areas of India (ATSDR, 2005b). In kidney and liver of turtles from Gladstone, Zn concentrations averaged 33 and 46 ppm ww (range 20-40 and 41-51 ppm ww), respectively. While these levels lay within the upper ranges of those reported previously from sea turtles, they are comparable to stranded specimens in Moreton Bay (average 21 and 40 ppm ww in kidney and liver, respectively) (Gordon et al., 1998), and moribund specimens from southeast Queensland (average 29 and 36 ppm ww, respectively) (van de Merwe et al., 2010). Similar Zn levels in kidney and liver have also been reported for several other green turtles around the world, e.g. Japan (average 34 and 58 ppm ww, respectively) (Sakai et al., 2000a), a captive specimen from Hawaii (32 and 38 ppm ww, respectively) (Aguirre et al., 1994), and specimens from Hong Kong (average 17 and 28 ppm ww, respectively ) (Lam et al., 2004). Zn concentrations in marine birds from New Zealand are typically around 88 ppm ww in liver. Elevated Zn liver levels of 890 ppm dw (approx. 220 ppm ww) have been reported in liver of heron from Rhode Island (Eisler, 2010). Mallards exposed to high levels of zinc 450 ppm body weight contained 217 ppm dw (approx. 54 ppm ww) in liver and 79 ppm dw (approx. 20 ppm ww) in kidney (Eisler, 2010). Zn concentrations in tissues of marine mammals are usually less than 210 ppm dw (approx. 53 ppm ww), but can range from 1.5-1390 ppm dw (or approx. 0.38-348 ppm ww). In human kidney and liver, background zinc levels are typically around 47 and 23 ppm ww, respectively. In exposed people, kidney and liver levels of 60 and 30 ppm ww, respectively, have been reported. TOXICITY AND EFFECTS Zinc is a trace mineral nutrient, and required in all animals for the function of several metalloenzymes, and as such is required for normal nucleic acid, protein, and membrane metabolism, as well as cell growth and division. Zinc deficiency can cause dermatitis, anorexia, growth retardation, impaired reproductive capacity, impaired immune function, and depressed mental function (ATSDR, 2005b). Chronic exposure to zinc has been shown to decrease the absorption of copper from the diet, resulting in development of copper deficiency. At low doses and intermediate exposure durations, subclinical changes in copper-sensitive enzymes can occur. Higher exposure levels result in more severe symptoms of copper deficiency, including anaemia, and lesions in liver, pancreas and kidneys, 69 Investigation of contaminant levels in green turtles from Gladstone infertility, developmental effects and skin irritations (ATSDR, 2005b). Oral exposure to zinc may also impair immune and inflammatory responses (ATSDR, 2005b). The oral LD50 in rats and mice for several zinc compounds range from 186 to 623 ppm/day (ATSDR, 2005b). Zinc acetate was the most lethal compound in these laboratory animals, respectively. Zn blood serum levels of 45,000 ppb were reported in a crocodile diagnosed with zinc poisoning; blood Zn levels dropped to 30,000 ppb after 18, and to 4,000 ppb after 39 days of treatment (Eisler, 2010). Similarly, Zn poisoned birds frequently contain 16,000 ppb in plasma and 75-156 ppm dw (approx. 19-39 ppm ww) in liver, versus <2 ppb and 21-33 ppm dw (approx. 5.3-8.3 ppm ww) in controls, respectively (Eisler, 2010). Tissue residues of Zn are not yet reliable indicators of contamination in mammals, although Zn intoxication is documented in terrestrial mammals when Zn exceeds 274 ppm dw (approx. 68 ppm ww) in kidney, and 465 ppm dw (appox 116 ppm ww) in liver (Eisler, 2010). Comparable data for marine mammals could not be identified, and zinc concentrations in marine mammals frequencly exceed 100 ppm ww without apparent damage to the animal (Eisler, 2010) SUMMARY The Zn levels in green turtles from Gladstone generally lay within the upper ranges, but are comparable to those reported for several other sea turtles from around the world. On the other hand, levels associated with Zn poisoning in crocodiles, birds or mammals are only slightly higher compared to the maximum concentrations detected in Gladstone green turtles, and chronic effect levels are unknown. However, it appears that sea turtles frequently accumulate elevated levels of Zn, and it is not possible to assess whether this may be a concern to these populations. 70 Investigation of contaminant levels in green turtles from Gladstone 5.3.10 Dioxins and PCBs SOURCES Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) comprise two different groups of tricyclic, aromatic ethers with 210 possible congeners. PCDD/Fs are produced as unintentional by-products of various combustion and industrial processes, e.g. during pesticide manufacture, bleaching of paper pulp and waste incineration. In addition, current-use pesticides may contain elevated levels of dioxins as impurities (Holt et al., 2010). Dioxins are released from these sources as complex mixtures and while each congener has slightly different physico-chemical properties, all PCDD/Fs display high lipophilicity and chemical stability (Mackay et al., 2006). Polychlorinated biphenyls (PCBs) are thermally stable, good insulators, and are relatively inflammable; hence they have been used widely as flame retardants, lubricants, coolants, and as dielectric fluids (NAS, 2001; EC, 2006). Intentional manufacture of PCBs has ceased in many parts of the world; however, PCBs remaining within stock piles still have the potential to enter the environment. Commercial PCB sources consist of complex mixtures of individual PCBs (up to 209 congeners), resulting in complex mixtures of these lipophilic compounds in the environment. The spatial distribution of PCCD/Fs and PCBs is related to the source location, type of emission source, physico-chemical properties and environmental processes. These compounds have the potential for dispersal throughout the environment, usually in association with mobile particles such as organic matter, for example via atmospheric transport or with river systems (Eitzer, 1993; Pearson et al., 1997; Gaus et al., 2001). Consequently, dioxins and PCBs can be found at trace levels in most environmental matrices (air, soil and water) (Wagrowski and Hites, 2000), and in particular, are known to accumulate in the marine system. TOXICOKINETICS Generally, exposure to PCDD/Fs and PCBs occurs mainly via ingestion. For herbivorous marine turtles, contaminated seagrasses, as well as incidental consumption of sediment bound PCDD/Fs and PCBs, represent the dominant uptake routes (Haynes et al., 1999; Gaus et al., 2004). After exposure, these highly lipophilic compounds can be found in most tissues with the highest quantities in the liver and fat (adipose tissue). Although some elimination can occur via faeces and to a lesser extent urine, body fat and possibly the liver can store PCDD/Fs and PCBs for years to decades (ATSDR, 1998, 2000). Absorption efficiency of PCDD/Fs and PCBs across the gastrointestinal tract vary depending on the physico-chemical properties of the congeners and generally increases with decreasing degree of chlorination (Niimi, 1996). The smaller congeners tend to be the more toxic congeners, and their accumulation can lead to increased tissue toxicity levels compared to surrounding sediments (Broman et al., 1992). Concentrations of mixtures of PCDD/Fs and PCBs are commonly reported on a toxic equivalency (TEQ) basis. Toxic equivalence factors (TEF), relative to the toxicity of tetra-dioxin (TCDD), have been assigned to 17 PCDD/F congeners and 12 PCBs. TEFs are not available for reptiles, and assessments for turtles rely on TEFs determined for mammalian and avian species. 71 Investigation of contaminant levels in green turtles from Gladstone Due to their lipophilicity and resistance to metabolism, PCDD/Fs and PCBs can bioaccumulate in biota, biomagnify through the food web, and transfer to offspring via gestation and/or lactation (Borgå et al., 2001; Boon et al., 2002; Falandysz et al., 2002). Lipid-normalised concentrations of PCBs in marine turtle blood have been shown to significantly correlate to levels found in matched fat samples, indicating blood to be a suitable marker for exposure to PCDD/Fs and PCBs (Keller et al., 2004a). Lipid-normalised PCDD/F and PCB concentrations in green turtles have been shown to closely reflect sediment contamination (Hermanussen et al., 2006). EXPOSURE CONCENTRATIONS IN GLADSTONE GREEN TURTLES Middle bound TEQs in blood of juvenile green turtles from Gladstone averaged 19 ppt lw (range <7.1- 39 ppt lw). These concentrations are comparable to those reported for juvenile green turtles from Shoalwater (average 27; range 24-29 ppt lw; n=2) and eastern Moreton Bays (average 17; range 6.0- 22 ppt lw) (Hermanussen, 2009). Higher TEQ levels have been reported from juvenile green turtles in Hervey Bay (average 33; range 9.6-71) and western Moreton Bay (average 78; range 37-120 ppt lw) (Hermanussen, 2009). Blood from the adult specimen in Gladstone contained considerably higher TEQ levels compared to juveniles (130 ppt lw), which is comparable to the upper concentrations reported from Hervey Bay and Western Moreton Bay (Hermanussen, 2009). It is interesting to note that the major proportion of this TEQ was derived from PCDD/Fs (120 ppt lw) while PCBs only contributed a minor fraction (7.9 ppt lw). As dioxins and PCBs bioaccumulate in organisms over their lifespan, these results suggest adult turtles may be exposed to chronically elevated levels of dioxins; however, further data from adult turtles would be required to evaluate chronic exposure in this region. No other TEQ levels have been reported for sea turtle blood or tissues. In dugongs from Queensland, TEQ levels were surprisingly elevated compared to many other marine biota, even higher trophic animals, ranging from 5-140 and 0.92-55 ppt lw in adult males and females, respectively (Gaus et al., 2004) TOXICITY AND EFFECTS PCDD/Fs and dioxin-like PCBs primarily exert toxic effects in animals by binding to the aryl hydrocarbon receptor (Ah receptor), and the ligand-activated Ah receptor acts as a transcription factor for the regulation of genes (Hahn, 1998). Limited information is available on the effect of dioxins and PCBs on reptiles; although field based epidemiological studies have indicated reproductive and developmental effects in freshwater turtles (Bishop et al., 1998; De Solla et al., 1998), and possible immune suppression in marine species (Keller et al., 2004b; Keller et al., 2006). The effects of PCDD/Fs and dioxin-like PCBs on humans and other mammals, including marine mammals, are well established. Effects include chloracne, liver and kidney damage, behavioural alterations, reproductive and developmental abnormalities, reduced fertility, tetragenicity, endocrine disruption and immune system suppression (ATSDR, 1998, 2000). TCDD has also been classified as a Group 1 carcinogen by IARC. Lowest observed adverse effect levels (LOAELs) of dioxins and PCBs are reported on a body burden basis – TEQ per kilogram of body weight (bw). LOAEL thresholds in mammals range from biochemical effects at 3 ng kg-1 bw which may or may not result in adverse health effects, immunological effects leading to increased viral sensitivity at 10 ng kg-1 bw, 72 Investigation of contaminant levels in green turtles from Gladstone developmental neurotoxicity at 21 ng kg-1 bw, and reproductive toxicity resulting in reduced sperm count at 28 ng kg-1 bw (WHO, 1998; USEPA, 2003). For birds, one of the most sensitive species is the domesticated chicken with a LOAEL of 9 ng kg-1 bw for developmental toxicity resulting in cardiac malformation (USEPA, 2003). PROBABILISTIC RISK ASSESSMENT A probabilistic approach can be used to estimate the proportion of the Gladstone turtle population at risk of adverse effects based on the reported PCDD/F and PCB blood levels. TEQ data (on a lipid basis in blood) for the turtle samples were transformed to body burdens by multiplying TEQ by the expected total body lipid percentage. The expected population distribution of TEQ body burdens was then determined using risk modelling software (Crystalball 2000 Decisioneering Inc.) and compared to LOAELs in mammals and avian species (in the absence of reptile-specific dose-response toxicological information). Total green turtle lipid percentage was assumed to vary uniformly between 4 and 12% for foraging benthic-phase animals not undergoing breeding migration, consistent with previously reported exposure assessments (Hermanussen, 2009). As only one adult blood sample was obtained, data from the 21 juvenile turtles were assessed separately to the adult. Lognormal frequency distributions are commonly observed for environmental pollutant concentrations in animals (Ott, 1990), and therefore lognormal distributions were fitted to lipid normalised TEQ concentrations for juveniles using mammalian and avian TEFs separately, and on both a middle and upper bound basis. Assuming that the juvenile turtles sampled in this study are representative of the Gladstone juvenile turtle population, the likelihood (% of population) of TEQ body burdens at or above levels where effects have been observed were determined. At middle bound TEQ, up to 6.6% of the juvenile population may be above the LOAELs where biochemical effects are expected in mammals; when considering the more conservative upper bound TEQ basis, this percentage increases to 29% (Figure 3). On an upper bound TEQ basis, up to 5% of the population may also be above the LOAEL for developmental toxicity effects in avian species (Figure 3). In contrast to juveniles, higher TEQs were observed in the adult blood sample. Probabilistic assessments cannot be performed; however, based on the expected total body lipid percentage (4 – 12%) the estimated body burden is in the range of 5.0-15 ng kg-1 bw (middle bound) and 5.6-17 ng kg-1 bw (upper bound) assuming mammalian TEFs. Using avian TEFs, the comparable ranges would be 4.7-14 ng kg-1 bw (middle bound) and 5.6-17 ng kg-1 bw (upper bound). This adult’s predicted body burden is in excess of the LOAEL for biochemical effects in mammals, and may exceed the LOAELs for immunological effects and developmental effects in mammals and birds, respectively. It is important to note that this risk assessment does not incorporate reptile-specific sensitivity to PCDD/Fs and PCBs. When the toxicity threshold for a different species (but from the same class) is used for risk assessment, the uncertainty is usually offset by dividing the LOAEL by a safety factor of 10 (WHO, 1998). In the case of this study, the uncertainty may be higher due to the class-difference between the measured LOAELs (mammalian and avian) and species of interest (reptilian). Safety factors have not been applied in the above assessment. 73 Investigation of contaminant levels in green turtles from Gladstone A) B) Figure 4 Probabilistic distributions of body burden (ng kg-1 bw (x-axis)) in juvenile green turtles from Gladstone; A) derived using mammalian TEFs and B) derived using avian TEFs. The blue portion of the graph depicts the fraction of the juvenile population at or above the LOAEL of A) 3 ng kg-1 bw for biochemical effects in mammals (29%) and B) 9 ng kg-1 bw for developmental toxicity in chickens (5.0%). 74 Investigation of contaminant levels in green turtles from Gladstone SUMMARY Based on limited comparable data for PCDD/Fs and PCBs in turtles, blood levels in juvenile turtles from Gladstone appear to be similar compared to green turtles from relatively low impacted areas in Queensland. The adult specimen, however, contained elevated TEQ levels, comparable to the highest concentrations identified for green turtles and dugongs; however, only one adult specimen was sampled from Gladstone. Probabilistic risk assessment for the juvenile population suggests that low proportions of the population may have body burdens in excess of LOAELs for biochemical effects in mammals, which may or may not result in adverse health effects (6.6-29%) and developmental toxicity in birds (0-5.0%). It should be noted, however, that no reptile-specific LOAELs are available and no uncertainty factors have been applied to the mammalian and avian LOAELs used. For the one adult turtle sampled, its estimated body burden was in excess of the LOAEL for biochemical effects in mammals, and exceeds the LOAELs for immunological effects and developmental effects in mammals and birds, respectively. 75 Investigation of contaminant levels in green turtles from Gladstone 6.0 CONCLUSIONS AND RECOMMENDATIONS The results of this study show that exposure concentrations for several organic contaminant groups and a range of metals are relatively low and unlikely to present a substantial hazard to the study population; these include bioaccumulative pesticides, organotins, perfluorinated compounds, brominated flame retardants, aluminium (Al), iron (Fe), manganese (Mn), and zinc (Zn). A number of contaminant groups were detected at levels that suggest elevated exposure may have occurred for a proportion of the green turtles from Boyne River estuary. These include dioxins and dioxin-like PCBs, silver (Ag), copper (Cu), chromium (Cr), molybdenum (Mo), and lead (Pb). Effects associated with exposure to these compounds may be possible, and may present a concern to the health of the green turtle population in Gladstone. Where available, tissue based concentrations for acute effects across vertebrate taxa are, however, considerably higher. Levels of the metals/metalloids arsenic (As), cadmium (Cd), cobalt (Co), mercury (Hg), nickel (Ni), selenium (Se), and vanadium (V) were clearly elevated in turtles from Gladstone and near or above tissue based effect concentrations were acute adverse effects have been reported across different vertebrate taxa. In the absence of information regarding the sensitivity of green turtles to such elements, these results suggest they should be considered of concern to the health of the population. Based on these results, monitoring of the health and contaminant levels in juvenile green turtle population is strongly recommended. As some of the contaminants investigated in this study are known to have tendencies to bioaccumulate with age of organisms, and biomagnify through the food chain it is additionally recommended to investigate the contaminant levels in adult sea turtles as well as higher trophic level marine organisms. This would additionally provide more information on whether acute high level, rather than chronic exposure occurred in this area. Analyses of varying storage tissues (e.g. carapace) may further assist evaluation of exposure duration. It is further recommended to identify and investigate suitable control populations, to provide a better understanding on typical baseline levels for metals/metalloids in green turtle populations from the wider Gladstone region, as the levels of some metals and metalloids may vary naturally across different locations. 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Dukou Sanitary and Anti-Epidemic Station [cited in Sun, 1987]. 86 Investigation of contaminant levels in green turtles from Gladstone 8.0 APPENDICES 8.1 RESULTS FOR INDIVIDUAL TURTLE SAMPLES 87 Investigation of contaminant levels in green turtles from Gladstone Table 10 Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs; ppt lw) in individual (n=22) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. EX Lipid D6 F5 F6 F7 TEQ † D4 D5 D7 D8 F4 F8 S PCDD/Fs 05 ID (%) 1 2 3 1 2 1 2 3 4 1 2 S PCDD/Fs Polychlorinated dibenzo-p -dioxins Polychlorinated dibenzofurans Totals Juveniles that were euthanised and necropsied 2 0.14 <4.0 <2.6 <3.5 <3.4 <3.6 30 100 <2.6 <1.5 <1.2 <0.80 <0.81 <1.3 <0.84 8.2 <3.1 55 390 4.8 3 0.22 <1.2 2.7 <2.5 3.7 3.9 32 140 3.7 <0.71 <0.53 <0.81 <0.82 <1.4 <0.92 8.8 <5.9 68 360 5.4 22 0.086 <10.0 4.8 <1.7 6.0 3.7 49 370 21 4.0 6.5 4.0 3.2 <2.7 <1.8 16 <2.3 57 ND 17 Live captured juveniles 7 0.062 (<7.0) (<11) (<13) (<16) (<16) (<96) (<370) (<22) <6.3 <6.5 <3.6 <4.4 <8.8 <7.4 26 10 97 ND (<16) 9 0.20 <0.74 4.5 <0.96 5.3 4.9 21 58 6.1 <0.44 <0.34 0.96 0.55 <0.53 0.61 4.0 1.6 25 200 7.1 13 0.12 <4.4 <5.0 <4.7 <4.6 9.3 36 150 <5.5 <3.1 <2.4 1.7 1.7 <2.6 2.9 7.6 <7.2 45 410 8.1 20 0.11 <8.4 6.7 <6.1 <5.8 <5.9 42 140 12 2.7 <1.6 <2.6 2.7 <3.6 <2.5 10 <3.7 36 ND 15 25 0.23 <0.97 <0.89 <1.7 4.0 3.4 24 130 3.7 <0.68 <0.53 <0.32 <0.31 <0.49 1.1 2.5 <1.0 25 240 2.7 30 0.13 <2.8 8.9 <2.1 7.9 10 53 150 21 6.7 <1.5 3.9 2.8 <2.5 3.0 10.0 4.4 65 470 17 32 0.20 <0.99 7.4 22 14 15 50 200 12 <0.56 2.4 1.2 1.6 <0.65 1.2 4.9 <1.1 37 520 16 34 0.070 <4.3 9.2 23 16 15 79 270 <2.8 <1.7 <1.2 <3.2 <3.2 <5.6 <3.2 9.3 <5.1 60 700 19 38 0.15 <1.8 5.0 12 10 5.9 38 140 13 <0.93 <0.69 <0.82 <0.81 <1.4 <0.84 6.5 <2.1 36 340 11 41 0.18 <2.8 <3.3 16 7.4 8.6 44 350 43 4.7 4.4 <1.7 <1.6 <2.7 <1.6 4.3 <2.2 57 600 13 42 0.23 <0.69 1.9 <1.1 2.8 2.7 18 75 14 2.5 2.0 1.2 0.74 <0.42 0.69 3.7 <1.5 27 220 5.4 43 0.11 <2.1 <2.1 <1.7 5.8 5.2 39 110 4.4 <2.0 7.7 6.5 4.7 <3.0 7.1 16 6.0 42 410 8.7 45 0.17 <4.4 5.5 <3.7 <3.5 5.3 33 110 <2.7 2.1 6.4 9.6 7.2 <2.5 4.8 19 <2.7 19 ND 14 46 0.17 <0.86 2.8 <0.22 3.7 3.1 23 85 2.1 <0.66 2.0 0.92 1.2 0.55 0.84 5.9 <1.7 31 250 5.4 47 0.14 <1.5 <1.4 <2.5 5.1 4.7 34 120 <1.2 <1.2 <0.90 <0.91 <0.90 <1.6 <0.92 4.2 <2.7 27 230 3.4 48 0.11 <2.5 7.5 <3.9 14 10 69 240 5.2 <1.7 <1.2 <1.8 <1.8 <3.2 <1.8 12 <5.2 62 600 13 50 0.12 (<5.9) (<9.5) (<11) (<14) (<14) (<81) (<320) (<19) <3.5 <7.7 <1.5 <1.9 <3.7 <3.8 17 7.5 98 ND (<13) 53 0.087 (<8.8) (<14) (<16) (<21) (<21) (<120) (<470) (<28) <6.2 <6.0 <14 <14 <26 <19 <20 <33 79 ND (<21) Live captured adult 36 0.15 <12 82 90 100 76 180 220 <6.6 <2.1 <1.6 2.9 2.6 <4.0 2.9 16 <5.9 38 ND 120 < Below the limit of detection (LOD) - the values given are the LOD; note: LOD is sometimes high, this is due to low volumes available for analysis and matrix problems (<) Values that could not be determined analytically mostly due to interferances in the chromatogram. Predicted values are shown, deduced from similar PCDD/F composition profiles observed across all other blood samples † Middlebound TEQ reported: TEQ values (pg TEQ/g lw) are calculated by including the non-quantified congeners at half the value of their LOQ or predicted value (indicated by <) ND No data 88 Investigation of contaminant levels in green turtles from Gladstone Table 11 Concentrations of polychlorinated biphenyls (WHO-PCBs; ppt lw) in individual (n=22) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. EX Lipid TEQ † 77 81 126 169 105 114 118* 123 156 157 167 189 05 ID (%) S PCBs Non-ortho PCBs Mono-ortho PCBs Juveniles that were euthanised and necropsied 2 0.14 <170 <55 <110 <170 <660 <220 <3300 <220 <660 <330 <440 <220 8.1 3 0.22 <97 <33 <65 <97 <390 <130 <2000 <130 <390 <200 <260 <130 4.8 22 0.086 (<200) (<78) <140 <210 <860 <290 <4300 <290 <860 <430 <570 <290 (<11) Live captured juveniles 7 0.062 (<290) (<110) (<210) <300 <1200 <620 <6000 <400 <1200 <600 <800 <400 (<15) 9 0.20 <75 <25 <50 <75 <300 <100 <1500 <100 <300 <150 250 <100 3.7 13 0.12 <160 <54 <110 <160 3300 <220 11000 390 2000 1300 1800 440 8.4 20 0.11 <170 <56 <180 <170 <670 <220 <3300 <220 <670 <330 <440 <220 11 25 0.23 <90 <49 <60 <90 <360 <120 <1800 <120 <360 <180 290 <120 4.4 30 0.13 <200 <65 <130 <200 <780 <260 <3900 <260 <780 <390 <520 <260 9.5 32 0.20 <100 <35 <69 <100 460 <140 <2100 <140 <410 <210 <280 <140 5.1 34 0.070 <230 <78 <160 <230 <940 <310 <4700 <310 <940 <470 800 <310 12 38 0.15 <130 <71 <86 <130 <510 <170 <2600 <170 <510 <260 <340 <170 6.3 41 0.18 <100 <57 <67 <100 440 <130 <2000 <130 <400 <200 <270 <130 4.9 42 0.23 <100 <44 <69 <100 <420 <140 <2100 <140 <420 <210 <280 <140 5.1 43 0.11 <140 <47 <94 <140 810 <190 2900 440 1000 400 1400 200 7.0 45 0.17 <110 <36 <150 <110 430 <150 <2100 <140 <430 <210 360 <140 9.0 46 0.17 <94 <31 <63 <94 <380 <130 <1900 <130 <380 <190 430 <130 4.6 47 0.14 <150 <51 <100 <150 <610 <200 <3100 <200 <610 <310 500 <200 7.5 48 0.11 <200 <65 <130 <200 <780 <260 <3900 <260 <780 <390 <520 <260 9.5 50 0.12 (<140) (<55) (<110) <150 <600 <360 <3000 <210 <600 330 590 230 (<7.6) 53 0.087 (<200) (<78) <290 <210 <860 <290 <4300 <290 <860 <430 <570 <290 (<18) Live captured adult 36 0.15 <130 <42 <110 <130 1900 180 5700 270 2600 1600 1800 520 7.9 < Below the limit of detection (LOD) - the values given are the LOD; note: LOD is sometimes high, this is due to low volumes available for analysis and matrix problems ( ) values that could not be determined analytically mostly due to interferances in the chromatogram. Predicted values are shown, deduced from similar PCB composition profiles observed across all other blood samples * Indicator PCB † Middlebound TEQ reported: TEQ values (pg TEQ/g lw) are calculated by including the non-quantified congeners at half the value of their LOQ (indicated by <) 89 Investigation of contaminant levels in green turtles from Gladstone Table 12 Concentrations of organotins (ppb ww) in individual (n=7) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. EX Lipid Monobutyltin Dibutyltin Tributyltin Tetrabutyltin Monooctyltin Dioctyltin Triphenyltin Tricyclohexyltin ID (%) MBT MBT-Sn DBT DBT-Sn TBT TBT-Sn TTBT TTBT-Sn MOT MOT-Sn DOT DOT-Sn TPhT TPhT-Sn TCHT TCHT-Sn Juveniles that were euthanised and necropsied 22 0.086 <6.8 <4.6 <6.8 <3.5 <20 <8.1 <15 <5.0 <6.8 <3.5 <27 <9.1 <6.8 <2.3 <39 <13 Live captured juveniles 7 0.06 <8.6 <5.8 <8.6 <4.4 <8.6 <3.5 <19 <6.5 <8.6 <4.4 <10 <3.5 <8.6 <2.9 <30 <9.7 20 0.11 <8.6 <5.8 <8.6 <4.4 <13 <5.1 <27 <9.3 <8.6 <4.4 <8.6 <2.9 <8.6 <2.9 <30 <9.6 45 0.17 <8.6 <5.8 <17 <8.9 <19 <7.7 <20 <6.8 <7.0 <3.6 <20 <6.8 <8.6 <2.9 <40 <13 50 0.12 <9.4 <6.3 <20 <10 <13 <5.3 <19 <6.4 <9.4 <4.8 <9.9 <3.4 <9.4 <3.2 <30 <9.6 53 0.09 <8.7 <5.9 <10 <5.1 <27 <11 <22 <7.6 <16 <8.3 <10 <3.5 <10 <3.4 <41 <13 Live captured adult 36 0.15 <8.7 <5.9 <10 <5.2 <13 <5.5 <20 <7.0 <11 <5.7 <8.7 <3.0 <8.7 <3.0 <31 <9.8 < Below the limit of detection (LOD) - the values given are the LOD; note: LOD is sometimes high, this is due to low volumes available for analysis and matrix problems 90 Investigation of contaminant levels in green turtles from Gladstone Table 13 Concentrations of bioaccumulative pesticides (ppb ww) in individual (n=7) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. EX Sample ID 22 7 20 45 50 53 36 Lipid (%) 0.086 0.062 0.11 0.17 0.12 0.090 0.15 Bioaccumulative Pesticides (ppb ww) Aldrin <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 α-chlordane <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 γ-chlordane <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 o,p-DDT <0.024 <0.021 <0.020 <0.027 <0.020 <0.020 <0.020 p,p'-DDT <0.029 <0.024 <0.022 <0.032 <0.020 <0.023 <0.021 Dieldrin <0.068 <0.058 <0.062 <0.079 <0.059 <0.063 <0.057 α-endosulfan <0.18 <0.12 <0.13 <0.18 <0.13 <0.12 <0.10 β-endosulfan <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Endosulfan sulphate <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Endrin <0.12 <0.10 <0.11 <0.14 <0.10 <0.11 <0.099 α-HCH <0.020 <0.020 0.14 <0.020 <0.020 <0.020 <0.020 β-HCH <0.022 <0.021 <0.021 <0.027 <0.020 <0.025 <0.020 γ-HCH <0.020 <0.020 <0.020 <0.021 <0.020 <0.023 <0.020 Heptachlor <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 cis -heptachlor epoxide <0.061 <0.043 <0.041 <0.052 <0.042 <0.053 <0.035 trans -heptachlor epoxide <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Hexachlorobenzene <0.030 <0.031 <0.045 <0.023 <0.026 <0.042 <0.028 Mirex <0.034 <0.024 <0.023 <0.029 <0.023 <0.030 <0.020 Octachlorostyrene <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Oxychlordane <0.092 <0.061 <0.070 <0.095 <0.068 <0.063 <0.052 Pentachlorobenzene <0.020 <0.020 <0.020 0.03 <0.020 <0.034 <0.020 Toxaphene, Parlar 26 <0.15 <0.11 <0.10 <0.13 <0.10 <0.13 <0.085 Toxaphene, Parlar 50 <0.31 <0.22 <0.21 <0.26 <0.21 <0.27 <0.18 Toxaphene, Parlar 62 <0.62 <0.44 <0.42 <0.53 <0.43 <0.54 <0.35 < Below the limit of quantification (LOQ) 91 Investigation of contaminant levels in green turtles from Gladstone Table 14 Concentrations of metals and metalloids (ppb ww) in individual (n=40) blood samples of green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. EX Ag Al As Cd Co Cr Cu Fe Hg Mn Mo Ni Pb Se V Zn ID Blood (ppb ww) Juveniles that were euthanised and necropsied 2 0.47 ND 1100 34 140 1.8 670 44000 <0.22 28 7.5 3.7 3.5 850 13 5200 3 0.89 ND 570 26 260 1.3 620 33000 0.90 23 5.6 3.2 0.20 850 4.0 3800 22 7.1 ND 650 100 110 180 1900 79000 9.9 33 6.8 6.5 19 3300 12 9300 Live captured juveniles 7 0.24 ND 20000 23 57 2.3 730 68000 8.6 24 7.5 1.7 6.6 2700 8.0 7900 8 0.15 ND 40 8.1 160 4.1 510 50000 <2.2 39 11 13 15 250 4.9 6500 9 0.20 ND 9300 61 220 3.8 740 78000 9.1 35 8.4 7.3 17 4500 8.2 9000 10 4.2 ND 2300 39 100 2.1 1200 66000 2.2 29 7.5 1.7 45 3100 4.9 6600 11 0.023 ND 1200 95 160 340 630 81000 28 43 7.3 7.2 19 3100 7.5 9600 13 0.72 ND 3500 62 46 3.8 950 61000 16 28 5.0 4.9 23 2200 19 7100 14 1.8 ND 610 30 73 1.9 1200 42000 5.4 24 7.0 1.7 3.8 1100 5.3 5700 15 0.13 ND 2400 54 120 2.3 790 57000 3.8 46 13 3.2 5.0 950 7.0 6700 20 <0.090 ND 3200 65 120 3.4 660 64000 4.7 28 10 9.0 8.0 2700 8.2 8400 21 0.14 ND 4100 37 99 3.2 610 66000 21 27 11 6.8 0.97 2000 7.0 7500 23 0.47 ND 2100 62 89 5.1 780 80000 12 39 5.5 6.3 38 5700 6.8 8800 24 <0.067 ND 5300 34 110 2.7 700 88000 38 47 11 0.67 13 8600 8.1 9000 25 0.057 ND 1200 38 250 3.5 550 49000 <0.72 23 6.1 7.6 7.5 1300 10 7200 26 0.040 ND 2000 56 95 3.5 720 73000 16 29 8.5 2.8 15 4400 9.9 9300 30 0.25 ND 260 12 440 7.1 600 68000 <0.90 41 5.8 4.2 76 170 10 9600 31 0.86 ND 87 14 160 3.4 1200 65000 0.66 38 5.4 4.8 36 960 35 9300 32 0.051 ND 280 9.7 360 4.2 700 91000 <1.9 36 16 17 10 120 17 12000 33 0.063 ND 600 38 140 3.1 830 80000 <0.96 73 13 5.8 21 670 37 11000 34 0.040 ND 1100 31 170 3.1 590 54000 1.2 23 19 5.8 13 620 7.2 8000 35 0.13 ND 230 9.0 220 4.0 770 79000 <2.5 32 9.3 3 56 350 21 11000 37 <0.10 ND 220 9.9 130 2.7 450 59000 <1.2 40 6.7 7.2 17 90 6.3 8100 38 0.20 ND 440 17 230 2.8 710 75000 <2.1 92 12 4.4 2.3 320 13 11000 39 0.38 ND 3000 44 68 1.9 910 47000 26 24 9.3 3.1 3.5 2600 4.5 5500 40 0.58 ND 130 78 50 2.8 1400 69000 0.68 26 16 4.0 36 2000 11 8300 41 <0.033 ND 170 15 210 4.1 680 73000 <0.44 58 9.5 6.9 15 220 5.7 10000 42 1.4 ND 1400 39 73 1.5 840 45000 11 16 4.6 1.0 <2.2 4600 3.5 5800 43 0.80 ND 6400 68 28 3.4 950 84000 35 19 83 3.4 15 8400 5.9 9800 44 1.2 ND 5000 28 67 1.8 470 51000 33 32 6.0 3.7 9.5 1600 13 5500 45 0.12 ND 1500 19 190 2.6 670 53000 1.3 27 6.7 7.6 19 640 8.2 7400 46 0.86 ND 900 41 43 1.7 790 51000 4.5 17 5.8 1.4 16 730 27 6200 47 0.36 ND 930 73 49 2.1 590 54000 25 22 4.9 4.1 22 770 30 6800 48 1.5 ND 330 10 340 3.7 740 82000 <2.0 51 16 10 13 84 6.8 11000 49 0.23 ND 2000 110 62 4.3 970 96000 6.0 36 11 1.4 34 1500 38 10000 50 0.34 ND 3200 65 110 3.4 580 70000 30 37 16 5.5 6.6 2300 14 9600 51 0.012 ND 790 19 260 3.6 530 64000 <2.4 34 7.4 5.7 17 350 6.5 8500 53 <0.14 ND 250 8.5 140 3.4 780 86000 <1.1 52 10 9.5 19 140 8.0 11000 Live captured adult 36 <0.011 ND 1400 8.6 150 2.7 530 70000 <2.9 22 9.7 0.86 33 430 14 11000 < Below the limit of detection (LOD), the values given are the LOD; note LOD is sometimes high, this is due to low volumes available for analysis and matrix problems ND No data 92 Investigation of contaminant levels in green turtles from Gladstone Table 15 Concentration of metals and metalloids (ppm ww) in liver and kidney of individual (n=3) green turtles (Chelonia mydas) from Boyne River estuary near Gladstone, Queensland. EX Ag Al As Cd Co Cr Cu Fe Hg Mn Mo Ni Pb Se V Zn ID Liver (ppm ww) Juveniles that were euthanised and necropsied 2 ND 2.4 2.0 13 0.95 0.092 84 1900 0.86 2.3 0.40 0.17 0.20 4.0 0.79 41 3 ND 3.5 2.0 15 0.93 0.29 67 1100 1.6 2.6 0.39 0.19 0.12 5.0 0.23 44 22 ND 2.4 2.0 24 2.3 0.16 100 2800 1.5 2.5 0.83 0.23 0.17 7.2 0.32 51 Kidney (ppm ww) Juveniles that were euthanised and necropsied 2 ND 0.48 1.2 17 0.99 0.18 9.4 11 0.15 0.48 0.062 26 0.15 0.62 0.34 20 3 ND 0.28 1.5 36 2.2 0.17 1.8 12 0.39 0.63 0.13 0.42 0.092 0.97 0.23 40 22 ND 0.40 0.88 90 3.2 0.62 2.1 21 0.72 0.87 0.30 0.89 0.047 2.4 0.34 39 ND No data 93 Investigation of contaminant levels in green turtles from Gladstone 8.2 COMPARISONS OF CONTAMINANT CONCENTRATIONS IN SEA TURTLES 94 Investigation of contaminant levels in green turtles from Gladstone 8.2.1 Aluminium (Al) Turtle Location/source Health & other n Country Location Age class Gender Mean Min Max Reference species information information Blood (ppb ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles ND ND ND This study moribund and healthy females Highly urbanised & Live captured Juveniles, Unknown Komoroske et Green 30 USA San Diego 150 ND ND contaminated estuary specimens Adults gender al 2011 Kidney (ppm ww) Unhealthy, incl. Males and Green 3 Australia Gladstone Industrialised port estuary Juveniles 0.39 0.28 0.48 This study moribund and healthy females Males and Aguirre et al Green 4 USA Hawaii Agricultural areas Stranded specimens 1.5 1.0 2.0 females 1994 Moribund specimens Males and Aguirre et al Green 5 USA Hawaii Agricultural areas with severe Juveniles 1.2 1.0 2.0 females 1994 fibropapilloma Generally considered relatively Juveniles Canary Islands, Mainly Torrent et al Loggerhead 78 Spain contaminated areas; high Ni Stranded and 0.72 0.030 7.6 Mediterranean females 2004 levels subadults Liver (ppm ww) Unhealthy, incl. Males and Green 3 Australia Gladstone Industrialised port estuary Juveniles 2.8 2.4 3.5 This study moribund and healthy females Males and Aguirre et al Green 3 USA Hawaii Agricultural areas Stranded specimens 4.0 3.0 5.0 females 1994 Moribund specimens Males and Aguirre et al Green 6 USA Hawaii Agricultural areas with severe Juveniles 1.7 1.0 3.0 females 1994 fibropapilloma 95 Investigation of contaminant levels in green turtles from Gladstone Aguirre et al Green 1 USA Control, captive Agricultural areas Captive specimen Adult Female 1.0 ND ND 1994 Generally considered relatively Juveniles Males and Torrent et al Loggerhead 78 Spain Canary Islands contaminated areas; high Ni Stranded and sub- 2.2 0.53 31 females 2004 levels adults 96 Investigation of contaminant levels in green turtles from Gladstone 8.2.2 Arsenic (As) Turtle Location/source Health & other n Country Location Age class Gender Mean Min Max Reference species information information Blood (ppb ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 2300 40 20000 This study moribund and healthy females Highly urbanised & Live captured Juveniles, Unknown Komoroske et Green 30 USA San Diego 160 ND ND contaminated estuary specimens Adults gender al 2011 Moribund, washed up van de Urbanised, potentially near Juveniles and Green 16 Australia Gold Coast, QLD specimens, ND 4400 94 20000 Merwe et al point sources subadults euthanised 2010a Generally considered relatively Stranded specimens, Males and Jerez et al Loggerhead 5 Spain Mediterranean SCL 29-47 cm 770 230 2600 " polluted some alive females 2010 Kidney (ppm ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 1.1793 0.88 1.5 This study moribund and healthy females Moreton Bay, QLD Urbanised port estuary; Cd (incl. n=1 each Stranded specimens; Juveniles and Gordon et al Green 23 Australia among the highest recorded ND 0.19 ND 0.69 from Shoalwater mainly unhealthy adults 1998 for marine vertebrates and Hervey Bays) Remote, very high Cd, Gladstone Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 0.42 0.070 1.2 elevated Co, Hg, Se 1996 Males (n=5), females Yaeyama Island, Cd concentrations considered Juveniles and Sakai et al Green 19 Japan Caught by fishermen (n=13) and 0.69 0.018 1.2 † Okinawa high adults 2000b unknown (n=2) 97 Investigation of contaminant levels in green turtles from Gladstone Hong Urban and industrial area; Lam et al Green 2 Kong, South China Sea exposed to relatively high Stranded specimens Juveniles ND 0.84 ND ND † 2004 China levels of Se Stranded specimens Southwest Generally considered relatively from nesting Adults and Mostly Kaska et al Green 14 Turkey 1.7 0.62 2.5 † Mediterranean contaminated population, mainly subadults females 2004 fishing related deaths SCL average Females Ishigaki Island, As levels higher or similar to 43.7 Agusa et al Green 6 Japan Caught by fishermen (n=17) and 2.0 ND ND † Okinawa other regions (females), 2008a males (n=3) 41.4 (males) Ishigaki Island, As levels higher or similar to SCL 38.6-53.4 Unknown Agusa et al Green 20 Japan Caught by fishermen 2.0 0.55 5.3 † Okinawa other regions cm gender 2008b Moribund, washed up van de Urbanised, potentially near Juveniles and Green 16 Australia Gold Coast, QLD specimens, ND 2.7 0.12 9.3 Merwe et al point sources subadults euthanised 2010a Males and Aguirre et al Green 1 USA Hawaii Agricultural areas Stranded specimens ND 6.8 ND ND females 1994 Urbanised port estuary; Cd Stranded specimens; Gordon et al Hawksbill 2 Australia Moreton Bay, QLD among the highest recorded Unknown ND ND 0.13 0.93 mainly unhealthy 1998 for marine vertebrates Females Yaeyama Island, (n=3) and Saeki et al Hawksbill 4 Japan As levels very high Caught by fishermen SCL 38-58 cm 3.4 1.0 4.4 † Okinawa unknown 2000 (n=1) Ishigaki Island, Extremely high As, particularly SCL average Agusa et al Hawksbill 6 Japan Caught by fishermen Females 5.4 ND ND † Okinawa in muscle 40.9 2008a Urbanised port estuary; Cd Stranded specimens; Gordon et al Loggerhead 3 Australia Moreton Bay, QLD among the highest recorded Unknown ND 0.71 0.24 1.2 mainly unhealthy 1998 for marine vertebrates 98 Investigation of contaminant levels in green turtles from Gladstone Females Cd concentrations considered Juveniles and (n=2) and Saeki et al Loggerhead 4 Japan North Pacific Caught by fishermen 1.1 0.48 2.4 † high adults unknown 2000 (n=2) Stranded specimens Southwest Generally considered relatively from nesting Adults and Kaska et al Loggerhead 20 Turkey ND 2.3 0.12 4.2 † Mediterranean contaminated population, mainly subadults 2004 fishing related deaths Mainly Canary Islands, Generally considered relatively Juveniles and Torrent et al Loggerhead 78 Spain Stranded females 14 1.2 120 Mediterranean contaminated areas subadults 2004 (n=67) Liver (ppm ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 2.0115 2.0 1.9662 This study moribund and healthy females Moreton Bay, QLD Urbanised port estuary; Cd (incl. n=1 each Stranded specimens; Juveniles and Gordon et al Green 23 Australia among the highest recorded ND 0.26 0.040 0.74 from Shoalwater mainly unhealthy adults 1998 for marine vertebrates and Hervey Bays) Males (n=5), females Yaeyama Island, Cd concentrations considered Juveniles and Sakai et al Green 19 Japan Caught by fishermen (n=13) and 0.39 0.10 1.2 † Okinawa high adults 2000b unknown (n=2) Hong Urban and industrial area; Lam et al Green 2 Kong, South China Sea exposed to relatively high Stranded specimens Juveniles ND 1.0 ND ND † 2004 China levels of Se SCL average Females Ishigaki Island, As levels higher or similar to 43.7 Agusa et al Green 5 Japan Caught by fishermen (n=17) and 1.1 ND ND † Okinawa other regions (females), 2008a males (n=3) 41.4 (males) 99 Investigation of contaminant levels in green turtles from Gladstone Ishigaki Island, As levels higher or similar to SCL 38.6-53.4 Unknown Agusa et al Green 20 Japan Caught by fishermen 1.2 0.20 2.1 † Okinawa other regions cm gender 2008b Ishigaki Island, Fujihara et al Green 5 Japan Caught alive ND ND 1.2 0.80 2.3 Okinawa 2003 Remote, very high Cd, Gladstone Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 1.5 0.42 4.3 elevated Co, Hg, Se 1996 Stranded specimens Southwest Generally considered relatively from nesting Adults and Mostly Kaska et al Green 22 Turkey 2.1 0.31 3.7 † Mediterranean contaminated population, mainly subadults females 2004 fishing related deaths Moribund, washed up van de Urbanised, potentially near Juveniles and Green 16 Australia Gold Coast, QLD specimens, ND 3.2 0.63 9.7 Merwe et al point sources subadults euthanised 2010a Males and Aguirre et al Green 2 USA Hawaii Agricultural areas Stranded specimens ND 3.7 0.90 6.4 females 1994 Females Yaeyama Island, (n=3) and Saeki et al Hawksbill 4 Japan As levels very high Caught by fishermen SC 38-58 CM 3.4 1.1 7.2 † Okinawa unknown 2000 (n=1) Ishigaki Island, Fujihara et al Hawksbill 5 Japan ND Caught alive ND ND 4.4 0.66 7.5 Okinawa 2003 Ishigaki Island, Extremely high As, particularly SCL average Agusa et al Hawksbill 10 Japan Caught by fishermen Females 5.5 ND ND † Okinawa in muscle 40.9 2008a Urbanised port estuary; Cd Stranded specimens; Gordon et al Hawksbill 2 Australia Moreton Bay, QLD among the highest recorded Unknown ND ND 0.18 1.9 mainly unhealthy 1998 for marine vertebrates Urbanised port estuary; Cd Stranded specimens; Gordon et al Loggerhead 6 Australia Moreton Bay, QLD among the highest recorded Unknown ND 0.46 ND 1.6 mainly unhealthy 1998 for marine vertebrates 100 Investigation of contaminant levels in green turtles from Gladstone Females Cd concentrations considered Juveniles and (n=2) and Saeki et al Loggerhead 4 Japan North Pacific Caught by fishermen 1.4 0.93 2.1 † high adults unknown 2000 (n=2) Stranded specimens Southwest Generally considered relatively from nesting Adults and Kaska et al Loggerhead 32 Turkey ND 3.1 0.48 5.4 † Mediterranean contaminated population, mainly subadults 2004 fishing related deaths Apulian coast Storelli & Weight 1.8-90 Loggerhead 7 Italy (South Adriatic Pooled sample Stranded specimens ND 6.9 14 ND Marcotrigiano kg sea) 2000 101 Investigation of contaminant levels in green turtles from Gladstone 8.2.3 Cadmium (Cd) Health & Turtle Location/source Age n Country Location other Gender Mean Min Max Reference species information class information Blood (ppb ww) Unhealthy, incl. Males and Green 3 Australia Gladstone Industrialised port estuary moribund and Juveniles 40 8.1 110 This study females healthy Highly urbanised & Live captured Juveniles, Unknown Komoroske et al Green 19 USA San Diego 13 ND ND contaminated estuary specimens Adults gender 2011 Relatively pristine, agriculture, shipyards & Live captured urban wastewater Unknown Labrada-Martagón Green 14 Mexico Bahia Magdalena specimens, Juveniles 30 10 50 ˄ discharge, 19th century gender et al 2011 apparently healthy mining; Cd, Zn, Cu and Pb high in sediments Moribund, washed Juveniles Urbanised, potentially near Males and van de Merwe et al Green 16 Australia Gold Coast, QLD up specimens, and 35 1.1 122 point sources females 2010a euthanised subadults Relatively pristine, agriculture, shipyards & Live captured urban wastewater Unknown Labrada-Martagón Green 42 Mexico Punta Abreojos specimens, Juveniles 60 8.0 120 ˄ discharge, 19th century gender et al 2011 apparently healthy mining; Cd, Zn, Cu and Pb high in sediments Young Ikonomopoulou et al Flatback 20 Australia Curtis Isl, QLD Off the coast of Gladstone Live, nesting adults to Females <0.1 ND ND 2011 adults 102 Investigation of contaminant levels in green turtles from Gladstone Various possible sources Paez-Osuna et al Olive Ridley 25 Mexico Oaxaca Live, nesting Adults Females 12 ND ND # along migration route 2010 Kidney (ppm ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary moribund and Juvenile 47 17 90 This study females healthy Pollution considered negligible (but 200 km Green 15 Brazil Cananeia Estuary Stranded Juvenile ND 0.12 ND ND † Barbieri et al 2009 south of major industrial area of Brazil) Pollution considered negligible (but 200 km Green 15 Brazil Cananeia Estuary Stranded Adult ND 0.26 ND ND † Barbieri et al 2009 south of major industrial area of Brazil) Hong Stranded Green 2 Kong, South China Sea Urban and industrial area Juveniles ND 0.30 ND ND † Lam et al 2004 specimens China Northern Cyprus, Generally contaminated, Stranded Green 1 Cyprus Juveniles ND 1.0 ND ND * Godley et al 1999 Mediterranean presence of natural Hg bed specimens Stranded specimens from Adults Southwest Generally considered Mostly Green 14 Turkey nesting population, and 1.9 0.66 2.8 † Kaska et al 2004 Mediterranean relatively contaminated females mainly fishing subadults related deaths Dead, nesting Tortuguero National Pooled Green 33 Costa Rica Cd considered background turtles, killed by ND 4.7 ND ND † Andreani et al 2008 Park, North Carribean sample jaguars Adreaiatic and Ionian Generally considered Unknown Green 7 Italy Stranded Juveniles 5.1 2.2 7.5 Storelli et al 2008 Seas, Mediterranean contaminated gender 103 Investigation of contaminant levels in green turtles from Gladstone Stranded Males and Green 5 USA Pelagic, Hawaii Agricultural areas ND 10 4.7 10 Aguirre et al 1994 specimens females 19th century mining - Cd, Zn, Cu and Pb in sediments Specimens Magdalena Bay, Baja SCL 47-77 Unknown Talavera-Saenz et al Green 8 Mexico above those in drowned in fishing 13 7.8 78 † California cm gender 2007 industrialised regions; Cd nets considered elevated Moreton Bay, QLD (incl. Urbanised port estuary; Cd Stranded n=1 each from among the highest Juveniles Green 38 Australia specimens; mainly ND 15 1.7 76 Gordon et al 1998 Shoalwater and Hervey recorded for marine and adults unhealthy Bays) vertebrates Green 1 USA Control, Captive Agricultural areas Captive specimen ND Female 22 ND ND Aguirre et al 1994 Remote, very high Cd, Green 7 Australia Waru, Torres Strait Caught alive ND ND 26 12 42 Gladstone et al 1996 elevated Co, Hg, Se Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 25 Japan Fishing nets 28 4.0 60 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Cd concentrations Caught by Juveniles Unknown Green 23 Japan Yaeyama Isl, Okinawa 39 7.3 81 Sakai et al 2000b considered high fishermen and adults gender HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Green 2 Japan Mature 41 37 46 Sakai et al 2000a Isl concentrations waters female Moribund Ahu-O-Laka, Kaneohe, specimens with Males and Green 6 USA Agricultural areas Juveniles 42 16 70 Aguirre et al 1994 HI severe females fibropapilloma Moribund, washed Juvenile Urbanised, potentially near van de Merwe et al Green 16 Australia Gold Coast, QLD up specimens, and ND 46 13 100 point sources 2010a euthanised subadult Hawksbill 3 Australia Moreton Bay, QLD Urbanised port estuary; Cd Stranded Unknown ND ND 3.6 13 Gordon et al 1998 among the highest specimens; mainly 104 Investigation of contaminant levels in green turtles from Gladstone recorded for marine unhealthy vertebrates Yaeyama Islands, Renal Cd levels considered Mostly Males and Hawksbill 19 Japan Fishing nets 18 4.0 60 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Cesenatico & Sicily Loggerhead 9 Italy Cd considered background Stranded ND ND 0.70 ND ND † Andreani et al 2008 Island, Mediterranean Stranded specimens from Adults Southwest Generally considered Mostly Loggerhead 20 Turkey nesting population, and 2.0 0.38 4.0 † Kaska et al 2004 Mediterranean relatively contaminated females mainly fishing subadults related deaths Generally considered Juveniles Mainly Canary Islands, Loggerhead 78 Spain relatively contaminated Stranded and females 5.0 0.010 61 Torrent et al 2004 Mediterranean areas subadults (n=67) Generally considered Adreaiatic and Ionian contaminated; Cd Mainly Unknown Loggerhead 19 Italy Stranded 8.4 1.3 16 Storelli et al 2005 Seas, Mediterranean considered high enough to juvenile gender affect health Northern Cyprus, Generally contaminated, Stranded Loggerhead 2 Cyprus Juveniles ND 8.5 5.3 12 * Godley et al 1999 Mediterranean presence of natural Hg bed specimens Loggerhead 5 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 13 1.7 36 Caurant et al 1999 Urbanised port estuary; Cd Stranded among the highest Juveniles Loggerhead 5 Australia Moreton Bay, QLD specimens; mainly ND 28 11 39 Gordon et al 1998 recorded for marine and adults unhealthy vertebrates Highest Cd in specimens Adults Females Fishing net Sakai et al 1995 Loggerhead 7 Japan Cape Ashizuri, Kochi with symptoms of kidney (SCL 76- (n=6) and 39 18 57 entanglement Sakai et al 2000a congestion 92) n=1 male 105 Investigation of contaminant levels in green turtles from Gladstone Leatherback 5 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 30 8.5 62 Caurant et al 1999 Urbanised port estuary; Cd Stranded among the highest Olive Ridley 1 Australia Moreton Bay, QLD specimens; mainly Unknown ND 30 ND ND Gordon et al 1998 recorded for marine unhealthy vertebrates Liver (ppm ww) Unhealthy, incl. Males and Green 3 Australia Gladstone Industrialised port estuary moribund and Juvenile 17 13 24 This study females healthy Pollution considered negligible (but 200 km Green 15 Brazil Cananeia Estuary Stranded Juvenile ND 0.061 ND ND † Barbieri et al 2009 south of major industrial area of Brazil) Sultanate Ras Al-Hadd Turtle Eggs collected from Green 50 ND Hatchling ND 0.21 ND ND Al-Rawahy et al 2007 of Oman Reserve nest Pollution considered negligible (but 200 km Green 15 Brazil Cananeia Estuary Stranded Adult ND 0.21 ND ND † Barbieri et al 2009 south of major industrial area of Brazil) Hong Stranded Green 2 Kong, South China Sea Urban and industrial area Juveniles ND 0.24 ND ND † Lam et al 2004 specimens China Hong Stranded Green 4 Kong, South China Sea Urban and industrial area Adults ND 0.32 ND ND † Lam et al 2004 specimens China Northern Cyprus, Generally contaminated, Stranded Green 6 Cyprus Juveniles ND 1.3 0.56 2.4 * Godley et al 1999 Mediterranean presence of natural Hg bed specimens 106 Investigation of contaminant levels in green turtles from Gladstone Stranded specimens from Adults Southwest Generally considered Green 22 Turkey nesting population, and ND 1.6 0.83 3.5 † Kaska et al 2004 Mediterranean relatively contaminated mainly fishing subadults related deaths Dead, nesting Tortuguero National Pooled Green 34 Costa Rica Cd considered background turtles, killed by ND 2.3 ND ND † Andreani et al 2008 Park, North Carribean sample jaguars Stranded Males and Green 5 USA Hawaii Agricultural areas ND 2.7 0.39 5.4 Aguirre et al 1994 specimens females Green 1 USA Hawaii Agricultural areas Captive specimen ND Female 3.1 ND ND Aguirre et al 1994 Agriculture and 19th century mining - Cd, Zn, Cu Specimens Magdalena Bay, Baja and Pb in sediments above SCL 47-77 Unknown Talavera-Saenz et al Green 8 Mexico drowned in fishing 3.7 Adreaiatic and Ionian Generally considered Unknown Green 7 Italy Stranded Juveniles 4.3 2.2 9.2 Storelli et al 2008 Seas, Mediterranean contaminated gender Cd concentrations Caught by Juveniles Green 50 Japan Yaeyama Isl, Okinawa Unknown 5.6 0.30 19 Sakai et al 2000b considered high fishermen and adults Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 26 Japan Fishing nets 5.6 1.1 12 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Green 2 Japan Mature 8.0 3.9 12 Sakai et al 2000a Isl concentrations waters female Remote, very high Cd, Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 11 6.0 17 Gladstone 1996 elevated Co, Hg, Se 107 Investigation of contaminant levels in green turtles from Gladstone Moreton Bay, QLD (incl. Urbanised port estuary; Cd Stranded n=1 each from among the highest Juveniles Green 38 Australia specimens; mainly ND 13 2.5 57 Gordon et al 1998 Shoalwater and Hervey recorded for marine and adults unhealthy Bays) vertebrates Moribund, washed Juvenile Urbanised, potentially near van de Merwe et al Green 16 Australia Gold Coast, QLD up specimens, and ND 14 4.3 32 point sources 2010a euthanised subadult Moribund specimens with Males and Green 6 USA Hawaii Agricultural areas Juveniles 16 5 26 Aguirre et al 1994 severe females fibropapilloma Yaeyama Islands, Renal Cd levels considered Mostly Males and Hawksbill 22 Japan Fishing nets 2.2 0.56 10 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Urbanised port estuary; Cd Stranded among the highest Hawksbill 3 Australia Moreton Bay, QLD specimens; mainly Unknown ND ND 2.4 6 Gordon et al 1998 recorded for marine unhealthy vertebrates Leatherback 18 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 6.8 0.60 15 Caurant et al 1999 Cesenatico & Sicily Loggerhead 11 Italy Cd considered background Stranded ND ND 0.53 ND ND † Andreani et al 2008 Island, Mediterranean Northern Cyprus, Generally contaminated, Stranded Loggerhead 4 Cyprus Juveniles ND 1.9 1.1 2.9 * Godley et al 1999 Mediterranean presence of natural Hg bed specimens Stranded specimens from Adults Southwest Generally considered Loggerhead 32 Turkey nesting population, and ND 2.4 0.7502 4.2 † Kaska et al 2004 Mediterranean relatively contaminated mainly fishing subadults related deaths Canary Islands, Loggerhead 78 Spain Generally considered Stranded Juveniles Mainly 2.5 0.040 22 Torrent et al 2004 Mediterranean relatively contaminated and females 108 Investigation of contaminant levels in green turtles from Gladstone areas subadults (n=67) Loggerhead 7 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 2.6 0.30 12 Caurant et al 1999 Generally considered Adreaiatic and Ionian contaminated; Cd Mainly Unknown Loggerhead 19 Italy Stranded 3.4 1.1 7 Storelli et al 2005 Seas, Mediterranean considered high enough to juvenile gender affect health Highest Cd in specimens Adults Females Fishing net Sakai et al 1995 Loggerhead 7 Japan Cape Ashizuri, Kochi with symptoms of kidney (SCL 76- (n=6) and 9.3 5.7 15 entanglement Sakai et al 2000a congestion 92) n=1 male Urbanised port estuary; Cd Moreton Bay, QLD (incl. Stranded among the highest Juveniles Loggerhead 8 Australia n=2 Shoalwater & specimens; mainly ND 16 7.3 35 Gordon et al 1998 recorded for marine and adults Hervey Bays) unhealthy vertebrates Urbanised port estuary; Cd Stranded among the highest Olive Ridley 1 Australia Moreton Bay, QLD specimens; mainly Unknown ND 6.4 ND ND Gordon et al 1998 recorded for marine unhealthy vertebrates 109 Investigation of contaminant levels in green turtles from Gladstone 8.2.4 Chromium (Cr) Turtle Location/source n Country Location Health & other information Age class Gender Mean Min Max Reference species information Blood (ppb ww) Unhealthy, incl. moribund and Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 16 1.3 340 This study healthy females Kidney (ppm ww) Unhealthy, incl. moribund and Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 0.32 0.17 0.62 This study healthy females Urban and industrial area; Hong Kong, Lam et al Green 2 South China Sea exposed to relatively high Stranded specimens Juveniles ND 0.13 ND ND † China 2004 levels of Se Stranded specimens from Southwest Generally considered Adults and Mostly Kaska et al Green 14 Turkey nesting population, mainly 0.31 0.079 1.4 † Mediterranean relatively contaminated subadults females 2004 fishing related deaths Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen ND Female 0.40 ND ND 1994 Yaeyama Islands, Renal Cd levels considered Mostly Males and Anan et al Green 25 Japan Fishing nets 0.43 0.27 0.74 ‡ Okinawa Prefecture extremely high juveniles females 2001 Yaeyama Islands, Renal Cd levels considered Mostly Males and Anan et al Hawksbill 19 Japan Fishing nets 0.31 0.059 0.57 ‡ Okinawa Prefecture extremely high juveniles females 2001 Stranded specimens from Southwest Generally considered Adults and Kaska et al Loggerhead 20 Turkey nesting population, mainly ND 0.25 0.14 0.34 † Mediterranean relatively contaminated subadults 2004 fishing related deaths Liver (ppm ww) Green 40 Australia Gladstone Industrialised port estuary Unhealthy, incl. moribund and Juveniles Males and 0.18 0.092 0.293 This study 110 Investigation of contaminant levels in green turtles from Gladstone healthy females Ahu-O-Laka, Moribund specimens with Males and Aguirre et al Green 3 USA Agricultural areas Juveniles 0.20 0.20 0.20 Kaneohe, HI severe fibropapilloma females 1994 Sultanate Ras Al-Hadd Turtle Substantial industrial and Al-Rawahy et Green 50 Hatchlings; control Hatchling ND 0.25 ND ND of Oman Reserve urban developments al 2007 Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen ND Female 0.50 ND ND 1994 Stranded specimens from Southwest Generally considered Adults and Mostly Kaska et al Green 22 Turkey nesting population, mainly 0.54 0.21 1.3 † Mediterranean relatively contaminated subadults females 2004 fishing related deaths Yaeyama Renal Cd levels considered Mostly Males and Anan et al Green 26 Japan Islands,Okinawa Fishing nets 0.68 0.46 1.1 ‡ extremely high juveniles females 2001 Prefecture Urban and industrial area; Hong Kong, Lam et al Green 2 South China Sea exposed to relatively high Stranded specimens Juveniles ND ND Yaeyama Islands, Renal Cd levels considered Mostly Males and Anan et al Hawksbill 22 Japan Fishing nets 0.26 0.065 0.65 ‡ Okinawa Prefecture extremely high juveniles females 2001 Stranded specimens from Southwest Generally considered Adults and Kaska et al Loggerhead 32 Turkey nesting population, mainly ND 0.61 0.29 1 † Mediterranean relatively contaminated subadults 2004 fishing related deaths 111 Investigation of contaminant levels in green turtles from Gladstone 8.2.5 Cobalt (Co) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Males Unhealthy, incl. moribund Green 40 Australia Gladstone Industrialised port estuary Juveniles and 150 28 440 This study and healthy females Juveniles Urbanised, potentially near point Moribund, washed up van de Merwe Green 16 Australia Gold Coast, QLD and ND 36 3.2 88 sources specimens, euthanised et al 2010a subadults Young Ikonomopoulou Flatback 20 Australia Curtis Isl, QLD Off the coast of Gladstone Live, nesting adults to Females <0.1 <0.1 <0.1 et al 2011 adults Kidney (ppm ww) Males Unhealthy, incl. moribund Green 40 Australia Gladstone Industrialised port estuary Juveniles and 2.1 0.99 3.2 This study and healthy females HahaJima/OgaSawara Male and Sakai et al Green 2 Japan Relatively high Cd concentrations Collected in coastal waters Mature 0.30 <0.03 0.57 Island female 2000a Males Yaeyama Islands, Renal Cd levels considered Mostly Green 25 Japan Fishing nets and 0.51 0.037 2.0 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Juveniles Cd concentrations considered Unknown Sakai et al Green 23 Japan Yaeyama Isl, Okinawa Caught by fishermen and 0.81 0.063 2.5 high gender 2000b adults Green 2 Hong South China Sea Urban and industrial area; Stranded specimens Juveniles ND 1.4 ND ND † Lam et al 2004 Kong, exposed to relatively high levels 112 Investigation of contaminant levels in green turtles from Gladstone China of Se Juveniles Urbanised, potentially near point Moribund, washed up van de Merwe Green 16 Australia Gold Coast, QLD and ND 1.5 0.13 5.5 sources specimens, euthanised et al 2010a subadults Males Yaeyama Islands, Renal Cd levels considered Mostly Hawksbill 19 Japan Fishing nets and 0.60 0.18 1.9 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Adults Females Sakai et al 1995 Highest Cd in specimens with Loggerhead 7 Japan Cape Ashizuri, Kochi Fishing net entanglement (SCL 76- (n=6) and 0.20 0.13 0.26 Sakai et al symptoms of kidney congestion 92) n=1 male 2000a Liver (ppm ww) Males Unhealthy, incl. moribund Green 40 Australia Gladstone Industrialised port estuary Juveniles and 1.4 0.93 2.3 This study and healthy females HahaJima/OgaSawara Male and Sakai et al Green 2 Japan Relatively high Cd concentrations Collected in coastal waters Mature <0.03 <0.03 <0.03 Island female 2000a Juveniles Cd concentrations considered Unknown Sakai et al Green 50 Japan Yaeyama Isl, Okinawa Caught by fishermen and 0.067 0.067 0.067 high gender 2000b adults Males Yaeyama Islands, Renal Cd levels considered Mostly Green 26 Japan Fishing nets and 0.077 0.023 0.40 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Sultanate Ras Al-Hadd Turtle Substantial industrial and urban Al-Rawahy et al Green 50 Hatchlings; control Hatchling ND 0.11 ND ND of Oman Reserve developments 2007 Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high levels Stranded specimens Juveniles ND 0.13 ND ND † Lam et al 2004 China of Se 113 Investigation of contaminant levels in green turtles from Gladstone Juveniles Urbanised, potentially near point Moribund, washed up van de Merwe Green 16 Australia Gold Coast, QLD and ND 0.61 0.080 3.2 sources specimens, euthanised et al 2010a subadults Males Yaeyama Islands, Renal Cd levels considered Mostly Hawksbill 22 Japan Fishing nets and 0.22 0.053 0.65 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Adults Females Sakai et al 1995 Highest Cd in specimens with Loggerhead 7 Japan Cape Ashizuri, Kochi Fishing net entanglement (SCL 76- (n=6) and <0.03 <0.03 <0.03 Sakai et al symptoms of kidney congestion 92) n=1 male 2000a 114 Investigation of contaminant levels in green turtles from Gladstone 8.2.6 Copper (Cu) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles 780 450 1900 This study females healthy Highly urbanised & Live captured Juveniles, Unknown Komoroske et Green 30 USA San Diego 750 ND ND contaminated estuary specimens Adults gender al 2011 Moribund, washed Juveniles Urbanised, potentially near van de Merwe Green 16 Australia Gold Coast, QLD up specimens, and ND 1000 400 1600 point sources et al 2010a euthanised subadults Young Ikonomopoulou Flatback 20 Australia Curtis Isl, QLD Off the coast of Gladstone Live, nesting adults to Females 7.7 4.0 10 et al 2011 adults French Industry, mining activities Guirlet et al Leatherback 78 French Guiana Nesting females Adult Females 1300 1100 1600 ˄ Guiana along migration path 2008 Various possible sources along Paez-Osuna et Olive Ridley 25 Mexico Oaxaca Live, nesting Adults Females 62 ND ND # migration route al 2010 Kidney (ppm ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles 4.4 1.8 9.4 This study females healthy Stranded specimens Southwest Generally considered relatively from nesting Adults and Mostly Kaska et al Green 14 Turkey 0.21 0.084 0.31 † Mediterranean contaminated population, mainly subadults females 2004 fishing related deaths 115 Investigation of contaminant levels in green turtles from Gladstone 19th century mining - Cd, Zn, Magdalena Bay, Baja Cu and Pb in sediments above Specimens drowned SCL 47-77 Unknown Talavera-Saenz Green 8 Mexico 0.70 0.24 1.4 † California those in industrialised regions; in fishing nets cm gender et al 2007 Cd considered elevated Tortuguero National Dead, nesting turtles, Andreani et al Green 33 Costa Rica Cd considered background ND ND 1.0 ND ND † Park, North Carribean killed by jaguars 2008 HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Sakai et al Green 2 Japan Mature 1.5 1.3 1.7 Isl concentrations waters female 2000a Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Juvenile ND 1.5 ND ND † 2009 industrial area of Brazil) Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Adult ND 1.6 ND ND † 2009 industrial area of Brazil) Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 25 Japan Fishing nets 1.6 0.47 3.7 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Urban and industrial area; Hong Kong, Green 2 South China Sea exposed to relatively high Stranded specimens Juveniles ND 1.8 ND ND † Lam et al 2004 China levels of Se Cd concentrations considered Juveniles Unknown Sakai et al Green 23 Japan Yaeyama Isl, Okinawa Caught by fishermen 2.2 0.95 3.9 high and adults gender 2000b Moribund, washed Juveniles Urbanised, potentially near van de Merwe Green 16 Australia Gold Coast, QLD up specimens, and ND 2.6 1.4 4.6 point sources et al 2010a euthanised subadults Moribund specimens Ahu-O-Laka, Agricultural areas; Se levels Males and Aguirre et al Green 6 USA with severe Juveniles 2.9 1.8 4.4 Kaneohe, HI considered "normal" females 1994 fibropapilloma Males and Aguirre et al Green 5 USA Pelagic, Hawaii Agricultural areas; relatively Stranded specimens ND 3.1 1.1 6.9 high Se in one pelagic females 1994 116 Investigation of contaminant levels in green turtles from Gladstone specimen, but otherwise considered "normal" Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive ND ND 7.4 0.81 45 Gladstone 1996 Co, Hg, Se Adreaiatic and Ionian Generally considered Unknown Storelli et al Green 7 Italy Stranded Juveniles 8.2 4.8 14 Seas, Mediterranean contaminated gender 2008 Agricultural areas; Se levels Aguirre et al Green 1 USA Control, Captive Captive specimen ND Female 11 ND ND considered "normal" 1994 Yaeyama Islands, Renal Cd levels considered Mostly Males and Hawksbill 19 Japan Fishing nets 1.4 0.95 3.5 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Caurant et al Leatherback 5 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 2.7 2.4 3.0 1999 Stranded specimens Southwest Generally considered relatively from nesting Adults and Mostly Kaska et al Loggerhead 20 Turkey 0.25 0.14 0.37 † Mediterranean contaminated population, mainly subadults females 2004 fishing related deaths Cesenatico & Sicily Andreani et al Loggerhead 9 Italy Island, Cd considered background Stranded ND ND 0.67 ND ND † 2008 Mediterranean Highest Cd in specimens with Females Sakai et al 1995 Fishing net Adults (SCL Loggerhead 7 Japan Cape Ashizuri, Kochi symptoms of kidney (n=6) and 1.3 0.99 1.6 Sakai et al entanglement 76-92) congestion n=1 male 2000a Caurant et al Loggerhead 5 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 2.2 1.8 2.8 1999 Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 4.6 0.13 49 Mediterranean contaminated areas 2004 subadults (n=67) Liver (ppm ww) 117 Investigation of contaminant levels in green turtles from Gladstone Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles 84 67 100 This study females healthy Stranded specimens Southwest Generally considered relatively from nesting Adults and Mostly Kaska et al Green 22 Turkey 0.38 0.12 0.66 † Mediterranean contaminated population, mainly subadults females 2004 fishing related deaths Sultanate of Ras Al-Hadd Turtle Substantial industrial and Al-Rawahy et al Green 50 Hatchlings; control Hatchling ND 2.2 ND ND Oman Reserve urban developments 2007 Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Juvenile ND 4.6 ND ND † 2009 industrial area of Brazil) Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Adult ND 8.8 ND ND † 2009 industrial area of Brazil) HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Sakai et al Green 2 Japan Mature 11 8.7 14 Isl concentrations waters female 2000a 19th century mining - Cd, Zn, Magdalena Bay, Baja Cu and Pb in sediments above Specimens drowned SCL 47-77 Unknown Talavera-Saenz Green 8 Mexico 17 1.5 28 † California those in industrialised regions; in fishing nets cm gender et al 2007 Cd considered elevated Tortuguero National Dead, nesting turtles, Andreani et al Green 34 Costa Rica Cd considered background ND ND 22 ND ND † Park, North Carribean killed by jaguars 2008 Urban and industrial area; Hong Kong, Green 2 South China Sea exposed to relatively high Stranded specimens Juveniles ND 29 ND ND † Lam et al 2004 China levels of Se Adreaiatic and Ionian Generally considered Unknown Storelli et al Green 7 Italy Stranded Juveniles 33 18 59 Seas, Mediterranean contaminated gender 2008 118 Investigation of contaminant levels in green turtles from Gladstone Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 26 Japan Fishing nets 43 11 110 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Cd concentrations considered Juveniles Unknown Sakai et al Green 50 Japan Yaeyama Isl, Okinawa Caught by fishermen 50 4.3 110 high and adults gender 2000b Agricultural areas; relatively high Se in one pelagic Males and Aguirre et al Green 1 USA Pelagic, Hawaii Stranded specimens ND 56 1.3 130 specimen, but otherwise females 1994 considered "normal" Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive ND ND 59 0.84 180 Gladstone 1996 Co, Hg, Se Moribund, washed Juveniles Urbanised, potentially near van de Merwe Green 16 Australia Gold Coast, QLD up specimens, and ND 91 38 150 point sources et al 2010a euthanised subadults Moribund specimens Ahu-O-Laka, Agricultural areas; Se levels Males and Aguirre et al Green 6 USA with severe Juveniles 120 36 190 Kaneohe, HI considered "normal" females 1994 fibropapilloma Agricultural areas; Se levels Aguirre et al Green 1 USA Control, Captive Captive specimen ND Female 120 ND ND considered "normal" 1994 Yaeyama Islands, Renal Cd levels considered Mostly Males and Hawksbill 22 Japan Fishing nets 17 2.6 180 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Caurant et al Leatherback 18 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 8.6 1.1 20 1999 Stranded specimens Southwest Generally considered relatively from nesting Adults and Mostly Kaska et al Loggerhead 32 Turkey 0.66 0.059 0.92 † Mediterranean contaminated population, mainly subadults females 2004 fishing related deaths Aguirre et al Loggerhead 1 USA Pelagic, Hawaii Fishing net entanglement Stranded specimens ND Female 2.8 ND ND 1994 119 Investigation of contaminant levels in green turtles from Gladstone Cesenatico & Sicily Andreani et al Loggerhead 11 Italy Island, Cd considered background Stranded ND ND 3.9 ND ND † 2008 Mediterranean Caurant et al Loggerhead 7 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 8.3 2.3 21 1999 Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 15 0.010 66 Mediterranean contaminated areas 2004 subadults (n=67) Highest Cd in specimens with Females Sakai et al 1995 Fishing net Adults (SCL Loggerhead 7 Japan Cape Ashizuri, Kochi symptoms of kidney (n=6) and 18 6.5 34 Sakai et al entanglement 76-92) congestion n=1 male 2000a 120 Investigation of contaminant levels in green turtles from Gladstone 8.2.7 Iron (Fe) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles 66000 33000 96000 This study females healthy Relatively pristine, agriculture, shipyards & urban wastewater Live captured Labrada- Unknown Green 14 Mexico Bahia Magdalena discharge, 19th century specimens, Juveniles 300000 230000 410000 ˄ Martagón et al gender mining; Cd, Zn, Cu and Pb high apparently healthy 2011 in sediments Relatively pristine, agriculture, shipyards & urban wastewater Live captured Labrada- Unknown Green 42 Mexico Punta Abreojos discharge, 19th century specimens, Juveniles 340000 110000 520000 ˄ Martagón et al gender mining; Cd, Zn, Cu and Pb high apparently healthy 2011 in sediments Kidney (ppm ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles 15 11 21 This study females healthy Stranded specimens from nesting Southwest Generally considered relatively Adults and Mostly Kaska et al Green 14 Turkey population, mainly 1.5 1.0 2.3 † Mediterranean contaminated subadults females 2004 fishing related deaths 121 Investigation of contaminant levels in green turtles from Gladstone 19th century mining - Cd, Zn, Magdalena Bay, Baja Cu and Pb in sediments above Specimens drowned SCL 47-77 Unknown Talavera-Saenz Green 8 Mexico 11 ND 66 † California those in industrialised regions; in fishing nets cm gender et al 2007 Cd considered elevated Moribund specimens Males and Aguirre et al Green 6 USA Hawaii Agricultural areas with severe Juveniles 12 8.8 15 females 1994 fibropapilloma HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Sakai et al Green 2 Japan Mature 14 13 15 Isl concentrations waters female 2000a Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen Female 16 ND ND 1994 Cd concentrations considered Juveniles Unknown Sakai et al Green 23 Japan Yaeyama Isl, Okinawa Caught by fishermen 23 11 59 high and adults gender 2000b Dead, nesting Tortuguero National Andreani et al Green 33 Costa Rica Cd considered background turtles, killed by ND ND 36 ND ND † Park, North Carribean 2008 jaguars Males and Aguirre et al Green 5 USA Hawaii Agricultural areas Stranded specimens 87 23 180 females 1994 Stranded specimens from nesting Southwest Generally considered relatively Adults and Kaska et al Loggerhead 20 Turkey population, mainly ND 1.8 1.1 2.5 † Mediterranean contaminated subadults 2004 fishing related deaths Highest Cd in specimens with Adults Females Sakai et al Fishing net Loggerhead 7 Japan Cape Ashizuri, Kochi symptoms of kidney (SCL 76- (n=6) and 36 11 51 1995Sakai et al entanglement congestion 92) n=1 male 2000a Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 38 0.29 270 Mediterranean contaminated areas 2004 subadults (n=67) 122 Investigation of contaminant levels in green turtles from Gladstone Cesenatico & Sicily Andreani et al Loggerhead 9 Italy Cd considered background Stranded ND ND 92 ND ND † Island, Mediterranean 2008 Liver (ppm ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles 1939 1090 2821 This study females healthy Stranded specimens from nesting Southwest Generally considered relatively Adults and Mostly Kaska et al Green 22 Turkey population, mainly 1.5 0.45 2.1 † Mediterranean contaminated subadults females 2004 fishing related deaths 19th century mining - Cd, Zn, Magdalena Bay, Baja Cu and Pb in sediments above Specimens drowned SCL 47-77 Unknown Talavera-Saenz Green 8 Mexico 42 ND 81 † California those in industrialised regions; in fishing nets cm gender et al 2007 Cd considered elevated HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Sakai et al Green 2 Japan Mature 140 13 15 Isl concentrations waters female 2000a Dead, nesting Tortuguero National Andreani et al Green 34 Costa Rica Cd considered background turtles, killed by ND ND 300 ND ND † Park, North Carribean 2008 jaguars Cd concentrations considered Juveniles Unknown Sakai et al Green 50 Japan Yaeyama Isl, Okinawa Caught by fishermen 460 33 1300 high and adults gender 2000b Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen Female 770 1994 Males and Aguirre et al Green 6 USA Hawaii Agricultural areas Stranded specimens 840 93 1700 females 1994 Moribund specimens Males and Aguirre et al Green 6 USA Hawaii Agricultural areas with severe Juveniles 1600 450 2500 females 1994 fibropapilloma 123 Investigation of contaminant levels in green turtles from Gladstone Stranded specimens from nesting Southwest Generally considered relatively Adults and Kaska et al Loggerhead 32 Turkey population, mainly ND 1.9 0.85 2.8 † Mediterranean contaminated subadults 2004 fishing related deaths Cesenatico & Sicily Andreani et al Loggerhead 11 Italy Cd considered background Stranded ND ND 150 ND ND † Island, Mediterranean 2008 Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 340 0.35 2200 Mediterranean contaminated areas 2004 subadults (n=67) Highest Cd in specimens with Adults Females Sakai et al Fishing net Loggerhead 7 Japan Cape Ashizuri, Kochi symptoms of kidney (SCL 76- (n=6) and 650 230 930 1995Sakai et al entanglement congestion 92) n=1 male 2000a 124 Investigation of contaminant levels in green turtles from Gladstone 8.2.8 Lead (Pb) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 18 0.20 76 This study moribund and healthy females Moribund, washed up Juveniles Urbanised, potentially near van de Merwe et Green 16 Australia Gold Coast, QLD specimens, and ND 22 6.3 60 point sources al 2010a euthanised subadults Highly urbanised & Live captured Juveniles, Unknown Komoroske et al Green 30 USA San Diego 1300 ND ND contaminated estuary specimens Adults gender 2011 Young Ikonomopoulou et Flatback 20 Australia Curtis Isl, QLD Off the coast of Gladstone Live, nesting adults to Females <0.1 <0.1 <0.1 al 2011 adults French Industry, mining activities along Leatherback 78 French Guiana Nesting females Adult Females 180 130 230 ˄ Guirlet et al 2008 Guiana migration path Live captured, SCL 49- Unknown Ley-Quinonex et al Loggerhead 22 Mexico Baja California Sur ND <10 <10 <10 ˄ clinically healthy 83 cm gender 2011 Kidney (ppm ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 0.10 0.047 0.15 This study moribund and healthy females Tortuguero National Dead, nesting turtles, Andreani et al Green 33 Costa Rica Cd considered background ND ND 0.0053 ND ND † Park, North Carribean killed by jaguars 2008 125 Investigation of contaminant levels in green turtles from Gladstone 19th century mining - Cd, Zn, Cu Magdalena Bay, Baja and Pb in sediments above Specimens drowned in SCL 47- Unknown Talavera-Saenz et Green 8 Mexico 0.0060 ND 0.21 † California those in industrialised regions; fishing nets 77 cm gender al 2007 Cd considered elevated Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high levels Stranded specimens Juveniles ND 0.037 ND ND † Lam et al 2004 China of Se Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 0.070 0.050 0.15 Gladstone 1996 Co, Hg, Se HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Green 2 Japan Mature 0.085 <0.03 0.14 Sakai et al 2000a Isl concentrations waters female Moribund, washed up Juveniles Urbanised, potentially near van de Merwe et Green 16 Australia Gold Coast, QLD specimens, and ND 0.090 Males Yaeyama Islands, Renal Cd levels considered Mostly Green 25 Japan Fishing nets and 0.16 0.031 0.46 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Juveniles Cd concentrations considered Unknown Green 23 Japan Yaeyama Isl, Okinawa Caught by fishermen and 0.18 0.050 0.28 Sakai et al 2000b high gender adults Stranded specimens Adults Southwest Generally considered relatively from nesting Mostly Green 14 Turkey and 0.24 0.076 0.81 † Kaska et al 2004 Mediterranean contaminated population, mainly females subadults fishing related deaths Males Yaeyama Islands, Renal Cd levels considered Mostly Hawksbill 19 Japan Fishing nets and 0.053 0.017 0.22 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Loggerhead 1 Japan Cape Ashizuri, Kochi ND Fishing net ND M <0.03 ND ND Sakai et al 2000a 126 Investigation of contaminant levels in green turtles from Gladstone Cesenatico & Sicily Andreani et al Loggerhead 9 Italy Island, Cd considered background Stranded ND ND 0.012 ND ND † 2008 Mediterranean Loggerhead 6 Japan Cape Ashizuri, Kochi ND Fishing net ND F 0.16 ND ND Sakai et al 2000a Stranded specimens Adults Southwest Generally considered relatively from nesting Loggerhead 20 Turkey and ND 0.48 0.11 1.3 † Kaska et al 2004 Mediterranean contaminated population, mainly subadults fishing related deaths Juveniles Mainly Canary Islands, Generally considered relatively Loggerhead 78 Spain Stranded and females 2.4 0.020 17 Torrent et al 2004 Mediterranean contaminated areas subadults (n=67) Northern Cyprus, Generally contaminated, Loggerhead 2 Cyprus Stranded specimens Juveniles ND ND Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 0.16 0.12 0.20 This study moribund and healthy females Juveniles Cd concentrations considered Unknown Green 50 Japan Yaeyama Isl, Okinawa Caught by fishermen and <0.03 <0.03 <0.03 Sakai et al 2000b high gender adults Tortuguero National Dead, nesting turtles, Andreani et al Green 34 Costa Rica Cd considered background ND ND 0.015 ND ND † Park, North Carribean killed by jaguars 2008 Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high levels Stranded specimens Juveniles ND 0.033 ND ND † Lam et al 2004 China of Se HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Green 2 Japan Mature 0.075 <0.03 0.12 Sakai et al 2000a Isl concentrations waters female 127 Investigation of contaminant levels in green turtles from Gladstone Moribund, washed up Juveniles Urbanised, potentially near van de Merwe et Green 16 Australia Gold Coast, QLD specimens, and 0.090 Males Yaeyama Islands, Renal Cd levels considered Mostly Green 26 Japan Fishing nets and 0.16 0.018 0.48 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Sultanate Ras Al-Hadd Turtle Eggs incubated in contaminated Eggs collected from Al-Rawahy et al Green 50 Hatchling ND 0.27 ND ND of Oman Reserve soil nest 2007 Stranded specimens Adults Southwest Generally considered relatively from nesting Mostly Green 22 Turkey and 0.54 0.26 3.0 † Kaska et al 2004 Mediterranean contaminated population, mainly females subadults fishing related deaths Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 0.59 0.070 1.1 Gladstone 1996 Co, Hg, Se Northern Cyprus, Generally contaminated, Green 6 Cyprus Stranded specimens Juveniles ND ND 19th century mining - Cd, Zn, Cu Magdalena Bay, Baja and Pb in sediments above Specimens drowned in SCL 47- Unknown Talavera-Saenz et Green 8 Mexico ND ND 0.015 † California those in industrialised regions; fishing nets 77 cm gender al 2007 Cd considered elevated Males Yaeyama Islands, Renal Cd levels considered Mostly Hawksbill 22 Japan Fishing nets and 0.052 0.0062 0.17 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Cesenatico & Sicily Andreani et al Loggerhead 11 Italy Island, Cd considered background Stranded ND ND 0.022 ND ND † 2008 Mediterranean Loggerhead 6 Japan Cape Ashizuri, Kochi ND Fishing net ND F 0.080 ND ND Sakai et al 2000a Loggerhead 1 Japan Cape Ashizuri, Kochi ND Fishing net ND M 0.21 ND ND Sakai et al 2000a 128 Investigation of contaminant levels in green turtles from Gladstone Stranded specimens Adults Southwest Generally considered relatively from nesting Loggerhead 32 Turkey and ND 0.78 0.26 1.2 † Kaska et al 2004 Mediterranean contaminated population, mainly subadults fishing related deaths Juveniles Mainly Canary Islands, Generally considered relatively Loggerhead 78 Spain Stranded and females 2.9 0.050 33 Torrent et al 2004 Mediterranean contaminated areas subadults (n=67) Northern Cyprus, Generally contaminated, Loggerhead 4 Cyprus Stranded specimens Juveniles ND ND 129 Investigation of contaminant levels in green turtles from Gladstone 8.2.9 Manganese (Mn) Turtle Location/source Health & other Age Mea Ma n Country Location Gender Min Reference species information information class n x Blood (ppb ww) Unhealthy, incl. moribund Juvenil Males and Green 40 Australia Gladstone Industrialised port estuary 35 16 92 This study and healthy es females Juvenil Highly urbanised & Unknown Komoroske et Green 30 USA San Diego Live captured specimens es, 460 ND ND contaminated estuary gender al 2011 Adults Kidney (ppm ww) Unhealthy, incl. moribund Juvenil Males and Green 40 Australia Gladstone Industrialised port estuary 0.87 0.66 0.48 This study and healthy es females 19th century mining - Cd, Zn, Cu and Pb in sediments above SCL Magdalena Bay, Baja Specimens drowned in Unknown Talavera-Saenz Green 8 Mexico those in industrialised 47-77 0.18 ND 0.93 † California fishing nets gender et al 2007 regions; Cd considered cm elevated Pollution considered negligible (but 200 km south Juvenil Barbieri et al Green 30 Brazil Cananeia Estuary Stranded ND 0.46 ND ND † of major industrial area of e 2009 Brazil) Pollution considered negligible (but 200 km south Barbieri et al Green 30 Brazil Cananeia Estuary Stranded Adult ND 0.50 ND ND † of major industrial area of 2009 Brazil) Tortuguero National Dead, nesting turtles, Pooled Andreani et al Green 33 Costa Rica n=35 ND 0.69 ND ND † Park, North Carribean killed by jaguars sample 2008 130 Investigation of contaminant levels in green turtles from Gladstone Males and Aguirre et al Green 5 USA Hawaii Agricultural areas Stranded specimens ND 0.70 0.48 1.2 females 1994 Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen ND Female 0.82 ND ND 1994 Mostly Yaeyama Islands, Renal Cd levels considered Males and Green 25 Japan Fishing nets juvenil 1.1 0.54 1.6 ‡ Anan et al 2001 Okinawa Prefecture extremely high females es Juvenil Cd concentrations considered Unknown Sakai et al Green 23 Japan Yaeyama Isl, Okinawa Caught by fishermen es and 1.2 0.72 2.3 high gender 2000b adults Moribund specimens with Juvenil Males and Aguirre et al Green 6 USA Hawaii Agricultural areas 1.2 1.1 1.4 severe fibropapilloma es females 1994 HahaJima/OgaSawara Relatively high Cd Collected in coastal Matur Male and Sakai et al Green 2 Japan 1.3 1.1 1.6 Island concentrations waters e female 2000a Urban and industrial area; Hong Kong, Juvenil Green 2 South China Sea exposed to relatively high Stranded specimens ND 1.4 ND ND † Lam et al 2004 China es levels of Se Mostly Yaeyama Islands, Renal Cd levels considered Males and Hawksbill 19 Japan Fishing nets juvenil 2.6 1.2 3.5 ‡ Anan et al 2001 Okinawa Prefecture extremely high females es Cesenatico & Sicily Cesenatico (n=7) & Sicily Pooled Andreani et al Loggerhead 9 Italy Stranded ND 0.84 ND ND † Island Island (n=4) sample 2008 Highest Cd in specimens with Adults Females Sakai et al Loggerhead 7 Japan Cape Ashizuri, Kochi symptoms of kidney Fishing net entanglement (SCL (n=6) and 1.6 0.81 2.0 1995Sakai et al congestion 76-92) n=1 male 2000a Liver (ppm ww) Unhealthy, incl. moribund Juvenil Males and Green 40 Australia Gladstone Industrialised port estuary 2.6 2.5 2.3 This study and healthy es females 131 Investigation of contaminant levels in green turtles from Gladstone Pollution considered negligible (but 200 km south Barbieri et al Green 30 Brazil Cananeia Estuary Stranded Adult ND 0.95 ND ND † of major industrial area of 2009 Brazil) Sultanate Ras Al-Hadd Turtle Substantial industrial and Hatchli Al-Rawahy et al Green 50 Hatchlings; control ND 1.5 ND ND of Oman Reserve urban developments ng 2007 Males and Aguirre et al Green 6 USA Hawaii Agricultural areas Stranded specimens ND 1.6 0.15 2.8 females 1994 Moribund specimens with Juvenil Males and Aguirre et al Green 6 USA Hawaii Agricultural areas 1.6 1.2 2.0 severe fibropapilloma es females 1994 Juvenil Cd concentrations considered Unknown Sakai et al Green 50 Japan Yaeyama Isl, Okinawa Caught by fishermen es and 1.9 0.70 5.4 high gender 2000b adults HahaJima/OgaSawara Relatively high Cd Collected in coastal Matur Male and Sakai et al Green 2 Japan 1.9 1.9 1.9 Island concentrations waters e female 2000a Tortuguero National Dead, nesting turtles, Pooled Andreani et al Green 34 Costa Rica Cd considered background ND 2.0 ND ND † Park, North Carribean killed by jaguars sample 2008 Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen ND Female 2.1 ND ND 1994 Mostly Yaeyama Islands, Renal Cd levels considered Males and Green 26 Japan Fishing nets juvenil ND 0.70 3.4 ‡ Anan et al 2001 Okinawa Prefecture extremely high females es 19th century mining - Cd, Zn, Cu and Pb in sediments above SCL Magdalena Bay, Baja Specimens drowned in Unknown Talavera-Saenz Green 8 Mexico those in industrialised 47-77 ND ND 1.2 † California fishing nets gender et al 2007 regions; Cd considered cm elevated Yaeyama Islands, Renal Cd levels considered Males and Hawksbill 22 Japan Fishing nets Mostly 2.6 1.2 5.5 ‡ Anan et al 2001 Okinawa Prefecture extremely high juvenil females 132 Investigation of contaminant levels in green turtles from Gladstone es Cesenatico & Sicily Pooled Andreani et al Loggerhead 11 Italy Cd considered background Stranded ND 1.6 ND ND † Island, Mediterranean sample 2008 Adults Highest Cd in specimens with Females Sakai et al 1995 (SCL Loggerhead 7 Japan Cape Ashizuri, Kochi symptoms of kidney Fishing net entanglement (n=6) and 2.1 1.4 2.9 Sakai et al 76-92 congestion n=1 male 2000a cm) 133 Investigation of contaminant levels in green turtles from Gladstone 8.2.10 Mercury (Hg) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 9.3 <0.22 38 This study moribund and healthy females Highly urbanised & Live captured Juveniles, Unknown Komoroske et al Green 30 USA San Diego 1.0 ND ND contaminated estuary specimens Adults gender 2011 Juveniles Urbanised, potentially near Moribund, washed up van de Merwe Green 16 Australia Gold Coast, QLD and ND 2.5 0.25 7.1 point sources specimens, euthanised et al 2010a subadults Young Ikonomopoulou Flatback 20 Australia Curtis Isl, QLD Off the coast of Gladstone Live, nesting adults to Females <0.1 <0.1 <0.1 et al 2011 adults South Carolina & Widespread Hg impaired Emaciated, moribund Loggerhead 13 USA ND ND 6.4 ND ND Day et al 2010 Florida waterways, incl. superfund sites specimens, stranded French Industry, mining activities along Guirlet et al Leatherback 78 French Guiana Nesting females Adult Females 11 8.0 14 ˄ Guiana migration path 2008 Live specimens, some Males South Carolina & Widespread Hg impaired highly contaminated Loggerhead 34 USA Adults and 29 5.0 190 Day et al 2005 Florida waterways, incl. superfund sites individuals, correlated females to point sources Subadults South Carolina & Widespread Hg impaired Free ranging specimens, Loggerhead 66 USA and ND 29 6.0 77 Day et al 2007 Florida waterways, incl. superfund sites high Hg adults South Carolina & Widespread Hg impaired Live-captured, Loggerhead 100 USA ND ND 30 ND ND Day et al 2010 Florida waterways, incl. superfund sites apparently healthy 134 Investigation of contaminant levels in green turtles from Gladstone Stranded specimens, Males South Carolina & Widespread Hg impaired very high Hg levels, Loggerhead 34 USA Adults and 99 40.0 310 Day et al 2005 Florida waterways, incl. superfund sites point sources present in females area Nesting Paez-Osuna et Olive Ridley 25 Mexico Oaxaca Near pristine environment Apparently healthy Adults 0.15 ND ND ! females al 2011 Kidney (ppm ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 0.42 0.15 0.72 This study moribund and healthy females Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 0.020 0.010 0.040 Gladstone 1996 Co, Hg, Se Moreton Bay, QLD Urbanised port estuary; Cd Juveniles (incl. n=1 each from Stranded specimens; Gordon et al Green 23 Australia among the highest recorded for and ND 0.020 ND 0.049 Shoalwater and mainly unhealthy 1998 marine vertebrates adults Hervey Bays) Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high levels Stranded specimens Juveniles ND 0.041 ND ND † Lam et al 2004 China of Se HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Sakai et al Green 2 Japan Mature 0.045 0.042 0.048 Island concentrations waters female 2000a Males Yaeyama Islands, Renal Cd levels considered Mostly Green 25 Japan Fishing nets and 0.059 0.064 0.11 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Juveniles Urbanised, potentially near Moribund, washed up van de Merwe Green 16 Australia Gold Coast, QLD and ND 0.060 Gulf of California & Kampalath et al Green 10 Mexico Near pristine environment Healthy Juveniles ND 0.089 0.0030 0.31 Magdalena Bay 2006 135 Investigation of contaminant levels in green turtles from Gladstone Juveniles Cd concentrations considered Unknown Sakai et al Green 21 Japan Yaeyama Isl, Okinawa Caught by fishermen and 0.13 0.029 0.25 high gender 2000b adults Males Yaeyama Islands, Renal Cd levels considered Mostly Hawksbill 19 Japan Fishing nets and 0.25 0.016 0.98 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Urbanised port estuary; Cd Stranded specimens; Gordon et al Hawksbill 2 Australia Moreton Bay, QLD among the highest recorded for Unknown ND ND 0.034 0.038 mainly unhealthy 1998 marine vertebrates Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 0.040 0.010 0.33 Mediterranean contaminated areas 2004 subadults (n=67) Urbanised port estuary; Cd Stranded specimens; Gordon et al Loggerhead 3 Australia Moreton Bay, QLD among the highest recorded for Unknown ND 0.045 0.033 0.067 mainly unhealthy 1998 marine vertebrates Gulf of California & Kampalath et al Loggerhead 2 Mexico Near pristine environment Healthy Juveniles ND 0.10 0.064 0.14 Magdalena Bay 2006 Adults Females Sakai et al 1995 Highest Cd in specimens with Fishing net Loggerhead 7 Japan Cape Ashizuri, Kochi (SCL 76- (n=6) and 0.25 0.040 0.44 Sakai et al symptoms of kidney congestion entanglement 92) n=1 male 2000a Northern Cyprus, Generally contaminated, Godley et al Loggerhead 2 Cyprus Stranded specimens Juveniles ND ND 0.036 0.22 ‡ Mediterranean presence of natural Hg bed 1999 Gulf of California & Kampalath et al Olive Ridley 3 Mexico Near pristine environment Healthy Juveniles 0.14 0.028 0.37 Magdalena Bay 2006 Liver (ppm ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 1.3 0.86 1.6 This study moribund and healthy females 136 Investigation of contaminant levels in green turtles from Gladstone Moreton Bay, QLD Urbanised port estuary; Cd Juveniles (incl. n=1 each from Stranded specimens; Gordon et al Green 23 Australia among the highest recorded for and ND 0.021 ND 0.052 Shoalwater and mainly unhealthy 1998 marine vertebrates adults Hervey Bays) Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 0.080 0.020 0.17 Gladstone 1996 Co, Hg, Se Gulf of California & Kampalath et al Green 11 Mexico Near pristine environment Healthy Juveniles ND 0.091 0.026 0.17 Magdalena Bay 2006 Males Yaeyama Islands, Renal Cd levels considered Mostly Green 26 Japan Fishing nets and 0.13 0.071 0.27 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high levels Stranded specimens Juveniles ND 0.17 ND ND † Lam et al 2004 China of Se Juveniles Urbanised, potentially near Moribund, washed up van de Merwe Green 16 Australia Gold Coast, QLD and ND 0.19 HahaJima/OgaSawara Relatively high Cd Collected in coastal Male and Sakai et al Green 2 Japan Mature 0.19 0.077 0.30 Isl concentrations waters female 2000a Sultanate Ras Al-Hadd Turtle Substantial industrial and urban Al-Rawahy et al Green 50 Hatchlings; control Hatchling 0.22 of Oman Reserve developments 2007 Juveniles Cd concentrations considered Unknown Sakai et al Green 46 Japan Yaeyama Isl, Okinawa Caught by fishermen and 0.29 0.053 0.64 high gender 2000b adults Northern Cyprus, Generally contaminated, Godley et al Green 6 Cyprus Stranded specimens Juveniles ND ND 0.059 0.30 ‡ Mediterranean presence of natural Hg bed 1999 Males Yaeyama Islands, Renal Cd levels considered Mostly Hawksbill 22 Japan Fishing nets and 0.27 0.015 2.7 ‡ Anan et al 2001 Okinawa Prefecture extremely high juveniles females 137 Investigation of contaminant levels in green turtles from Gladstone Urbanised port estuary; Cd Stranded specimens; Gordon et al Hawksbill 2 Australia Moreton Bay, QLD among the highest recorded for Unknown ND ND 0.036 0.048 mainly unhealthy 1998 marine vertebrates Urbanised port estuary; Cd Stranded specimens; Gordon et al Loggerhead 6 Australia Moreton Bay, QLD among the highest recorded for Unknown ND 0.015 ND 0.032 mainly unhealthy 1998 marine vertebrates Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 0.040 0.0010 0.47 Mediterranean contaminated areas 2004 subadults (n=67) Gulf of California & Kampalath et al Loggerhead 4 Mexico Near pristine environment Healthy Juveniles ND 0.15 0.12 0.18 Magdalena Bay 2006 Adults Females Sakai et al 1995 Highest Cd in specimens with Fishing net Loggerhead 7 Japan Cape Ashizuri, Kochi (SCL 76- (n=6) and 1.5 0.25 8.2 Sakai et al symptoms of kidney congestion entanglement 92) n=1 male 2000a Northern Cyprus, Generally contaminated, Godley et al Loggerhead 5 Cyprus Stranded specimens Juveniles ND ND 0.18 1.7 † Mediterranean presence of natural Hg bed 1999 Gulf of California & Kampalath et al Olive Ridley 6 Mexico Near pristine environment Healthy Juveniles ND 0.21 0.057 0.80 Magdalena Bay 2006 138 Investigation of contaminant levels in green turtles from Gladstone 8.2.11 Molybdenum (Mo) Turtle Location/source Health & other n Country Location Age class Gender Mean Min Max Reference species information information Blood (ppb ww) Unhealthy, incl. Males and Green 40 Gladstone Australia Industrialised port estuary Juveniles 11 4.6 83 This study moribund and healthy females Young Ikonomopoulou Flatback 20 Curtis Isl, QLD Australia Off the coast of Gladstone Live, nesting adults to Females <0.1 <0.1 <0.1 et al 2011 adults Kidney (ppm ww) Unhealthy, incl. Males and Green 40 Gladstone Australia Industrialised port estuary Juveniles 0.16 0.062 0.30 This study moribund and healthy females Urban and industrial area; Hong Kong, Green 2 South China Sea exposed to relatively high Stranded specimens Juveniles ND 0.094 ND ND † Lam et al 2004 China levels of Se Aguirre et al Green 1 Control, Captive USA Agricultural areas Captive specimen ND Female 0.10 1994 Males and Aguirre et al Green 3 Hawaii USA Agricultural areas Stranded specimens ND 0.13 0.10 0.20 females 1994 Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 25 Okinawa Japan Fishing nets 0.13 0.053 0.30 ‡ Anan et al 2001 extremely high juveniles females Prefecture Moribund specimens Males and Aguirre et al Green 6 Hawaii USA Agricultural areas with severe Juveniles 0.25 0.20 0.30 females 1994 fibropapilloma Renal Cd levels considered Mostly Males and Hawksbill 19 Yaeyama Islands, Japan Fishing nets 0.28 0.084 0.58 ‡ Anan et al 2001 Okinawa extremely high juveniles females 139 Investigation of contaminant levels in green turtles from Gladstone Prefecture Liver (ppm ww) Unhealthy, incl. Males and Green 40 Gladstone Australia Industrialised port estuary Juveniles 0.54 0.39 0.83 This study moribund and healthy females Aguirre et al Green 1 Control, Captive USA Agricultural areas Captive specimen ND Female 0.10 ND ND 1994 Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 26 Okinawa Japan Fishing nets 0.17 0.024 0.37 ‡ Anan et al 2001 extremely high juveniles females Prefecture Males and Aguirre et al Green 2 Hawaii USA Agricultural areas Stranded specimens ND 0.25 0.20 0.30 females 1994 Urban and industrial area; Hong Kong, Green 2 South China Sea exposed to relatively high Stranded specimens Juveniles ND 0.27 ND ND † Lam et al 2004 China levels of Se Moribund specimens Males and Aguirre et al Green 6 Hawaii USA Agricultural areas with severe Juveniles 0.30 0.20 0.60 females 1994 fibropapilloma Yaeyama Islands, Renal Cd levels considered Mostly Males and Hawksbill 22 Okinawa Japan Fishing nets 0.36 0.061 1.3 ‡ Anan et al 2001 extremely high juveniles females Prefecture 140 Investigation of contaminant levels in green turtles from Gladstone 8.2.12 Nickel (Ni) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 5.2 0.67 17 This study moribund and healthy females Young Ikonomopoulou Flatback 20 Australia Curtis Isl, QLD Off the coast of Gladstone Live, nesting adults to Females <0.1 <0.1 <0.1 et al 2011 adults Olive Various possible sources along Paez-Osuna et al 25 Mexico Oaxaca Live, nesting Adults Females 76 ND ND # Ridley migration route 2010 Kidney (ppm ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 9.0 0.42 26 This study moribund and healthy females Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Juvenile ND 0.011 ND ND † 2009 industrial area of Brazil) Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Adult ND 0.023 ND ND † 2009 industrial area of Brazil) Hong Urban and industrial area; exposed Green 2 Kong, South China Sea Stranded specimens Juveniles ND 0.024 ND ND † Lam et al 2004 to relatively high levels of Se China Magdalena Bay, Baja 19th century mining - Cd, Zn, Cu Specimens drowned in SCL 47- Unknown Talavera-Saenz Green 8 Mexico 0.38 0.14 3.0 † California and Pb in sediments above those in fishing nets 77 cm gender et al 2007 industrialised regions; Cd 141 Investigation of contaminant levels in green turtles from Gladstone considered elevated HahaJima/OgaSawara Collected in coastal Male and Green 2 Japan Relatively high Cd concentrations Mature 0.51 0.46 0.56 Sakai et al 2000a Isl waters female Juveniles Unknown Green 23 Japan Yaeyama Isl, Okinawa Cd concentrations considered high Caught by fishermen and 0.62 0.12 1.3 Sakai et al 2000b gender adults Moribund specimens Males Ahu-O-Laka, Aguirre et al Green 5 USA Agricultural areas with severe Juveniles and 0.78 0.50 0.90 Kaneohe, HI 1994 fibropapilloma females Aguirre et al Green 1 USA Pelagic, Hawaii Agricultural areas Stranded specimen ND Female 0.80 ND ND 1994 Stranded specimens Adults Southwest Generally considered relatively from nesting Mostly Green 14 Turkey and 1.2 0.51 1.7 † Kaska et al 2004 Mediterranean contaminated population, mainly females subadults fishing related deaths Adults Females Highest Cd in specimens with Fishing net Sakai et al 1995 Loggerhead 7 Japan Cape Ashizuri, Kochi (SCL 76- (n=6) and 0.16 <0.03 0.27 symptoms of kidney congestion entanglement Sakai et al 2000a 92) n=1 male Stranded specimens Adults Southwest Generally considered relatively from nesting Loggerhead 20 Turkey and ND 1.2 0.52 1.5 † Kaska et al 2004 Mediterranean contaminated population, mainly subadults fishing related deaths Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 5.8 0.040 48 Mediterranean contaminated areas; high Ni levels 2004 subadults (n=67) Liver (ppm ww) Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles Males 0.20 0.17 0.23 This study moribund and healthy and 142 Investigation of contaminant levels in green turtles from Gladstone females Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Juvenile ND 0.029 ND ND † 2009 industrial area of Brazil) Hong Urban and industrial area; exposed Green 2 Kong, South China Sea Stranded specimens Juveniles ND 0.059 ND ND † Lam et al 2004 to relatively high levels of Se China Pollution considered negligible Barbieri et al Green 30 Brazil Cananeia Estuary (but 200 km south of major Stranded Adult ND 0.062 ND ND † 2009 industrial area of Brazil) Juveniles Unknown Green 50 Japan Yaeyama Isl, Okinawa Cd concentrations considered high Caught by fishermen and ND 0.060 0.31 Sakai et al 2000b gender adults HahaJima/OgaSawara Collected in coastal Male and Green 1 Japan Relatively high Cd concentrations Mature 0.065 0.059 0.071 Sakai et al 2000a Isl waters female Sultanate Ras Al-Hadd Turtle Substantial industrial and urban Al-Rawahy et al Green 50 Hatchlings; control Hatchling ND 0.090 ND ND of Oman Reserve developments 2007 Stranded specimens Adults Southwest Generally considered relatively from nesting Mostly Green 22 Turkey and 2.0 1.3 2.8 † Kaska et al 2004 Mediterranean contaminated population, mainly females subadults fishing related deaths 19th century mining - Cd, Zn, Cu Magdalena Bay, Baja and Pb in sediments above those in Specimens drowned in SCL 47- Unknown Talavera-Saenz Green 8 Mexico ND ND 6.8 † California industrialised regions; Cd fishing nets 77 cm gender et al 2007 considered elevated Adults Females Highest Cd in specimens with Fishing net Sakai et al 1995 Loggerhead 7 Japan Cape Ashizuri, Kochi (SCL 76- (n=6) and <0.03 ND ND symptoms of kidney congestion entanglement Sakai et al 2000a 92) n=1 male 143 Investigation of contaminant levels in green turtles from Gladstone Stranded specimens Adults Southwest Generally considered relatively from nesting Loggerhead 32 Turkey and ND 2.5 1.2 3.7 † Kaska et al 2004 Mediterranean contaminated population, mainly subadults fishing related deaths Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 2.9 0.010 14 Mediterranean contaminated areas 2004 subadults (n=67) 144 Investigation of contaminant levels in green turtles from Gladstone 8.2.13 Selenium (Se) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 1900 84 8600 This study moribund and healthy females Highly urbanised & contaminated Live captured Juveniles, Unknown Green 30 USA San Diego 780 ND ND Komoroske et al 2011 estuary specimens Adults gender Relatively pristine, agriculture, shipyards & urban wastewater Live captured Unknown Labrada-Martagón et Green 40 Mexico Punta Abreojos discharge, 19th century mining; specimens, Juveniles 1600 30 5700 ˄ gender al 2011 Cd, Zn, Cu and Pb high in apparently healthy sediments Relatively pristine, agriculture, shipyards & urban wastewater Live captured Unknown Labrada-Martagón et Green 14 Mexico Bahia Magdalena discharge, 19th century mining; specimens, Juveniles 1800 150 4700 ˄ gender al 2011 Cd, Zn, Cu and Pb high in apparently healthy sediments Moribund, washed up Juveniles Urbanised, potentially near point Van de Merwe et al Green 16 Australia Gold Coast, QLD specimens, and ND 2400 68 9100 sources 2010a euthanised subadults Kidney (ppm ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 1.3 0.62 2.4 This study moribund and healthy females Ahu-O-Laka, Agricultural areas; Se levels Green 6 USA Moribund specimens Juveniles Males 0.42 0.21 0.96 Aguirre et al 1994 Kaneohe, HI considered "normal" with severe and 145 Investigation of contaminant levels in green turtles from Gladstone fibropapilloma females Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive ND ND 0.45 0.16 1.3 Gladstone 1996 Co, Hg, Se Moreton Bay, QLD Urbanised port estuary; Cd among Juveniles (incl. n=1 each Stranded specimens; Green 23 Australia the highest recorded for marine and ND 0.59 0.090 1.9 Gordon et al 1998 from Shoalwater mainly unhealthy vertebrates adults and Hervey Bays) Agricultural areas; Se levels Green 1 USA Control, Captive Captive specimen ND Female 0.70 ND ND Aguirre et al 1994 considered "normal" Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high levels of Stranded specimens Juveniles ND 0.71 ND ND † Lam et al 2004 China Se Agricultural areas; relatively high Males Green 5 USA Pelagic, Hawaii Se in one pelagic specimen, but Stranded specimens ND and 0.75 0.19 1.6 Aguirre et al 1994 otherwise considered "normal" females Stranded specimens Adults Southwest Generally considered relatively from nesting Mostly Green 14 Turkey and 0.94 0.31 1.4 † Kaska et al 2004 Mediterranean contaminated population, mainly females subadults fishing related deaths Yaeyama Islands, Males Renal Cd levels considered Mostly Green 25 Japan Okinawa Fishing nets and 1.0 0.41 2.1 ‡ Anan et al 2001 extremely high juveniles Prefecture females Moribund, washed up Juveniles Urbanised, potentially near point Van de Merwe et al Green 16 Australia Gold Coast, QLD specimens, and ND 1.7 0.29 5.1 sources 2010a euthanised subadults Urbanised port estuary; Cd among Stranded specimens; Hawksbill 2 Australia Moreton Bay, QLD the highest recorded for marine Unknown ND ND 2.2 2.5 Gordon et al 1998 mainly unhealthy vertebrates 146 Investigation of contaminant levels in green turtles from Gladstone Yaeyama Islands, Males Renal Cd levels considered Mostly Hawksbill 19 Japan Okinawa Fishing nets and 5.5 1.8 15 ‡ Anan et al 2001 extremely high juveniles Prefecture females Stranded specimens Adults Southwest Generally considered relatively from nesting Mostly Loggerhead 20 Turkey and 0.93 0.31 1.7 † Kaska et al 2004 Mediterranean contaminated population, mainly females subadults fishing related deaths Urbanised port estuary; Cd among Juveniles Stranded specimens; Loggerhead 3 Australia Moreton Bay, QLD the highest recorded for marine and ND 1.5 1.3 1.8 Gordon et al 1998 mainly unhealthy vertebrates adults Liver (ppm ww) Males Unhealthy, incl. Green 40 Australia Gladstone Industrialised port estuary Juveniles and 5.4 4.0 7.2 This study moribund and healthy females Sultanate Ras Al-Hadd Turtle Substantial industrial and urban Green 12 Hatchlings; control Hatchling ND 0.22 ND ND Al-Rawahy et al 2007 of Oman Reserve developments Moribund specimens Males Ahu-O-Laka, Agricultural areas; Se levels Green 6 USA with severe Juveniles and 0.55 0.14 0.90 Aguirre et al 1994 Kaneohe, HI considered "normal" fibropapilloma females Agricultural areas; relatively high Males Green 5 USA Pelagic, Hawaii Se in one pelagic specimen, but Stranded specimens ND and 0.79 0.14 2.53 Aguirre et al 1994 otherwise considered "normal" females Agricultural areas; Se levels Green 1 USA Control, Captive Captive specimen ND Female 1.0 ND ND Aguirre et al 1994 considered "normal" Remote, very high Cd, elevated Green 7 Australia Waru, Torres Strait Caught alive ND ND 1.1 0.34 3.4 Gladstone 1996 Co, Hg, Se Urbanised port estuary; Cd among Juveniles Moreton Bay, QLD Stranded specimens; Green 23 Australia the highest recorded for marine and ND 1.2 0.070 2.7 Gordon et al 1998 (incl. n=1 each mainly unhealthy from Shoalwater vertebrates adults 147 Investigation of contaminant levels in green turtles from Gladstone and Hervey Bays) Yaeyama Islands, Males Renal Cd levels considered Mostly Green 26 Japan Okinawa Fishing nets and 1.6 0.62 3.1 ‡ Anan et al 2001 extremely high juveniles Prefecture females Stranded specimens Adults Southwest Generally considered relatively from nesting Green 22 Turkey and ND 2.3 0.22 4.2 † Kaska et al 2004 Mediterranean contaminated population, mainly subadults fishing related deaths Moribund, washed up Juveniles Urbanised, potentially near point Van de Merwe et al Green 16 Australia Gold Coast, QLD specimens, and ND 4.0 0.52 10 sources 2010a euthanised subadults Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high levels of Stranded specimens Juveniles ND 5.6 ND ND † Lam et al 2004 China Se Urbanised port estuary; Cd among Stranded specimens; Hawksbill 2 Australia Moreton Bay, QLD the highest recorded for marine Unknown ND ND 2.7 3.7 Gordon et al 1998 mainly unhealthy vertebrates Yaeyama Islands, Males Renal Cd levels considered Mostly Hawksbill 22 Japan Okinawa Fishing nets and 15 3.7 46 ‡ Anan et al 2001 extremely high juveniles Prefecture females Urbanised port estuary; Cd among Juveniles Stranded specimens; Loggerhead 6 Australia Moreton Bay, QLD the highest recorded for marine and ND 2.2 1.4 2.7 Gordon et al 1998 mainly unhealthy vertebrates adults Stranded specimens Adults Southwest Generally considered relatively from nesting Mostly Loggerhead 32 Turkey and 2.8 0.70 4.9 † Kaska et al 2004 Mediterranean contaminated population, mainly females subadults fishing related deaths 148 Investigation of contaminant levels in green turtles from Gladstone 8.2.14 Silver (Ag) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 0.66 0.011 7.1 This study moribund and healthy females Highly urbanised & contaminated Live captured Juveniles, Unknown Komoroske et Green 30 USA San Diego 1.6 ND ND estuary specimens Adults gender al 2011 Kemp's Live captured Males and Kenyon et al 106 USA USA Texas and Louisiana ND 0.94 0 3 Ridley specimens females 2001 Kidney (ppm ww) Unhealthy, incl. Males and Green 3 Australia Gladstone Industrialised port estuary Juveniles ND ND ND This study moribund and healthy females Yaeyama Islands, Renal Cd levels considered Mostly Males and Anan et al Green 25 Japan Okinawa Fishing nets 0.0035 0.00036 0.014 ‡ extremely high juveniles females 2001 Prefecture Hong Urban and industrial area; exposed Green 2 Kong, South China Sea Stranded specimens Juveniles ND 0.007 ND ND † Lam et al 2004 to relatively high levels of Se China Yaeyama Islands, Renal Cd levels considered Mostly Males and Anan et al Hawksbill 19 Japan Okinawa Fishing nets 0.0023 0.0011 0.0046 ‡ extremely high juveniles females 2001 Prefecture Liver (ppm ww) Unhealthy, incl. Males and Green 3 Australia Gladstone Industrialised port estuary Juveniles ND ND ND This study moribund and healthy females Yaeyama Islands, Green 26 Japan Renal Cd levels considered Fishing nets Mostly Males and 0.70 0.15 2.0 ‡ Anan et al Okinawa 149 Investigation of contaminant levels in green turtles from Gladstone Prefecture extremely high juveniles females 2001 Hong Urban and industrial area; exposed Green 2 Kong, South China Sea Stranded specimens Juveniles ND 0.78 ND ND † Lam et al 2004 to relatively high levels of Se China Yaeyama Islands, Renal Cd levels considered Mostly Males and Anan et al Hawksbill 22 Japan Okinawa Fishing nets 0.31 0.037 0.73 ‡ extremely high juveniles females 2001 Prefecture 150 Investigation of contaminant levels in green turtles from Gladstone 8.2.15 Vanadium (V) Turtle Location/source Health & other n Country Location Age class Gender Mean Min Max Reference species information information Blood (ppb ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 12 3.5 38 This study moribund and healthy females Urbanised, potentially near Males and Green 9 Australia Moreton Bay Live captured Juveniles 2.8 0.29 8.5 Unpublished data point sources females Kidney (ppm ww) Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 0.30 0.23 0.34 This study moribund and healthy females Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high Stranded specimens Juveniles ND 0.058 ND ND † Lam et al 2004 China levels of Se Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 25 Japan Okinawa Fishing nets 0.31 0.045 0.70 ‡ Anan et al 2001 extremely high juveniles females Prefecture Moribund specimens Males and Green 2 USA Hawaii Agricultural areas with severe Juveniles 0.50 0.30 0.70 Aguirre et al 1994 females fibropapilloma Males and Green 1 USA Hawaii Agricultural areas Stranded specimens ND 2.5 ND ND Aguirre et al 1994 females Yaeyama Islands, Renal Cd levels considered Mostly Males and Hawksbill 19 Japan Okinawa Fishing nets 0.090 0.019 0.23 ‡ Anan et al 2001 extremely high juveniles females Prefecture Liver (ppm ww) 151 Investigation of contaminant levels in green turtles from Gladstone Unhealthy, incl. Males and Green 40 Australia Gladstone Industrialised port estuary Juveniles 0.45 0.23 0.79 This study moribund and healthy females Hong Urban and industrial area; Green 2 Kong, South China Sea exposed to relatively high Stranded specimens Juveniles ND 0.13 ND ND † Lam et al 2004 China levels of Se Yaeyama Islands, Renal Cd levels considered Mostly Males and Green 26 Japan Okinawa Fishing nets 0.29 0.020 0.74 ‡ Anan et al 2001 extremely high juveniles females Prefecture Green 1 USA Control, Captive Agricultural areas Captive specimen Female 0.30 ND ND Aguirre et al 1994 Sultanate Ras Al-Hadd Substantial industrial and Al-Rawahy et al Green 50 Hatchlings; control Hatchling ND 0.36 ND ND of Oman Turtle Reserve urban developments 2007 Males and Green 4 USA Hawaii Agricultural areas Stranded specimens ND 0.53 0.20 0.90 Aguirre et al 1994 females Moribund specimens Males and Green 6 USA Hawaii Agricultural areas with severe Juveniles 0.83 0.30 1.5 Aguirre et al 1994 females fibropapilloma Yaeyama Islands, Renal Cd levels considered Mostly Males and Hawksbill 22 Japan Okinawa Fishing nets 0.11 0.017 0.34 ‡ Anan et al 2001 extremely high juveniles females Prefecture 152 Investigation of contaminant levels in green turtles from Gladstone 8.2.16 Zinc (Zn) Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppb ww) Unhealthy, incl. Males Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles and 8400 3800 12000 This study healthy females Relatively pristine, agriculture, Live captured Labrada- shipyards & urban wastewater Unknown Green 42 Mexico Punta Abreojos specimens, Juveniles 14000 460 20000 ˄ Martagón et al discharge, 19th century mining; Cd, gender apparently healthy 2011 Zn, Cu and Pb high in sediments Relatively pristine, agriculture, Live captured Labrada- shipyards & urban wastewater Unknown Green 14 Mexico Bahia Magdalena specimens, Juveniles 14000 11000 19000 ˄ Martagón et al discharge, 19th century mining; Cd, gender apparently healthy 2011 Zn, Cu and Pb high in sediments Moribund, washed Juveniles Urbanised, potentially near point van de Merwe Green 16 Australia Gold Coast, QLD up specimens, and ND 7900 3500 12000 sources et al 2010a euthanised subadults Young Ikonomopoulou Flatback 20 Australia Curtis Isl, QLD Off the coast of Gladstone Live, nesting adults to Females 150 98 210 et al 2011 adults French Industry, mining activities along Guirlet et al Leatherback 78 French Guiana Nesting females Adult Females 11000 11000 11000 ˄ Guiana migration path 2008 Kidney (ppm ww) Unhealthy, incl. Males Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles and 33 20 40 This study healthy females 153 Investigation of contaminant levels in green turtles from Gladstone HahaJima/OgaSawara Collected in coastal Male and Sakai et al Green 2 Japan Relatively high Cd concentrations Mature 34 33 35 Isl waters female 2000a Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen ND Female 32 ND ND 1994 Moribund Males specimens with Aguirre et al Green 6 USA Hawaii Agricultural areas Juveniles and 26 20 38 severe 1994 females fibropapilloma 19th century mining - Cd, Zn, Cu and Magdalena Bay, Baja Pb in sediments above those in Specimens drowned SCL 47- Unknown Talavera-Saenz Green 8 Mexico 23 12 34 † California industrialised regions; Cd considered in fishing nets 77 cm gender et al 2007 elevated Hong Urban and industrial area; exposed to Green 2 Kong, South China Sea Stranded specimens Juveniles ND 17 ND ND † Lam et al 2004 relatively high levels of Se China Males Aguirre et al Green 5 USA Hawaii Agricultural areas Stranded specimens ND and 16 16 16 1994 females Dead, nesting Tortuguero National Andreani et al Green 33 Costa Rica Cd considered background turtles, killed by ND ND 9.3 ND ND † Park, North Carribean 2008 jaguars Juveniles Unknown Sakai et al Green 23 Japan Yaeyama Isl, Okinawa Cd concentrations considered high Caught by fishermen and 30 18 45 gender 2000b adults Moribund, washed Juveniles Urbanised, potentially near point van de Merwe Green 16 Australia Gold Coast, QLD up specimens, and ND 29 18 48 sources et al 2010a euthanised subadults Adreaiatic and Ionian Unknown Storelli et al Green 7 Italy Generally considered contaminated Stranded Juveniles 26 15 38 Seas, Mediterranean gender 2008 154 Investigation of contaminant levels in green turtles from Gladstone Remote, very high Cd, elevated Co, Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 24 19 28 Gladstone 1996 Hg, Se Moreton Bay, QLD Urbanised port estuary; Cd among Juveniles (incl. n=1 each from Stranded specimens; Gordon et al Green 30 Australia the highest recorded for marine and ND 21 15 32 Shoalwater and mainly unhealthy 1998 vertebrates adults Hervey Bays) Males Yaeyama Islands, Renal Cd levels considered extremely Mostly Hawksbill 19 Japan Fishing nets and 23 16 39 ‡ Anan et al 2001 Okinawa Prefecture high juveniles females Urbanised port estuary; Cd among Stranded specimens; Gordon et al Hawksbill 3 Australia Moreton Bay, QLD the highest recorded for marine Unknown ND ND 13 21 mainly unhealthy 1998 vertebrates Caurant et al Leatherback 5 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 26 19 34 1999 Adults Females Sakai et al 1995 Highest Cd in specimens with Fishing net Loggerhead 7 Japan Cape Ashizuri, Kochi (SCL 76- (n=6) and 26 19 30 Sakai et al symptoms of kidney congestion entanglement 92) n=1 male 2000a Caurant et al Loggerhead 5 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 24 17 34 1999 Cesenatico & Sicily Andreani et al Loggerhead 9 Italy Island, Cd considered background Stranded ND ND 14 ND ND † 2008 Mediterranean Juveniles Mainly Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded and females 9.1 0.070 39 Mediterranean contaminated areas 2004 subadults (n=67) Urbanised port estuary; Cd among Stranded specimens; Gordon et al Loggerhead 5 Australia Moreton Bay, QLD the highest recorded for marine Unknown ND 18 17 21 mainly unhealthy 1998 vertebrates Urbanised port estuary; Cd among Olive Ridley 1 Australia Moreton Bay, QLD Stranded specimens; Unknown ND 19 ND ND Gordon et al the highest recorded for marine 155 Investigation of contaminant levels in green turtles from Gladstone vertebrates mainly unhealthy 1998 Liver (ppm ww) Unhealthy, incl. Males Green 40 Australia Gladstone Industrialised port estuary moribund and Juveniles and 46 41 51 This study healthy females Dead, nesting Tortuguero National Andreani et al Green 34 Costa Rica Cd considered background turtles, killed by ND ND 18 ND ND † Park, North Carribean 2008 jaguars 19th century mining - Cd, Zn, Cu and Magdalena Bay, Baja Pb in sediments above those in Specimens drowned SCL 47- Unknown Talavera-Saenz Green 8 Mexico 20 9.2 24 † California industrialised regions; Cd considered in fishing nets 77 cm gender et al 2007 elevated Males Aguirre et al Green 6 USA Hawaii Agricultural areas Stranded specimens ND and 23 15 40 1994 females Sultanate Ras Al-Hadd Turtle Substantial industrial and urban Al-Rawahy et al Green 50 Hatchlings; control Hatchling ND 23 ND ND of Oman Reserve developments 2007 Males Yaeyama Islands, Renal Cd levels considered extremely Mostly Green 26 Japan Fishing nets and 27 13 51 ‡ Anan et al 2001 Okinawa Prefecture high juveniles females Hong Urban and industrial area; exposed to Green 2 Kong, South China Sea Stranded specimens Juveniles ND 28 ND ND † Lam et al 2004 relatively high levels of Se China Juveniles Unknown Sakai et al Green 50 Japan Yaeyama Isl, Okinawa Cd concentrations considered high Caught by fishermen and 30 18 47 gender 2000b adults Males Yaeyama Islands, Renal Cd levels considered extremely Mostly Green 25 Japan Fishing nets and 33 17 69 ‡ Anan et al 2001 Okinawa Prefecture high juveniles females 156 Investigation of contaminant levels in green turtles from Gladstone Adreaiatic and Ionian Unknown Storelli et al Green 7 Italy Generally considered contaminated Stranded Juveniles 35 19 54 Seas, Mediterranean gender 2008 Moribund, washed Juveniles Urbanised, potentially near point van de Merwe Green 16 Australia Gold Coast, QLD up specimens, and ND 36 21 47 sources et al 2010a euthanised subadults Moribund Males specimens with Aguirre et al Green 6 USA Hawaii Agricultural areas Juveniles and 37 25 46 severe 1994 females fibropapilloma Aguirre et al Green 1 USA Control, Captive Agricultural areas Captive specimen ND Female 38 ND ND 1994 Remote, very high Cd, elevated Co, Green 7 Australia Waru, Torres Strait Caught alive Unknown ND 39 24 52 Gladstone 1996 Hg, Se Moreton Bay, QLD Urbanised port estuary; Cd among Juveniles (incl. n=1 each from Stranded specimens; Gordon et al Green 30 Australia the highest recorded for marine and ND 40 17 93 Shoalwater and mainly unhealthy 1998 vertebrates adults Hervey Bays) HahaJima/OgaSawara Collected in coastal Male and Sakai et al Green 2 Japan Relatively high Cd concentrations Mature 58 57 60 Isl waters female 2000a Urbanised port estuary; Cd among Stranded specimens; Gordon et al Hawksbill 3 Australia Moreton Bay, QLD the highest recorded for marine Unknown ND ND 18 30 mainly unhealthy 1998 vertebrates Males Yaeyama Islands, Renal Cd levels considered extremely Mostly Hawksbill 22 Japan Fishing nets and 34 16 95 ‡ Anan et al 2001 Okinawa Prefecture high juveniles females Caurant et al Leatherback 18 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 29 22 37 1999 Canary Islands, Generally considered relatively Torrent et al Loggerhead 78 Spain Stranded Juveniles Mainly 13 0.090 91 Mediterranean contaminated areas and females 2004 157 Investigation of contaminant levels in green turtles from Gladstone subadults (n=67) Cesenatico & Sicily Andreani et al Loggerhead 11 Italy Island, Cd considered background Stranded ND ND 23 ND ND † 2008 Mediterranean Urbanised port estuary; Cd among Stranded specimens; Gordon et al Loggerhead 5 Australia Moreton Bay, QLD the highest recorded for marine Unknown ND 23 14 33 mainly unhealthy 1998 vertebrates Caurant et al Loggerhead 7 France French Atlantic Coast Cd considered high Stranded, dead Juvenile ND 25 15 38 1999 Adults Females Sakai et al 1995 Highest Cd in specimens with Fishing net Loggerhead 7 Japan Cape Ashizuri, Kochi (SCL 76- (n=6) and 28 23 35 Sakai et al symptoms of kidney congestion entanglement 92) n=1 male 2000a Urbanised port estuary; Cd among Stranded specimens; Gordon et al Olive Ridley 1 Australia Moreton Bay, QLD the highest recorded for marine Unknown ND 15 ND ND mainly unhealthy 1998 vertebrates 158 Investigation of contaminant levels in green turtles from Gladstone 8.2.17 Dioxins Turtle Location/source Health & other Age n Country Location Gender Mean Min Max Reference species information information class Blood (ppt lw) Unhealthy, incl. moribund Males and Green 21 Australia Gladstone Industrialised port estuary Juveniles 19 <7.1 39 This study and healthy females Green 1 Australia Gladstone Industrialised port estuary Unhealthy Adult Unknown 130 This study Distant to urban and port Live captured specimens, Males and Hermanussen Green 4 Australia Shoalwater Adults 14 9.0 21 development mostly apparently healthy females 2009 Eastern Relatively distant to urban and Live captured specimens, Males and Hermanussen Green 14 Australia Adults 15 5.4 24 Moreton Bay port development mostly apparently healthy females 2009 Eastern Relatively distant to urban and Live captured specimens, Hermanussen Green 6 Australia Juveniles Females 17 6.0 22 Moreton Bay port development mostly apparently healthy 2009 Distant to urban and port Live captured specimens, Hermanussen Green 2 Australia Shoalwater Juveniles Unknown 27 24 29 development mostly apparently healthy 2009 Relatively close to urban and Live captured specimens, Males and Hermanussen Green 6 Australia Hervey Bay Adults 33 9.6 71 port development mostly apparently healthy females 2009 Western Close to urban and port Live captured specimens, Males and Hermanussen Green 10 Australia Juveniles 40 22 79 Moreton Bay development mostly apparently healthy females 2009 Relatively close to urban and Live captured specimens, Males and Hermanussen Green 9 Australia Hervey Bay Juveniles 78 37 120 port development mostly apparently healthy females 2009 Western Close to urban and port Live captured specimens, Males and Hermanussen Green 4 Australia Adults 130 16 290 Moreton Bay development mostly apparently healthy females 2009 159 Investigation of contaminant levels in green turtles from Gladstone † Converted x0.12 (kidney) x0.22 (liver) according to values of this study ‡ Converted x0.195 (kidney) x0.309 (liver) according to Anan et al 2001 # Converted x0.027 (blood) according to Paez-Osuna et al 2010 * Converted x0.28 (kidney) x0.22 (liver) according to Godley et al 1998 ! Converted x0.251 (blood) according to Paez-Osuna et al 2011 ˄ Converted from ppm (originally reported on mass basis) ND No data 160 Queensland Government response to the Gladstone Fish Health Scientific Advisory Panel’s Final Report Queensland Government response to the Gladstone Fish Health Scientific Advisory Panel’s Final Report Background On 16 September 2011, Fisheries Queensland (part of the Department of Employment Economic Development and Innovation) put a temporary closure in place on all fishing in an area centred on Gladstone Harbour while the Queensland Government investigated a condition affecting some locally caught fish. Symptoms included cloudy eyes, skin discoloration and lesions. Some commercial fishers also reported concerns that human health illnesses experienced by them were related to water quality. This closure was lifted on Friday 7 October 2011. In response to the fish health issues, the Queensland Government set up an investigation program which included fish and water quality sampling and testing, investigation into human health concerns, the establishment of a number of reference groups and committees to provide regular communication with peak stakeholder groups and a range of public communication methods including web portals and regular media updates. On 27 September 2011, the Queensland Minister for Main Roads, Fisheries and Marine Infrastructure announced that the Gladstone Fish Health Scientific Advisory Panel (the panel) would be established to provide independent scientific advice to the government. The panel reviewed the Queensland Government’s monitoring regimes, results and analysis primarily focusing on fish health in Gladstone Harbour and surrounds, and also considered water quality monitoring and human health issues where relevant and appropriate. On 6 January 2012, the panel released its final report which concluded that after an extensive review of available data and literature, it was not able to provide a conclusive view on the cause of the fish conditions observed in Gladstone Harbour. In reviewing the Queensland Government’s response, the panel acknowledged and supported the government’s ongoing investigation of the issue and noted that good progress has been made to date. The panel recommended that further monitoring and research is undertaken to aid in identifying the cause of the fish health issues being experienced in Gladstone, while noting that: • identifying the cause(s) of the disease(s) and prevalence of parasites on fish in Gladstone Harbour is a complex and difficult task • determining conclusively whether any environmental changes have anything to do with the reported fish health problems is a formidable and perhaps impossible undertaking; and • the Queensland Government has already acted upon some of its recommendations including undertaking analysis of dissolved metals but notes that there is no evidence of heavy metal impacts on fish. Government response In a statement issued by the Minister for Main Roads, Fisheries and Marine Infrastructure on 6 January 2012, the government accepted the recommendations of the panel for further research in a range of areas and will implement these through an Integrated Aquatic Investigation Program for Gladstone Harbour. The program builds on the work already undertaken by the Queensland Government agencies. Most of the recommendations were either complete, underway or under consideration at the time of the report’s release. The table below details the panel’s recommendations and the Queensland Government’s response. 1 Queensland Government response to the Gladstone Fish Health Scientific Advisory Panel’s Final Report Scientific Advisory Panel’s recommendations—Government response Recommendation Government response Fish health 1. Ongoing focus on fish The Queensland Government accepts the recommendation. health Activities to date: The fish health issue should . Studies into fish health issues in Gladstone Harbour and surrounding areas have been undertaken since be the ongoing focus of September 2011. Queensland Government studies. . Samples taken have been provided to Biosecurity Queensland for gross pathology, histology, bacteriology, metals, and toxicity testing. . All fish sampling, test results and reports are made publically available at 2 Queensland Government response to the Gladstone Fish Health Scientific Advisory Panel’s Final Report Recommendation Government response 5. Experimental work The Queensland Government accepts the recommendation. with diseased fish and Activities to date: Neobenedenia . In-field measurements were taken in October 2011 comparing the numbers of parasites on individual fish Consideration of with the degree of skin discolouration. experimental work with diseased fish and . James Cook University has been undertaking research on Neobenedenia biology and pathogenesis. Neobenedenia to better Further activities: understand the parasite’s . Increase understanding of fish parasite biology and pathogenesis through research project. taxonomy, biology and . Work with James Cook University to further research the parasite. pathogenesis; studies on wild fish with lesions held in captivity. Water quality 6. Dissolved metals The Queensland Government accepts the recommendation. Water quality monitoring is Activities to date: expanded to include . Monthly monitoring for dissolved metals by the government commenced in September 2011. analysis for dissolved metals. . Monitoring of sediment metal concentrations was completed by the government during the week of 26 September 2011. . Gladstone Ports Corporation (GPC) data of sediment sampling undertaken in 2008–2009 (pre-dredging) has been obtained. Further activities: . Continue monitoring for dissolved metals and repeat sediment sampling for metals as part of the integrated investigation program. . Analysis of GPC data of sediment sampling undertaken in 2008–2009 (pre-dredging). . Obtain and analyse additional data from GPC and other sources. 7. Continued water The Queensland Government accepts the recommendation. quality monitoring Activities to date: Water quality monitoring . Monthly water quality monitoring has been undertaken since September 2011. program to continue. . All water quality monitoring data and reports are made publically available at 3 Queensland Government response to the Gladstone Fish Health Scientific Advisory Panel’s Final Report Recommendation Government response 10. Adaptive management The Queensland Government accepts the recommendation. of monitoring Activities to date: program . The monitoring program has been re-assessed and amended based on feedback, including incorporating DERM to re-assess and monitoring of dissolved metals and sediment metal concentrations in September. amend the monitoring program as necessary, as . All relevant government investigation and monitoring programs have been reviewed and evaluated. more information becomes . Other relevant investigation and monitoring programs have been identified and review and evaluation of available. these programs have commenced. Further activities: . The government will consult the Chair of the Scientific Advisory Panel, Professor Ian Poiner, and other panel members as appropriate, on the development of the integrated investigation program. . Panel members will also be approached to assess the conceptual model, the design of the extended fish health and water quality sampling and the progress of other relevant panel recommendations. 11. Engagement with The Queensland Government accepts the recommendation. PCIMP and other Activities to date: industries . Preliminary discussions regarding collaboration and integration with existing institutional, industry and The Queensland community based, research and monitoring such as the Port Curtis Integrated Monitoring Program Government should engage (PCIMP). with the Port Curtis Integrated Monitoring . In 2011, PCIMP members pursued a governance change to formalise the program. The monitoring is Program (PCIMP) and currently undergoing a review. Government departments are providing input into this process to ensure its industries around Gladstone scope and methodologies are adapted to suit the increasing pressures on the Port Curtis. to ensure monitoring Further activities: programs have the ability to . Continued and expanded collaboration and integration with existing institutional, industry and community detect potential impacts of based, research and monitoring including: the multiple stressors on • Port Curtis Integrated Monitoring Program Gladstone Harbour. • Gladstone Ports Corporation • CQ University • Gladstone Industry Leadership Group • CSIRO. Human health 12. Baseline for illness in The Queensland Government accepts the recommendation. commercial fishers Further activities: A study be conducted to . Identify options to progress a study to establish a baseline for illness in commercial fishers in Gladstone establish a baseline for and possibly other areas of Queensland. commercial fishers in Gladstone and possibly other areas of Queensland. 13. OH&S statistics for The Queensland Government accepts the recommendation. commercial fishers Further activities: Appropriate OH&S . Investigate mechanisms to capture work-related injury and disease data for commercial fishing industry statistics be routinely capture work-related injury and disease data for commercial fishing industry. collected for the Queensland commercial fishing industry. 14. OH&S guidelines for The Queensland Government accepts the recommendation. fishing Activities to date: Appropriate best practice . OH&S information has been developed and published on DEEDI Gladstone web page OH&S guidelines for 4 Queensland Government response to the Gladstone Fish Health Scientific Advisory Panel’s Final Report Gladstone Harbour Integrated Aquatic Investigation Program The Gladstone Harbour Integrated Aquatic Investigation Program (the program) has been established to further the work already undertaken by the Queensland Government and implement the recommendations of the independent Gladstone Fish Health Scientific Advisory Panel. The program aims to identify the cause(s) of the fish health issues being experienced in the Gladstone region through further monitoring and research. The program also seeks to expand overall knowledge of the aquatic ecosystem at Gladstone and build on existing monitoring and research activities by developing an expanded investigative program. Key elements of this program include: • Building on the existing monitoring effort by developing an expanded investigative program focused on testing well formed hypotheses and conceptual models about potential causal factors and to improve our understanding of aquatic ecosystems. • Commissioning and reviewing scientific research to inform the above studies, and investigating the use of alternate testing methodologies where appropriate. • Ensuring collaboration and integration with existing institutional, industry and community based, research and monitoring such as the Port Curtis Integrated Monitoring Program (PCIMP). The Queensland Government will consult the Chair of the Scientific Advisory Panel, Professor Ian Poiner, and other panel members as appropriate, on its development. Panel members will also be approached to assess the conceptual model, the design of the extended fish health and water quality sampling and the progress of other relevant panel recommendations. The program will involve regular public reporting, including, but not limited to: • regular progress reports at stakeholder meetings • status updates or report cards published in brochure format • updates on the Department of Environment and Resource Management and Department of Employment Economic Development and Innovation websites 5 Jan Arens Bsc hons Geology Grad.dip. Engineering Management Grad.dip. Process Engineering 85 Batts Rd Winfield QLD 4670 Phone 07 41566757 To: Hon Tony Burke MP, Email [email protected] Minister for Sustainability, Environment, Water, Population and Communities. Email: [email protected] PO Box 6022 House of Representatives Parliament House Canberra ACT 2600 13th March 2011 Queensland Coordinator General approval of Hummock Hill Island Development EIS Dear Hon Tony Burke MP, I must admit that I am absolutely gutted by the Coordinator General’s approval of the Hummock Hill Island development proposal. The Island is such a beautiful part of our coast, it deserves better. I find it distressing to think it may not be there for future generations. White-anting of biodiversity sustaining ecosystems As you are aware the region already suffers unreasonable industrial development pressure including unnecessary dredging in the Dugong protection area of Gladstone harbour. At what point do we say enough. Clearly environmental impact assessments and precautionary principles don’t work to stem the white-anting of the biodiversity sustaining ecosystems in our care. Are you prepared to do the right thing and apply the law as intended for the protection of the environment? Prostituting coastal ecosystems to fund unviable tourism venture The basis for the HHI project is purported to be tourism, yet the project claims that residential development is “crucial” to the viability of the tourist development. This was a prominent consideration in the Coordinator General’s approval but the substantiating material was not made public. The Coordinator General acknowledges that freeholding of crown land and subsequent real estate sales is required to fund the tourism component of the proposal because it cannot stand on it’s own feet. The project and the state government will effectively be prostituting our precious coastal ecosystems to prop up a questionable tourism venture. None of the benefits of state significance are uniquely linked to Hummock Hill Island and can be derived elsewhere. Developing Hummock Hill Island (HHI) erodes the very essence of its natural beauty and is counter to maintaining the area as an attractant for tourists. The Coliseum Inlet - Hummock Hill Island system has significant environmental sustainability value. Even in a reductionist “money making” sense, the relatively un-spoilt character of the area is far more important than the artificiality of golf courses, private airstrips and salt mining operations. Concatenating these artificial attractions and residential development to existing infrastructure elsewhere would significantly reduce the financial burden on society while preserving an environment infinitely more valuable. Inappropriate authority to consider environmental values with intrinsic bias in favor of development Declaring the project of state significance removed the epa as a concurrency agent. The very instrument charged with the protection of the environment, compelled to uphold our environmental laws no longer has a decisive role. The Coordinator General’s office, representing Planning & Development for the Queensland government has a clear and obvious development agenda. This department also lacks the requisite skills to understand environmental finesse to make determinations on environmental impacts. This has led to undue bias and erroneous conclusions. e.g. the Coordinator General states that he is satisfied that surveys did not identify species of national significance and therefore the action poses no risk. This of course is wrong at many levels: 1) National significance is derived from the fact that we have driven species to the edge of extinction. They are per definition rare. Not finding them in remnant ecosystems typically known to represent their habitat is a statistical probability and by no means proof that they do not occur there or rely on that area. 2) We tabulate species on lists and label tem “of concern” or “endangered”, but our capacity (funding levels) to accurately determine their condition at any one time is very uncertain. 3) Impacts are never limited to footprint. 4) Ecosystems are not defined by legal constructs. They function across legal and jurisdictional boundaries. A competent environmentalist even someone with a genuine concern for the environment would understand this. It is unlikely that an epa (free of political interference) would have erred in this regard. Black Breasted Button Quail are present on the island, claiming that they were not found within the “footprint” of the development is disingenuous. I am happy to provide the service of a competent bird atlasser to show you where they live, including the presence of their activity. I can also recommend a competent expert regarding the location of Paradelma orientalis. Both species are listed for protection and fall under your jurisdiction. Lip service to public input I cannot but conclude from the Coordinator General’s decision that he has not considered the matters I raise in my submission. If he had understood the information I provided, he could not in good conscience have approved the eis. I resubmit the document for your information and sincerely hope that you and your advisors give it better attention. I am more than willing to spend time with whoever it may concern, to ensure the principles are understood. (HHI EIS Response Final.pdf) Gross errors in engineering calculations approved, salt mining approved. On page 22 of my submission I provide an analysis of the water supply proposed, viz desalination. The engineering calculations are grossly erroneous, mistaking weekly evaporation rates for daily rates, resulting in proposed evaporation ponds undersized by orders of magnitude. Should evaporative salt recovery even be possible (they also failed to consider precipitation), the volume of salt they need to deal with amounts to 64 tons/day which the proponents suggest they could direct to land fill. While the supplementary eis euphemistically refers to the calculations as “preliminary” it fails to correct the error and ultimately is now approved without comment. I suspect that the object to have a zero brine return to the environment is designed to avoid triggering consideration of the impact on world heritage listed water. I hope you see through this distraction. Should the proponents implement the action as approved, it will result in unacceptable emissions of brine into the world heritage area. This clearly should not have been accepted and demonstrates a number of issues: 1) The technical detail of the eis is questionable as to its accuracy in fact. 2) The Coordinator General failed to detect basic errors of fact in the eis. 3) The Coordinator General failed to consider submissions from the public and thus breached the public consultation process required by the terms of reference. Death by a thousand cuts I made the point earlier that recent approvals for developments in our region represent a major assault on the environment. I am particularly disappointed in your approval of dredging in Dugong protection area of Gladstone. It is a substantial blunder given that the Queensland Government’s own analysis indicates that dredging is not required to accommodate the increased shipping for LNG. I hope that you at least acknowledge the erosion of Dugong habitat that will result from the dredging. Page 17 & 18 of my submission puts this in context with the Hummock Hill Island proposal. Sea-grass beds just 50 meters off the beach in front of the area earmarked for residential development were not identified in the eis. (HummockHillIsland Seagrass & CoralReef within 50m of proposed development.pdf) It highlights a negligent lack of understanding of the Dugong habitat in the region, let alone any understanding of impacts on it. Sea-grass beds were decimated by residential development at Poona. There is a very high likelihood that Dugong will be adversely affected should this development be allowed. The cumulative impacts on Dugong in the region will be substantial and must not be marginalized. Plans? What plans? The Coordinator General states that detailed environmental management plans adequately mitigate the risks identified. But when we actually look at the detail of these plans, they constitute little more than generic expressions of intent to monitor. Monitoring does not avoid harm. Seeing the decline of sea-grass proves that harm has occurred, not that it was avoided. Where the plans go beyond mere monitoring, measures will be taken to avoid repetition but no commitments are made to correct damage or to withdraw from the site if mitigation is deemed impractical. Demonstrated behavior to circumvent regulation On pages 28 to 30 of my submission I provide an analysis showing the unsuitability of the residential development of low lying land and in erosion prone areas. A storm surge of 5.5m such as that caused by Yasi’s visit to Port Hinchinbrook would see significant parts of the proposed residential development inundated. This should have cast doubt in the Coordinator General’s mind. However, I raise it here to draw your attention to the proponent’s attempts to get around the requirements for buffering in erosion prone areas. They persist, even when their own consultant’s report advices against it. This is most alarming given that the Coordinator General is relying on special conditions to deal with the inadequacies of the eis and here we see behavior with intent to seek a way around them. Approval “conditions” are ineffectual The Queensland system for the protection of the environment is woefully inadequate. Lungfish were rightfully deemed important enough to suspend the Queensland Government’s Traveston Dam project. The Paradise Dam project did not afford this species similar prerogative; its eis was approved with conditions. I would have thought that to guarantee lungfish unimpeded ability to move up and down its habitat was a simple enough concept. Despite this, many days of wrangling between many lawyers in court, lungfish were still denied an adequately functioning fish-way. The judge gave weight to a candid comment by one of the “experts”, stating in court “It is often an iterative process in which cost efficiencies are balanced with ecological outcomes”. We now have a legal precedent undermining every conditional eis. It has weakened the efficacy of conditions as protective mechanisms to address shortcomings of eia’s. It elevates the need for rejection where eis’ fail to address risks adequately. Approvals with “conditions” facilitate substandard environmental impact assessment By law the precautionary principle applies where full scientific understanding is not available. Environmental impact assessment should identify our level of understanding of the environment and what the consequences will be of any proposed action. If the action poses potential harm and there is scientific uncertainty, the action has to be refused. A problem arises when rejection conflicts with policy or any other ulterior motive in which case the Coordinator General issues an approval with "conditions" as we see with the approval of the HHI eis. Every condition imposed on an eis flags a failure of that eis to adequately address the risks. i.e. the more conditions the more compromises were made for approval. It demonstrates in my opinion, complicity with the proponents and the extent of abrogation of the Coordinator General’s duty. The high number of conditions was used to somehow convince us that it represents a heightened protection of the environment when it in fact it achieves quite the opposite. Failure of the Queensland regulatory framework The Coordinator General’s decision cannot be challenged on merit and we are left to rely on the bureaucratic system to actually protect the environment and the people in it. Four Corners’ “The Gas Rush” paints a disturbing picture of an environment on the run. The program showed the failure of the industry to declare fracking chemicals, failure to provide materiel safety data (MSDS), failure to account for the volumes of agents injected into aquifers, failure to declare license breaches, obfuscation and lying. The failure of the Queensland government to regulate is undeniable. The Coordinator General superimposing a huge number of special conditions for an already bumbling regulator to manage, in the midst of an industrial development boom can only result in disastrous consequences for the environment. In The Gas Rush case the regulatory failures concern a hazardous industry. It can be reasonably foreseen that a “benign” industry is likely to receive even less attention. Interjurisdictional dysfunction I felt a little embarrassed for that minister on Four Corners’ “The Gas Rush” program when he floundered when asked to explain the MSDS breaches. My sympathy quickly dissipated when he played the "I am not the expert" card and blamed "relevant authorities", what a jelly back. Even though unacceptable, buck passing is a reality of the system, it can be reasonably foreseen that this will expose the heritage values of the Hummock Hill Island area to unacceptable risk viz. the inability of those in charge to accept accountability for implementing the principles of environmental protection. Sweetheart dealing I am aware of an operating smelter quite recently, in Queensland having bypassed their fume scrubbers for weeks apparently perfectly legal and within their permit to operate. Who writes these permits? When the ethereal "experts" in the relevant "authorities" of which their political leadership seem to know so little, draft up the permits, how many of the Coordinator General’s conditions will be negotiated away. How many of the conditions will be enforced only "if practical". Who balances cost efficiencies with ecological outcomes? No evidence that Sophie’s chosen one will be spared I note the management plans include offsets to mitigate environmental damage. Offsets are an environmental Sophie’s choice. It is a moral depravity to approve destruction of significant ecological systems on the basis that similarly endangered ecologies will be spared assault elsewhere. I challenge you to come up with one offset arrangement in Queensland that has maintained ecological values let alone one that has resulted in a net improvement of the environment. The HHI eis certainly does not provide such evidence. In the absence of demonstrated efficacy, offsets should be considered purely speculative and refused on precautionary principle. Their suggestion that the project will “enhance” the environment is downright offensive. Many important reasons to preserve, no reason to sacrifice There are very good reasons not to develop the island as I set out in detail in my submission. These include matters of national and international significance. (Why Hummock Hill Island should be protected Main Map.pdf) The reasons in support of the development of the HHI area are far from clear, even suspect, by the proponents own reckoning. Multiple failed attempts to develop in the past and the stigma associated with an over-industrialized Gladstone exposes the futility of the sacrifice asked of the Hummock Hill Island ecosystem. Opportunistically cashing in on freeholding of public land during a boom sentiment precipitated by irresponsible over-promotion of Gladstone’s industry should not be facilitated by government, let alone promoted. A matter of ecological sustainability I ask that you not reduce your purview on the basis of “terms of reference” or a narrow interpretation of statute; I ask that you consider my submission holistically. We can reduce habitat to a cage and demonstrate scientifically that the cage will not harm the bird, but we hang an albatross around our neck by undermining the “self” in self sustaining. Sustaining a broken ecosystem relies on us spending our ever diminishing resources to prop it up, resources we don’t even seem to have for flood & storm recovery. Hummock Hill Island is part of a coastal estuarine ecological system which for the time being still functions reasonably well. Pushing development of this type into the area cannot but have a significant impact. The white-anting will demand it’s toll. The HHI eis makes no effort to tie the region’s systems together. There is no scientific certainty that the proposed action will not irreversibly damage the self sustaining integrity of these ecological systems. Obfuscating euphemisms Terms like “minimal”, “insignificant”, “negligible” are used with disturbing regularity throughout the HHI eis and seis documents. They don’t add value in any meaningful way and should be seen for what they represent - failure to quantify environmental impact. As a quantitative assessment of environmental impact, the HHI eis fails miserably. Emotively it seems to satisfy those with vested interest. It certainly “satisfied” the Coordinator General sufficiently to approve it, despite a dearth of scientific certainty. Please don’t let this happen. Sincerely, Jan Jan Arens 85 Batts Rd Winfield QLD 4670 Phone 07 41566757 Email [email protected] Gladstone Fish Health Scientific Advisory Panel Final Report 5 January 2012 1 Acknowledgments The Gladstone Fish Health Scientific Advisory Panel would like to extend its thanks to those commercial and recreational fishers who assisted in providing information and samples, the Gladstone Area Water Board for its assistance and to Ben Westlake and Christina Schmid of Fisheries Queensland for secretariat support to the Panel. 2 Table of contents Summary of investigation ...... 4 Reporting process...... 4 Executive summary ...... 4 Findings and recommendations...... 6 Introduction ...... 11 Queensland Government assessment, response and conclusions to date...... 12 Timeline of events and potential stressors ...... 17 Scientific Advisory Panel ...... 22 Membership ...... 22 Meetings of the Scientific Advisory Panel ...... 23 Findings and recommendations...... 23 Appendices...... 31 3 Summary of investigation Reporting process This report has been prepared by the Gladstone Fish Health Scientific Advisory Panel (the Panel) for the Honourable Craig Wallace MP, Minister for Main Roads, Fisheries and Marine Infrastructure, Queensland. The report is based on information provided to the Panel by the Queensland Government and other stakeholders relating to the fish health issues observed in Gladstone Harbour and surrounding areas in the latter half of 2011 (Appendix 1) and the Panel’s scientific expertise and relevant scientific literature. The conclusions and recommendations presented in this report represent those formulated by members of the Panel. The views of government and non-government “invitees” in relation to conclusions reached and recommendations made by the Panel have been taken into consideration. Executive summary Background In 2011, the Queensland Government received reports (primarily by commercial fishers) of barramundi fish and subsequently other species being caught with obvious signs of disease, including bulging/red eyes, blindness, severe skin lesions and skin discolouration. The Government then undertook an investigation of Gladstone Harbour and surrounding areas following reports that commercial fishers were sick with what appeared to be bacterial infections on their arms, feet and legs following contact with, or abrasions and fish spikes from net-caught barramundi that were exhibiting evidence of disease. At that time, the Queensland Government was concerned about the potential food safety issues of consuming the diseased fish, given the type of disease remained unknown. Furthermore, there were concerns about the possibility of the transfer of the disease from affected fish to other fish and consequently its entry into the food chain. Queensland Government Response On 16 September 2011, Fisheries Queensland closed Gladstone Harbour and the surrounding area to fishing under section 46 of the Fisheries Act 1994 in response to concerns about human health and the transfer of disease between fish and entry into the food chain. The emergency fisheries declaration closed Gladstone Harbour and the surrounding area to all forms of commercial and recreational fishing for a period of 21 days between 16 September 2011 and 7 October 2011. From the initial testing of nine diseased barramundi, two conditions were identified that were affecting barramundi in the Gladstone area; 1. Red-spot disease (epizootic ulcerative syndrome (EUS)), which is a fungus endemic to fin fish species of mainland Australia. This condition was only confirmed in one fish from Port Alma. 2. An external parasitism due to the fluke Neobenedenia sp, which was affecting the eye and skin particularly in the barramundi in Gladstone Harbour. This parasite has previously been found in Queensland waters in Hinchinbrook Channel between Hinchinbrook Island and mainland Queensland where barramundi are in high densities. In September 2011, Gladstone Area Water Board staff reported that an estimated 30,000 barramundi between 90 and 130cm in length (equivalent to approximately 300 tonnes) were washed over the Awoonga Dam wall into the Boyne River estuary between December and March 2011. This was an unusual event, as it was the first time the dam had spilled over since 2002. Subsequently the commercial catches of barramundi demonstrated these high numbers of barramundi in the Boyne River and Gladstone 4 Harbour as the 2011 catch was 18 times that of the average annual catch from 2005 to 2010. Based on the available scientific literature, the Queensland Government concluded the high levels of external Neobenedenia sp parasitism and bacterial infections in barramundi were likely to disappear as water temperatures increased. The Queensland Government reported neither condition is detrimental to human health. Fisheries Queensland, in cooperation with commercial fishers, conducted a survey of fish health status across a number of sites in the Gladstone area in early October 2011. It was found that while it seemed the relative number of barramundi with deep lesions had decreased, the numbers affected by the parasitic fluke and skin discolouration (redness) was still a significant problem in the Harbour fish. The Boyne River remained the site of the highest number of barramundi affected by the parasite compared to the other sites sampled. Of the 24 non-barramundi fish and sharks caught, two fish from the Boyne River and two lemon sharks from Wild Cattle Island to the south of the Boyne River mouth had some skin discolouration. Queensland Health received reports from 37 people who were concerned they might have been unwell or had infections or other skin conditions as a result of contact with diseased fish or seawater. The majority of interviewees reported infected injuries and skin infections. However, a range of symptoms were described by interviewees, including flu-like illnesses, infected injuries, boils, eye discharge and redness/rashes on the hands and feet. No link was identified between the conditions found in fish and the human health issues. While bacterial infections are occasionally associated with the handling of fish, there are no major zoonoses (illnesses transmitted to humans from animals) in the literature related to the handling of fish. In early October 2011, the Queensland Government released a report outlining the water quality conditions in Port Curtis. This report indicated that water quality in the Harbour and the two estuaries (Boyne River Estuary and Calliope River Estuary) was consistent with historical trends, apart from the impacts of flooding in January 2011, which saw much lower salinities over an extended period beyond what had been observed in the last three decades. In October 2011, the Queensland Government lifted all fishing bans noting that: 1. the disease in fish did not appear to be of human health significance; 2. the identification of likely causes of the lesions in the fish; and 3. the test results of the fishers and Gladstone Harbour water revealed no significant issues that warranted continuation of the fishing ban. All forms of fishing were permitted in Gladstone Harbour and surrounding areas from Friday 7 October 2011. During this period, subsequently and currently commercial fishers remained concerned about the health of seafood species caught in Gladstone Harbour and surrounding areas. Fishers have raised concerns over the health of other fish species, besides barramundi, sharks and invertebrates such as crabs, prawns and scallops. In response, the Queensland Government continues to monitor Gladstone Harbour and surrounding areas and conduct additional laboratory testing of fish, scallops and crustacean samples. The Queensland Government’s explanations for what is being observed in Gladstone Harbour are as following: 1. An estimated 30,000 large barramundi suffered physical stress including wounds to the body when washed over Awoonga Dam. The stress of their forced relocation, the increased crowding and competition for food due to the dramatic increase in barramundi numbers in the area and colder water temperature during winter would have stressed the fish and made them susceptible to disease. 5 2. Monitoring of other species of fish indicated that 5% of fish have lesions ranging from mild skin conditions, fin damage to skin discolouration. This is a low level of prevalence, which may be caused by a number of stressors, but quite significantly were the extreme natural events that occurred earlier in the year resulting in severe flooding. 3. The parasites and hyperaemia (redness) observed in sharks is a widespread general condition given that Fisheries Queensland Observers have recorded it in sharks caught in other areas to the north and south of Gladstone. 4. The shell erosion disease of mud crabs previously observed and documented in Gladstone Harbour may be a natural phenomenon. 5. There is no evidence to suggest that the erosive shell disease or the gill parasite observed in prawns is any greater than that observed in other prawn species from areas outside of Gladstone. Following the suggestion of the Panel to develop a conceptual model of the cause-effect relationship to help guide studies and eliminate potential causal factors, the Queensland Government summarised the potential stressors on fish species being reported for Gladstone Harbour, including key questions arising from the reports and the available evidence. This and other information was used to develop a set of indicative diagrams in relation to the fish health issue in Gladstone Harbour and surrounding areas during 2011. The concept maps and diagrams are provided in this report. Scientific Advisory Panel On 27 September 2011, the Queensland Minister for Main Roads, Fisheries and Marine Infrastructure announced that the Gladstone Fish Health Scientific Advisory Panel (the Panel) would be established to provide independent scientific advice to the Government. The primary role of the Panel is to review the Queensland Government's existing monitoring programs and examine the available information with a view to identifying a possible cause(s) of the fish health issues being observed in Gladstone Harbour and its surrounds, with a secondary role being to consider the water quality monitoring programs currently in place and human health issues where appropriate. A list of the documents, reports and datasets considered by the Panel is provided in Appendix 1. The Panel comprised eminent scientists, from the government and academic sectors, with recognised expertise and research publications concerning: aquatic environmental science including water quality; fish health and toxicology; and human health especially in relation to potential for transmission of diseases from marine species to humans. Several government scientists and a representative of the commercial fishing sector were invited to participate in Panel meetings and inter-sessional activities. The Panel was appointed for a three month term and asked to report to the Minister by the end of December 2011. The Panel’s Terms of Reference are provided in Appendix 2. The Panel convened four times between 6 October 2011 and 9 December 2011 and undertook inter-sessional activities. Findings and recommendations The Panel noted that identifying the cause(s) of the disease(s) and prevalence of parasites on fish in Gladstone Harbour is a complex and difficult task. This task is further complicated by the extreme flood events of the 2010-2011 summer and the historical and ongoing industrial development of the Harbour, which have changed the local environment. Determining conclusively whether any environmental changes have anything to do with the reported fish health problems is a formidable and perhaps impossible undertaking given the available data for fish and human diseases has been collected using descriptive study designs (e.g. case series, cross sectional surveys) without the benefit 6 of normal baseline values for fish and human diseases making determination of causation difficult. Nevertheless, it is the Panel’s view there is an issue of concern around the health of some species of fish in Gladstone Harbour and this is possibly caused by environmental factors. In reviewing the Queensland Government’s response, the Panel acknowledges and supports the Government’s ongoing investigation of the issue and notes that good progress has been made to date. Having reviewed the available data and reports and provided advice on the future investigations of Gladstone Harbour, the Panel notes that the Queensland Government has acted or is acting based upon earlier advice provided by the Panel. The Panel has made specific comments and recommendations in relation to the issues of fish health, water quality and human health with a view to identifying a possible cause(s) of the fish health issues being observed in Gladstone Harbour. The Panel has also provided suggestions to the Queensland Government for its consideration on ways ongoing studies could be expanded in the future to increase the possibility of determining whether any environmental changes have anything to do with the reported fish health problems. Fish Health Fish are normally good integrative indicators of eco-system and environmental health. The Panel concluded there is an issue of concern around the health of some species of fish in Gladstone Harbour and this is possibly caused by environmental factors, but the extent of the issue is currently not known. The data for barramundi indicates this species may be stressed, but it is less clear for other fish species. The Panel reviewed the Queensland Government’s explanations for what is being observed in Gladstone Harbour, but the lack of historical baselines and/or good comparative baseline information in areas to the north and south of Gladstone on the level of skin abnormalities in fish species makes it difficult to determine if the Gladstone data is an anomaly until further surveys are completed. The Panel proposed to the Queensland Government an assessment of the hypothesis that there is a yet unknown factor (or factors) causing stress in some fish species. Barramundi appear to be more strongly affected because of the additional population stress associated with the introduction of an estimated 30,000 barramundi into already stressed (flooded) Gladstone Harbour between 12 December 2010 and March 2011 with the overflow of the Awoonga Dam. The Panel recommends that the identification of potential causal agent(s) should be the focus of future investigations. The pathology data and other information available to date indicate that some species of fish in Gladstone Harbour may be stressed and potentially immuno-compromised. However, this is only a hypothesis and it is necessary to continue Fisheries Queensland and other studies to determine the extent to which populations of barramundi and other fish species in Gladstone Harbour have been stressed and potentially compromised. Furthermore, it will also be necessary to determine whether a causal relationship can be definitively established between what is being observed in the fish in Gladstone Harbour and water quality and sediment. This has not been established to date. While the Panel agreed the observed parasitic infections, lesions and skin discolouration in fish taken from Gladstone Harbour indicates that these fish may be stressed, the Panel also noted there are a range of possible causes for this including human induced mechanical damage, chemical damage, nutritional issues and physical issues that need to be investigated. The Panel emphasised the need for comparative information from similar unaffected systems to determine the scale of the problem being observed in barramundi and other 7 fish species in the Gladstone area. This includes establishing baselines and trends during “normal” periods, and appropriate areas outside the Harbour to act as a form of control for comparative analysis i.e. the use of more sophisticated study designs. The Panel suggested that ongoing pathology studies are a priority to support epidemiological studies and as a component of more in-depth investigations, including the development of a case definition for the observed skin discoloration or “reddening”. The Panel reviewed the data for the parasite ( Neobenedenia sp.) which was affecting the eye and skin particularly in the barramundi. The parasite has been reported previously in Australia and has a wide host specificity and is known to cause mass mortalities in aquaculture cages in many countries. Reports of high prevalences in wild fish are unusual, but may simply be a reporting issue. While the presence of Neobenedenia on barramundi explains many of the lesions reported, the reasons for the current high prevalence and abundance of the parasite are unclear but outbreaks are known to occur including in Hinchinbrook Channel, Queensland but not to the extent seen in this instance. Recommendations The fish health issue should be the ongoing focus of Queensland Government studies. As a priority, a conceptual model should be completed of possible cause-effect relationship(s) to help guide studies and eliminate potential causal factors. The development of the concept maps (Appendix 3) and the set of indicative diagrams (Figures 7-10) is the first step in developing the conceptual model. There is an immediate need to develop a case definition for the observed skin discolouration (“reddening”) in fish. The ongoing monitoring of the prevalence of the parasite, lesions and skin discoloration and the associated pathology investigations should continue as a priority and be guided by the conceptual model. Consideration should be given to experimental work with diseased fish and fish with Neobenedenia to better understand the parasite’s taxonomy, biology and pathogenesis; and studies on wild fish with lesions held in captivity and exposed to water of different quality. Water Quality The Panel reviewed the available water quality data and reports and agreed that the data provided by the Queensland Government was appropriately collected and analysed. The Panel concluded that the water quality results received to date indicate the observed values of the measured water quality parameters are not unusual (compared to historical values and trends), except for extremely low salinity during the 2010-2011 wet season. A number of areas of the Harbour, including the Boyne River, had zero or close to zero salinity for extended periods of time. The measured water quality parameters provide no insights into the cause of the high parasitic levels, lesions and skin discoloration observed in the fish. The Panel recommended the water quality monitoring be expanded to include analysis for dissolved metals (operationally defined as the fraction of metals in the water column that pass through a 0.45 µm filter). The Queensland Department of Environment and Resource Management (DERM) completed additional monitoring including dissolved metals during the week of 26 September 2011. The values observed were within the expected ranges for Australian tropical/sub-tropical coastal environments and not expected to cause adverse biological effects. The total (acid extractable) metals data from the sediment samples indicate the metal concentrations are at levels that would not 8 be expected to cause adverse biological effects. One sediment site, QE3, had higher concentrations of aluminium, arsenic, barium and iron, which appears to be due to a different type of mineralization at this site. The Panel noted the lack of monitoring data for metals in sediments and the apparent lack of monitoring data for organic chemicals in sediments and water, and suggested these should be considered for inclusion in the monitoring program. Given the focus of the monitoring programs, the Panel discussed whether the available water quality data is fit for purpose. The Panel noted the current parameters measured may not provide an appropriate trigger for ecosystem health problems that may be responsible for the observed fish health issues in Gladstone Harbour. Water quality parameters need to be selected on the basis that they will provide a trigger for biological investigations at the chronic (or if possible sub-chronic) level. The Panel recommended that the Queensland Government commission or conduct a comprehensive literature review on the potential of chemicals to cause the observed signs in fish and then design a test program for metals and organic chemicals, as well as natural toxins that targets the chemicals that may be associated with the observed signs in fish. The Panel noted that this case highlights the need for monitoring programs to align with some form of hypothesis testing (or conceptual model). It is noted that many of the chemicals that could contribute to health problems in fish (e.g. chemical induced immune-suppression) are hydrophobic and thus highly bio-accumulative and the chemical concentration in sediments would possibly provide a better surrogate than the water phase. Thus testing of sediments should accompany future water quality sampling campaigns. However, the Panel emphasised there is no evidence from the histopathology reports of heavy metal impacts on fish tissues. The Panel noted that the current sampling does not include organic chemicals or broad scale bacterial (prokaryotes) and microalgal (eukaryotes) assessment and recommends the Queensland Government assess the usefulness of including surveys of prokaryotic and eukaryotic community structure and composition using DNA bulk sequencing techniques and organic chemicals in the ongoing monitoring program. Recommendations The Panel recommended the water quality monitoring be expanded to include analysis for dissolved metals (operationally defined as the fraction of metals in the water column that pass through a 0.45 µm filter). The dissolved metal fraction will potentially contain the readily bio-available fraction of metals (the fraction of metals that are readily taken up by aquatic organisms). DERM completed additional monitoring including dissolved metals during the week of 26 September 2011. The Panel recommended continued water quality monitoring by the Queensland Government as an indicator of the general health of the Gladstone Harbour and surrounding areas and the program is continuing. The Queensland Government commission or conduct a comprehensive literature review on the potential of chemicals to cause the observed signs in fish and then design a test program for metals and organic chemicals, as well as natural toxins that targets the chemicals that may be associated with the observed signs in fish. The Panel recommended a one-off quantification of legacy persistent organic pollutants (such as polychlorinated dibenzodioxins, chlorinated pesticides and polychlorinated biphenyls) in sediments and (if possible) fish lipid tissue. 9 DERM should re-assess and amend the monitoring program as necessary, as more information becomes available (framed as an adaptive management approach). The Queensland Government should engage with Port Curtis Integrated Monitoring Program Inc. (PCIMP) and industries around Gladstone Harbour to ensure monitoring programs do have the ability to detect potential impacts of the multiple potential stressors on Gladstone Harbour. The concept maps (Appendix 3) and indicative diagrams (Figures 7-10) could provide the basis for this engagement. Human Health To assess the human health impacts, the Panel was provided with a Queensland Health report on a group of instances of illness in fishers from the Gladstone area that could potentially indicate an outbreak, and one Panel member undertook a detailed assessment of the report. This included access to the de-identified line listing of the cases that formed the basis of the Queensland Health report and enabled the accuracy of the summarised data in the Queensland Health report to be confirmed from the original data. The Panel concluded that Queensland Health had conducted an appropriate and adequate investigation of the fishers. The Panel agreed with Queensland Health that the cases described did not form a single outbreak of one disease. The Panel agreed that there was no indication of an outbreak of disease in fishers that could be linked with disease in fish in Gladstone Harbour and agreed that additional investigations by Queensland Health of this group of fishers was not warranted. The Panel noted the occurrence of non-multiresistant Staphylococcus aureus (nmMRSA) in commercial fishers is an issue that warrants further investigation in collaboration with the commercial fishing industry. Recommendations That a study be conducted to establish a baseline incidence for illness in commercial fishers in the Gladstone area and possibly other areas of Queensland. This is essential if any outbreak of disease is to be identified in the future. That appropriate OH&S statistics be routinely collected for the Queensland commercial fishing industry. That appropriate best practice OH&S guidelines for fishing and fish handling be developed in collaboration with the commercial fishing industry. 10 Introduction Following reports (primarily by commercial fishers) of barramundi fish ( Lates calcarifer ) in the Gladstone region (Figure 1) being caught with obvious signs of disease including bulging/red eyes, blindness, severe skin lesions and skin discolouration (Figures 2, 3 and 4), Fisheries Queensland organised for diseased barramundi to be provided to Biosecurity Queensland for testing. Fisheries Queensland is the lead agency in developing the policy framework to protect and conserve fisheries resources while maintaining profitable commercial and enjoyable recreational fishing sectors (see www.fisheries.qld.gov.au ). One of Biosecurity Queensland’s roles is to coordinate the Queensland Government's efforts to prevent, respond to, and recover from pests and diseases that threaten the economy and environment (see www.biosecurity.qld.gov.au ). The fish were provided by commercial fishers through the Gladstone Fish Markets. Nine fish were received for testing by Biosecurity Queensland on 28 August 2011. Figure 1: Map depicting Gladstone, Gladstone Harbour and surrounding areas. On 13 September 2011, the Queensland Seafood Industry Association (QSIA) advised Fisheries Queensland that at least six commercial fishers were sick with what appeared to be bacterial infections on their arms, feet and legs following contact with, or abrasions and fish spikes from net-caught barramundi that were exhibiting evidence of disease. The QSIA is the peak industry body representing the Queensland Seafood Industry. Its members include professional fishers, seafood processors, marketers, retailers and other businesses associated with the seafood industry (see http://www.qsia.com.au/ ). With this information, Queensland Health and Safe Food Production Queensland were concerned about the potential food safety issues of consuming the diseased fish, given that at that time the type of disease remained unknown. Furthermore, there were concerns about the possibility of the transfer of the disease from affected fish to other fish and consequently its entry into the food chain. Safe Food Production Queensland 11 (SFPQ) works in partnership with Queensland Health (QH) across the entire food chain to ensure Queensland’s food supply is safe (see www.safefood.qld.gov.au/ ). Queensland Government assessment, response and conclusions to date On 16 September 2011, Fisheries Queensland closed Gladstone Harbour and the surrounding area to fishing under section 46 of the Fisheries Act 1994 over concerns of potential impacts on human health and food safety issues of consuming the diseased fish. This followed a meeting of officers from Fisheries Queensland, Biosecurity Queensland, Safe Food Production Queensland, Queensland Health and the Department of Environment and Resource Management. The closure was put in place to avoid any possibility of unsafe product entering the seafood supply chain, and to further prevent infections from handling diseased fish. The emergency fisheries declaration closed Gladstone Harbour and the surrounding area to all forms of commercial and recreational fishing for a period of 21 days between 16 September 2011 and 7 October 2011. From the initial testing of the nine diseased barramundi, two conditions were identified that were affecting barramundi in the Gladstone area. The first was red-spot disease (epizootic ulcerative syndrome (EUS)) which is a fungus endemic to fin fish species of mainland Australia. This condition was only confirmed in one fish from Port Alma. The second condition was external parasitism due to the fluke Neobenedenia sp, which was affecting the eye and skin particularly in the barramundi in Gladstone Harbour. This parasite has previously been found in Queensland waters in Hinchinbrook Channel between Hinchinbrook Island and mainland Queensland where barramundi are in high densities 1. In September 2011 the Gladstone Water Area Board staff 2 reported that an estimated 30,000 barramundi between 90 and 130cm in length (equivalent to approximately 300 tonnes) entered the Boyne River estuary when the Awoonga Dam (Figure 1) spilled over between December 2010 and June 2011. This was the first time the Dam had spilled over since 2002. Barramundi were reported being washed over the Dam wall from 12 December 2010 to March 2011. Catches of barramundi demonstrated that the numbers of barramundi in the Boyne River and Gladstone Harbour (Figure 1) well exceeded the catch recorded in previous years, with each monthly catch in 2011 exceeding the annual catch for each of the previous six years. The commercial catch records received to date indicate that the 2011 catch was 18 times that of the average annual catch from 2005 to 2010 (Figure 5). 1 Deveney MR, Chisholm LA, Whittington ID. (2001) First published record of the pathogenic monogenean parasite Neobenedenia melleni (Capsalidae) from Australia. Dis Aquat Organ., 461:79-82. 2 Gladstone Water Board official, personal communication, September 2011. 12 Figure 2: Photograph of a barramundi depicting the bulging red eyes typical of that observed in some fish taken from the Gladstone area. Figure 3: Photograph of a barramundi depicting a skin lesion typical of that observed in some fish taken from the Gladstone area. 13 Figure 4: Photograph of a barramundi depicting the skin discolouration typical of that observed in some fish taken from the Gladstone area. Catch of barramundi (t) Gladstone 45 40 35 30 t) 25 ( h tc a C 20 15 10 5 0 234567891023456789102345678910234567891023456789102 3456789102345678 2005 2006 2007 2008 2009 2010 2011 Figure 5: Monthly catch in tonnes of barramundi in Gladstone from 2005 to 2011. Note the marked increase in barramundi catch in each month of 2011. 14 Based on the available scientific literature, the Queensland Government concluded the high levels of external Neobenedenia sp parasitism 3 and bacterial infections 4 in barramundi were likely to disappear as water temperatures increased. The Queensland Government reported neither condition is detrimental to human health. Fisheries Queensland conducted a survey of fish health status across a number of sites in the Gladstone area in early October 2011 to determine the distribution of sick fish, particularly barramundi as it was the primary species of concern at that time. In addition, any ill fish from any species caught were collected for testing (Figure 6). The survey was conducted with commercial barramundi fishermen using 6 to 8 inch mesh nets. Fish health condition was recorded for each fish caught including presence of lesions, eye condition and skin discolouration. Photographs were taken of each fish and samples were taken where fish were displaying signs of illness. The survey found that while it seemed the relative number of barramundi with deep lesions had decreased, the numbers affected by the parasitic fluke and skin discolouration (redness) were still a significant problem in the Harbour fish. The Boyne River remained the site of the highest number of barramundi affected by the parasite compared to the other sites sampled. Of the 24 non-barramundi fish and sharks caught, two fish from the Boyne River and two lemon sharks from Wild Cattle Island to the south of the Boyne River mouth (Figure 1) had some skin discolouration. Fisheries Queensland continues to work with commercial net, trawl and crab fishers to observe catches and take samples of fish, crustaceans and molluscs over several sites within and outside Gladstone Harbour (Figures 6 and 11 to 14). Queensland Health received reports from 37 people who were concerned they might have been unwell or had infections or other skin conditions as a result of contact with diseased fish or seawater. Most of these people were interviewed by Queensland Health to establish whether there was any clear pattern of illness among interviewees and to identify possible links between diseased fish and risks to human health. The majority of interviewees reported infected injuries and skin infections. However, a range of symptoms were described by interviewees, including flu-like illnesses, infected injuries, boils, eye discharge and redness/rashes on the hands and feet. No link was identified between the conditions found in fish and the human health issues. While bacterial infections are occasionally associated with the handling of fish 5, there are no major zoonoses (illnesses transmitted to humans from animals) in the literature related to the handling of fish. In addition to the testing of diseased fish and reviewing the medical conditions of the fishers, the Department of Environment and Resource Management released a report on 4 October 2011 outlining the water quality conditions in Port Curtis. This report indicated that water quality in the Harbour and the two estuaries (Boyne River Estuary and 3 Hirazawa, Noritaka ; Takano, Ryoko ; Hagiwara, Hiroko ; Noguchi, Mitsuyo ; Narita, Minoru; 2010. The influence of different water temperatures on Neobenedenia girellae (Monogenea) infection, parasite growth, egg production and emerging second generation on amberjack Seriola dumerili (Carangidae) and the histopathological effect of this parasite on fish skin. Aquaculture 299:2-7. 4 Bromage, Erin; 2004. The humoral immune response of Lates calcarifer to Streptococcus iniae 2004. PhD Thesis, James Cook University. 5 Lowry, T. and Smith S.A. (2007). Aquatic zoonoses associated with food, bait, ornamental, and tropical fish JAVMA, V 231, No. 6. 15 Calliope River Estuary) was consistent with historical trends apart from the impacts of flooding in January 2011, which saw much lower salinities over an extended period beyond what had been observed in the last three decades. In October 2011, the Queensland Government lifted all fishing bans noting that: • the disease in fish did not appear to be of human health significance; • the identification of likely causes of the lesions in the fish; and • the test results of the fishers and Gladstone Harbour water revealed no significant issues that warranted continuation of the fishing ban. All forms of fishing were permitted in Gladstone Harbour and surrounding areas from Friday 7 October 2011. During this period, subsequently and currently commercial fishers remained concerned about the health of seafood species caught in Gladstone Harbour and surrounding areas In early August 2011, fishers raised concerns over the health of other fish species, besides barramundi, sharks and invertebrates such as crabs, prawns and scallops (Figure 6). In response to these ongoing concerns, Fisheries Queensland is continuing to monitor Gladstone Harbour and surrounding areas and arranged for the additional laboratory testing of fish, scallops and crustacean samples to assess the extent of affected seafood in the Gladstone area. Sampling is also occurring to the north and south of Gladstone to provide a baseline to compare fish heath in the Harbour (Figure 6). Figure 6: Map depicting Gladstone and surrounding areas highlighting the location of reports of fish health issues received by Fisheries Queensland and the location of surveys undertaken by Fisheries Queensland in response to the reports. Safe Food Production Queensland continues to engage with accreditation holders to ensure that they are aware of their food safety obligations under the legislation. Safe Food Production Queensland accreditation categories included wild animal harvester, producer or processor. A seafood supplier must be accredited with Safe Food Production Queensland before they can legally supply seafood in Queensland (see http://www.safefood.qld.gov.au/index ). Safe Food Production Queensland also continues 16 to respond on a regular basis to particular questions raised by persons accredited with it under its Seafood Food Safety Scheme. The Fisheries Queensland's hypothesis is that an estimated 30,000 large barramundi (between 90 and 130cm in length and equivalent to approximately 300 tonnes) suffered physical stress including wounds to the body when washed over Awoonga Dam. The stress of their forced relocation, the increased crowding and competition for food due to the dramatic increase in barramundi numbers in the area, and colder water temperature during winter would have stressed the fish and made them susceptible to disease. In response to concerns about the health of other species, Fisheries Queensland monitoring indicated that approximately 95% of a total of nearly 2,000 non-barramundi fish caught in the Gladstone area were in good health. Of the remaining 5%, which was comprised of a variety of species, lesions observed ranged from mild skin conditions, fin damage to skin discolouration. No one bacterial, parasitic or fungal pathogen has been identified from the over 20 fish samples tested by Biosecurity Queensland. The presence of viral agents was assessed histologically to determine if further specific testing was indicated. However, no viral testing was done. The Department’s hypothesis is that the low level of prevalence may be caused by a number of stressors, but quite significantly included the extreme natural events that occurred earlier in the year resulting in severe flooding. Fisheries Queensland's hypothesis for sharks is that the parasites and hyperaemia (redness) observed may be a more widespread general condition given that Fisheries Queensland observers have recorded it in sharks caught in other areas to the north and south of Gladstone. Fisheries Queensland also concluded the shell erosion disease comprising up to 6% of mud crabs ( Scylla serrata ) caught across Gladstone Harbour in Fisheries observations has been previously observed and documented in a 2001 study of the area. The study found affected mud crabs comprised up to 21% of the catch and concluded that it may be a natural phenomenon 6. Fisheries Queensland concluded there was no evidence to suggest that the erosive shell disease or the gill parasite observed in prawns is any greater than that observed in other prawn species from areas outside of Gladstone. The 2011 banana prawn (Fenneropenaeus merguiensis ) catches in the Gladstone area have exceeded previous years. Until the results from testing including toxicology of the scallops are available, no conclusions can be made in regard to scallops. Timeline of events and potential stressors Following the request of the Panel to develop a conceptual model of the cause-effect relationship to help guide studies and eliminate potential causal factors, the Queensland Government summarised the potential stressors on fish species being reported for Gladstone Harbour including key questions arising from the reports and the available evidence. The approach taken was guided by the Panel’s advice about the range of potential causes of stress on fish species. Initially the Queensland Government developed concept maps that summarised current information in the fish health investigation according to five potential stressors: (i) mechanical; (ii) nutritional/fitness; (iii) biological; (iv) physical and (v) chemical. The approach taken was guided by the Panel’s advice about the range of potential causes of stress on fish species. This was done for barramundi, fin fish and sharks, and prawns and crabs and these are provided 6 Andersen, L., Norton, J., 2001. Port Curtis mud crab shell disease: nature, distribution and management. FRDC Project No. 98/210. Central Queensland University, Gladstone. 17 in Appendix 3. This and other relevant information was used to develop the following set of indicative diagrams in relation to the fish health issue in Gladstone Harbour and surrounding areas during 2011: • Port Curtis baseline condition (Figure 7); • Port Curtis Dec 2010 – Mar 2011 (Figure 8); • Port Curtis Apr 2011 – Jun 2011 (Figure 9); and, • Port Curtis Jul 2011 – Sep 2011 (Figure 10). The diagrams summarise the known events or activities that could potentially have been a contributing factor to the fish health issue observed in the region. Figure 7: Graphic depicting events, activities and observations from the Gladstone area prior to the occurrence of the fish health issue. 18 Figure 8: Graphic depicting events, activities and observations from the Gladstone area between December 2010 and March 2011. 19 Figure 9: Graphic depicting events, activities and observations from the Gladstone area between April 2011 and June 2011. 20 Figure 10 : Graphic depicting events, activities and observations from the Gladstone area between July 2011 and September 2011. 21 Scientific Advisory Panel Terms of Reference On 27 September 2011, the Queensland Minister of Main Roads, Fisheries and Marine Infrastructure announced that the Gladstone Fish Health Scientific Advisory Panel (the Panel) would be established to provide independent scientific advice to the Government. The primary role of the Panel is to review the Queensland Government's existing monitoring programs and examine the available information with a view to identifying a possible cause(s) of the fish 7 health issues 8 being observed in Gladstone Harbour and its surrounds with a secondary role being to consider the water quality monitoring programs currently in place and human health issues where appropriate. Specifically, the Panel was requested to: Review the available test results, and assess previous water quality data and the current water quality and sediment monitoring regime. Review the pathology and toxicology testing of seafood. Investigate the potential impacts, if any, on human health. Advise Government as to whether there is a need for additional testing or investigations. Advise Government whether there are any identifiable reasons, based on the information supplied to the Panel and the expertise of its members, for the health issues affecting seafood species (fin fish and crustaceans) in the Gladstone area and the evidence for links to human health issues. The Panel was appointed for a three month term and asked to report to the Minister by the end of December 2011. The Panel’s Terms of Reference is provided in Appendix 2. Membership The Panel was chaired by Dr Ian Poiner from the Australian Institute of Marine Science, and comprised eminent scientists, from the government and academic sectors, with recognised expertise and research publications concerning: aquatic environmental science including water quality; fish health and toxicology; and human health especially in relation to potential for transmission of diseases from marine species to humans. Several government scientists and a representative of the Commercial Fishers sector were invited to participate in Panel meetings and inter- sessional activities. A list of Panel members and invited participants and their areas of expertise is provided in Appendix 2. 7 The use of the word, ”fish” in this report is taken to have the same meaning as defined in the Queensland Fisheries Act 1994 and therefore includes species other than fin fish such as sharks, crustaceans and invertebrates. 8 Green turtle and dugong were not included in the Panel’s TORs as they were being assessed elsewhere as part of the Queensland Government’s response to the observed increase in stress on turtle and dugong populations in Queensland waters following the widespread loss of seagrass, their primary food source, due to the 2011 flooding events. 22 Meetings of the Scientific Advisory Panel The Panel convened four times between 6 October 2011 and 9 December 2011 to assess the available scientific information relating to the investigations being undertaken and develop recommendations. The Panel established a GovDex site to facilitate inter-sessional activity and communications within the Panel. A list of the documents, reports and datasets considered by the Panel is provided in Appendix 1. An account of the Panel’s conclusions and recommendations is provided below for consideration by the Minister. Findings and recommendations General The Panel noted that identifying the cause(s) of the disease(s) and prevalence of parasites on fish in Gladstone Harbour is a complex and difficult task. This task is further complicated by the extreme flood events of the 2010-2011 summer (Figure 8) and the historical and ongoing industrial development of the Harbour (Figure 7), which have changed the local environment. For example, the extreme flood events of the 2010-2011 summer negatively and significantly affected Gladstone Harbour’s seagrass beds. Determining conclusively whether any environmental changes have anything to do with the reported fish health problems is a formidable and perhaps impossible undertaking. The Panel noted all data for fish and human diseases has been collected using descriptive study designs (e.g. case series, cross sectional surveys) without normal baseline values for fish and human diseases, and that, although these provide valuable evidence, the quality of evidence is low in the hierarchy of evidence. This makes determination of causation difficult. Nevertheless, it is the Panel’s view there is an issue of concern around the health of some species of fish in Gladstone Harbour and this is possibly caused by environmental factors. Queensland Government’s Response As noted above determining conclusively whether any environmental changes have anything to do with the reported fish health problems is a formidable and perhaps impossible undertaking. However, the Panel acknowledges and supports the Queensland Government’s ongoing investigation of the issue and notes that good progress has been made to date. The locations sampled by Fisheries Queensland in Gladstone Harbour and the surrounding areas and a summary of the incidence of fish health issues observed (i.e. fish displaying cloudy eyes, skin discolouration or lesions) is provided in Figures 11, 12, 13 and 14. Having reviewed the available data and reports and provided advice on the future investigations of Gladstone Harbour, the Panel notes that the Queensland Government has acted or is acting based upon the advice provided by the Panel. In response to concerns about the health of other species, Fisheries Queensland monitoring indicated that approximately 95% of a total of nearly 2,000 non- barramundi fish caught in the Gladstone area were in good health. Of the remaining 5%, which was comprised of a variety of species, lesions observed ranged from mild skin conditions and fin damage to skin discolouration. No one bacterial, parasitic or fungal pathogen has been identified from the over 20 fish samples tested by Biosecurity Queensland. The presence of viral agents was assessed histologically, 23 however further viral testing was not required. Figure 11 : Barramundi: Map of Gladstone Harbour and the surrounding area showing the locations sampled by Fisheries Queensland and the prevalence of health issues (i.e. cloudy eyes, skin discolouration and other lesions) observed in sampled barramundi. The Department’s hypothesis is that the low level of prevalence may be caused by a number of stressors, but quite significantly included the extreme natural events that occurred earlier in the year resulting in severe flooding. With a lack of historical baselines and/or good comparative baseline information in areas to the north and south of Gladstone on the level of skin abnormalities in fish species, it is difficult to determine if the Gladstone data is an anomaly until further surveys are completed. The Panel has also provided suggestions to the Queensland Government for its consideration on ways ongoing studies could be expanded in the future to increase the possibility of determining whether any environmental changes have anything to do with the reported fish health problems. 24 Figure 12 : Other finfish: Map of Gladstone Harbour and the surrounding area showing the locations sampled by Fisheries Queensland and the prevalence of health issues (i.e. skin discolouration and other lesions) observed in sampled fin fish other than barramundi. Figure 13 : Sharks and rays: Map of Gladstone Harbour and the surrounding area showing the locations sampled by Fisheries Queensland and the prevalence of health issues (i.e. skin discolouration and other lesions) observed in sampled sharks and rays. 25 Figure 14 : Banana prawns: Map of Gladstone Harbour and the surrounding area showing the locations sampled by Fisheries Queensland and the prevalence of health issues (i.e. gill parasite and blemishes) observed in sampled banana prawns. The following outlines the Panel’s specific comments and recommendations in relation to the issues of Fish Health, Water Quality and Human Health with a view to identifying a possible cause(s) of the fish health issues being observed in Gladstone Harbour; consideration of the water quality monitoring programs currently in place; and the reported human health issues. Fish Health The Panel reviewed the available fish health data and reports and noted the data provided by the Queensland Government was appropriately collected and analysed. The Panel noted that fish are normally good integrative indicators of eco-system and environmental health, and having noted there may be an issue of concern in Gladstone Harbour the Panel undertook a more in-depth analysis of the fish health issue. The Panel concluded there is an issue of concern around the health of some species of fish in Gladstone Harbour and this is possibly caused by environmental factors. The extent of the issue is currently not known. The data for barramundi indicates this species may be stressed, but it is less clear for other fish species. This highlights the need for systematic data collection in Gladstone Harbour and other places to establish baselines, which requires ongoing investigation by the Queensland Government. While according to the reviewed reports, barramundi presented the clearest evidence of ill health, the problems are apparently not confined to this fish species. Therefore, the Panel proposed to the Queensland Government an assessment of the hypothesis that there is a yet unknown factor (or factors) causing stress in some fish species, but that barramundi appear to be more strongly affected because of the additional population stress associated with the introduction of an estimated 30,000 barramundi into Gladstone Harbour between 12 December 2010 and March 2011 with the overflow of the Awoonga Dam. 26 The addition of an estimated 30,000 large barramundi into an already stressed environment (floods) is likely to have caused a general environmental impact affecting barramundi and possible other species as a result of increased competition for food, and increased harassment by predators. The Panel noted the reports of disease from mud crabs and prawns concluded the incidence of bacterial infections and parasites observed were not unusual compared to previous studies in Gladstone Harbour and elsewhere. There were also concerns raised by commercial fishers about scallops caught near the spoil grounds outside Gladstone Harbour, and this is currently being assessed by Fisheries Queensland. Samples were collected for toxicological testing. Collection of comparative information The collection of comparative information is necessary in order to determine the scale of the problem being observed in barramundi and other fish species in the Gladstone area compared to what could be expected in a similar unaffected system. The data also allows an assessment of temporal changes and the identification of trends. Fish pathology The pathology data and other information available to date indicate that some species of fish 9 in Gladstone Harbour may be stressed and potentially immuno- compromised. However, this is only a hypothesis and it is necessary to continue Fisheries Queensland and other studies to determine the extent to which populations of barramundi and other fish species in Gladstone Harbour have been stressed and potentially compromised. Furthermore, it will also be necessary to determine whether a causal relationship can be definitively established between what is being observed in the fish in Gladstone Harbour and water quality and sediment. This has not been established to date. While the Panel agreed the observed parasitic infections, lesions and skin discolouration in fish taken from Gladstone Harbour indicates that these fish may be stressed, the Panel also noted there are a range of possible causes for this including: • Human induced mechanical damage (e.g. nets and cuts); • Chemical damage (e.g. exposure to toxins (metals, organic chemicals and natural toxins); low pH; turbidity); • Nutritional issues (e.g. poor nutrition); and • Physical issues (e.g. mechanical damage to the skin and or gills from algal blooms; insult by parasites or bacteria; salinity through its impact on a fish’s ability to osmoregulate; low dissolved oxygen; high carbon dioxide). This being the case, the Panel recommends that the identification of potential causal agent(s) should be the focus of future investigations. In reviewing the fish health data and reports, the Panel noted that at this time there is no evidence to indicate the fish with parasites, lesions and/or skin redness are a risk to human health via handling (see “Human Health” below for further information). However, the Panel noted that under the standard food guidelines, no fish with signs of disease should be consumed at any time in Gladstone Harbour or elsewhere. The Panel emphasises the importance of establishing baselines and trends during “normal” periods, and suggests ongoing studies should include appropriate areas outside the Harbour to act as a form of ‘control’ for comparative analysis i.e. use 27 more sophisticated study designs. The Panel suggests that ongoing pathology studies are a priority to support epidemiological studies and as a component of more in-depth investigations. In instances of disease outbreaks in wild populations where the pattern of lesions do not match known diseases, more sophisticated studies (possibly beyond that expected of a diagnostic laboratory) could be considered including eliminating viruses as causal agents 10 . The parasite ( Neobenedenia sp.) has been reported previously in Australia and has a wide host specificity. It is known to cause mass mortalities in aquaculture cages in many countries. Reports of high prevalences in wild fish are unusual, but may simply be a reporting issue 11 . While the presence of Neobenedenia on barramundi explains many of the lesions reported, the reasons for the current high prevalence and abundance of the parasite are unclear, but outbreaks are known to occur including in Hinchinbrook Channel, Queensland 12 but not to the extent seen in this instance. Neobenedenia melleni is a widespread pathogen of many teleost species in aquaria and aquaculture 13 . Most Monogenea have strict host-specificity but N. melleni has the broadest host-specificity of any monogenean species, having been recorded from over 100 species in more than 30 families from five orders of captive and wild fish 14 . The Panel also highlights the need to develop a case definition for the observed skin discolouration or “reddening”. For example, was the shark or fish live or was it post- mortem lividity; and, what is the location and extent of the “reddening”. “Reddening” on live animals is of interest, post-mortem lividity is likely to be of less interest. Recommendations : The fish health issue should be the ongoing focus of Queensland Government studies. As a priority, a conceptual model should be completed of possible cause-effect relationship(s) to help guide studies and eliminate potential causal factors. The development of the concept maps (Appendix 3) and the set of indicative diagrams (Figures 7-10) is the first step in developing the conceptual model. There is an immediate need to develop a case definition for the observed skin discolouration (“reddening”) in fish. 10 Skerratt, L, Speare R, Berger L. Mitigating the impact of diseases affecting biodiversity - Retrospective on the outbreak investigation for chytridiomycosis. EcoHealth 2011;7(Supplement: 1):S26-S26. 11 Jones, J.B. 2005. Chapter 10: Mass mortalities in the ocean. Pp 371-374. In : Rohde, K (ed) Marine parasites . CSIRO Publishing, Canberra. 12 Deveney MR, Chisholm LA, Whittington ID. (2001) First published record of the pathogenic monogenean parasite Neobenedenia melleni (Capsalidae) from Australia. Dis Aquat Organ., 461:79-82. 13 Deveney MR, Chisholm LA, Whittington ID. (2001) First published record of the pathogenic monogenean parasite Neobenedenia melleni (Capsalidae) from Australia. Dis Aquat Organ., 461:79-82. 14 Whittington, I. D. 2004. The Capsalidae (Monogenea : Monopisthocotylea): a review of diversity, classification and phylogeny with a note about species complexes. Folia Parasitologica 51:109-122. 28 The ongoing monitoring of the prevalence of the parasite, lesions and skin discolouration and the associated pathology investigations should continue as a priority and be guided by the conceptual model. Consideration should be given to experimental work with diseased fish and fish with Neobenedenia to better understand the parasites taxonomy, biology and pathogenesis; and studies on wild fish with lesions held in captivity and exposed to water of different quality. Water Quality The Panel reviewed the available water quality data and reports and agreed that the data provided by the Queensland Government was appropriately collected and analysed. The Panel concluded that the water quality results received to date indicate the observed values of the measured water quality parameters are not unusual (compared to historical values and trends), except for extremely low salinity during the 2010-2011 wet season. A number of areas of the Harbour, including the Boyne River, had zero or close to zero salinity for extended periods of time. The measured water quality parameters provide no insights into the cause of the high parasitic levels, lesions and skin discoloration observed in the fish. Changes to salinity can affect marine species that are unable to avoid the changes. Freshwater species need to constantly lose water gained through osmosis while marine species need to constantly drink (to make up for osmotic loss). The changes in osmolarity and particularly the changes in sodium and potassium caused by changes in salinity can be lethal. However, barramundi are adapted to moving from fresh to salt water and also to sub-optimal water quality (such as found in summer in billabongs and in floods and freshes). It is because they are such “tough” fish that they are so successful as aquaculture species. The Panel discussed the focus on total (particulate plus dissolved) metals data in water and a lack of monitoring data for metals in sediments and the apparent lack of monitoring data for organic chemicals in sediments and water. Given the focus of the monitoring programs, the Panel discussed whether the available water quality data is fit for purpose. The Panel noted the current parameters measured may not provide an appropriate trigger for ecosystem health problems that may be responsible for the observed fish health issues in Gladstone Harbour. For example, mercury (Hg), which can be highly toxic due to formation of methyl mercury, was not included in the list of tested metals. Even if Hg is not likely to be introduced via the current industrial activities, there might be other sources that cannot be ruled out upfront. Likewise, legacy persistent organic pollutants could have been remobilised during dredging. While these possibilities are highly speculative , they warrant further exploration. Water quality parameters need to be selected on the basis that they will provide a trigger for biological investigations at the chronic (or if possible sub-chronic level). Thus it is recommended that the Queensland Government commission or conduct a comprehensive literature review on the potential of chemicals to cause the observed signs in fish and then design a test program for metals and organic chemicals as well as natural toxins that targets the chemicals that may be associated with the observed signs in fish. The Panel noted that this case highlights the need for monitoring programs to align with some form of hypothesis testing (or conceptual model). It is noted that many of the chemicals that could contribute to health problems in fish (e.g. chemical induced immune-suppression) are hydrophobic and thus highly bio-accumulative and the chemical concentration in sediments would possibly provide a better surrogate than 29 the water phase. Thus testing of sediments should accompany future water quality sampling campaigns. However, the Panel emphasised there is no evidence from the histopathology reports of heavy metal impacts on fish tissues. Most of the common heavy metals have a documented tissue pathology, which the Queensland Government pathologists would have recognised. The Panel noted that the current sampling does not include organic chemicals or broad scale bacterial (prokaryotes) and microalgal (eukaryotes) assessment and recommends the Queensland Government assess the usefulness of including surveys of prokaryotic and eukaryotic community structure and composition using DNA bulk sequencing techniques and organic chemicals in the ongoing monitoring program. Recommendations : The Panel recommended the water quality monitoring be expanded to include analysis for dissolved metals (operationally defined as the fraction of metals in the water column that pass through a 0.45 µm filter). The dissolved metal fraction will potentially contain the readily bio-available fraction of metals (the fraction of metals that are readily taken up by aquatic organisms). DERM completed additional monitoring including dissolved metals during the week of 26 September 2011. The values observed were within the expected ranges for Australian tropical/sub-tropical coastal environments and not expected to cause adverse biological effects. The total (acid extractable) metals data from the sediment samples indicate the metal concentrations are at levels that would not be expected to cause adverse biological effects. One sediment site, QE3, had higher concentrations of aluminium, arsenic, barium and iron, which appears to be due to a different type of mineralization at this site. The Panel recommended continued water quality monitoring by the Queensland Government as an indicator of the general health of the Gladstone Harbour and surrounding areas, and the program is continuing. The Queensland Government commission or conduct a comprehensive literature review on the potential of chemicals to cause the observed signs in fish and then design a test program for metals and organic chemicals as well as natural toxins that targets the chemicals that may be associated with the observed signs in fish. The Panel recommended a one-off quantification of legacy persistent organic pollutants (such as polychlorinated dibenzodioxins, chlorinated pesticides and polychlorinated biphenyls) in sediments and (if possible) fish lipid tissue. DERM should re-assess and amend the monitoring program as necessary, as more information becomes available (framed as an adaptive management approach). The Queensland Government should engage with Port Curtis Integrated Monitoring Program Inc. (PCIMP) 15 and industries around Gladstone Harbour 15 The Port Curtis Integrated Monitoring Program (PCIMP) is the first collaborative holistic monitoring program to be undertaken for the whole of Port Curtis. PCIMP was established in 2001 as a consortium of members from 16 bodies representing industry, government (both local and state), research institutions and other stakeholders to develop a cooperative, monitoring program for assessing the ecosystem health of Port Curtis, and to 30 to ensure monitoring programs do have the power to detect potential impacts of the multiple potential stressors on Gladstone Harbour. The concept maps (Appendix 3) and indicative diagrams (Figures 7-10) could provide the basis for this engagement. Human Health To assess the human health impacts the Panel was provided with a report on a group of instances of illness in fishers from the Gladstone area that could potentially indicate an outbreak (see Queensland Health_HHRA Final 7 Oct.doc ). In addition, Panel member, Prof Rick Speare undertook an assessment of the Queensland Health report (see Illness in Fishers-Rick_Speare-15Oct11.pdf ). Queensland Health provided Prof Speare access to the de-identified line listing of the cases, which formed the basis of the Queensland Health report. This enabled the accuracy of the summarised data in the Queensland Health report to be confirmed from the original data. The Panel concluded that Queensland Health had conducted an appropriate and adequate investigation of the fishers. The Panel agreed with Queensland Health that the cases described did not form a single outbreak of one disease. The Panel agreed that there was no indication of an outbreak of disease in fishers that could be linked with disease in fish in Gladstone Harbour. The Panel agreed that additional investigations by Queensland Health of this group of fishers was not warranted. The Panel noted the occurrence of non-multiresistant Staphylococcus aureus (nmMRSA) in commercial fishers is an issue that warrants further investigation in collaboration with the commercial fishing industry. Workplace Health and Safety Queensland is engaging with the industry to try to address some the multiple risk factors for transmission among this group of mainly men who are cramped together for long periods with limited access to fresh water. Recommendations : That a study be conducted to establish a baseline incidence for illness in commercial fishers in the Gladstone area and possibly other areas of Queensland. This is essential if any outbreak of disease is to be identified in the future. That appropriate OH&S statistics should be routinely collected for the Queensland commercial fishing industry. That appropriate best practice OH&S guidelines for fishing and fish handling be developed in collaboration with the commercial fishing industry. Appendices Appendix 1 - List of documents, reports and datasets considered by the Panel. Appendix 2 - Terms of Reference and a list of Panel members and invited participants and their areas of expertise. Appendix 3 – Concept maps developed by the Queensland Government summarising the available information on the Gladstone fish health issue. ensure the environmental sustainability of the Port of Gladstone (see http://www.pcimp.com.au/ ). 31 Appendix 1 - List of documents, reports and datasets considered by the Gladstone Fish Health Scientific Advisory Panel Details of information/documents provided to the Panel (and made available through GovDex) Name of document Description Author/Provided by Date of upload Fish Health FH – Concept Concept Map (Shellfish).jpg Concept Map – shellfish Fisheries Queensland Nov 29 Mapping FH – Concept Concept Map (Finfish sharks).jpg Concept Map – finfish and sharks Fisheries Queensland Nov 29 Mapping FH – Concept Concept Map (Barra).jpg Concept Map – barramundi Fisheries Queensland Nov 29 Mapping FH – Fisheries FQ_GladstoneCrabSamplingMap Ver3.jpg Graphic depiction of fish sampling results – Fisheries Queensland Dec 14 sampling mud crab - updated FH – Fisheries FQ_GladstoneMudCrabs7-12-2011.jpg Graphic depiction of fish sampling results – Fisheries Queensland Dec 08 Sampling mud crabs. FH – Fisheries Fisheries sampling - Sharks and Rays.jpg Graphical depiction of fish sampling results Fisheries Queensland Nov 30 Sampling – sharks and rays FH – Fisheries Fisheries sampling - Other Finfish.jpg Graphical depiction of fish sampling results Fisheries Queensland Nov 30 Sampling – other finfish FH – Fisheries Fisheries sampling - Barramundi.jpg Graphical depiction of fish sampling results Fisheries Queensland Nov 30 Sampling – barramundi FH – Fisheries Fisheries sampling - Banana Prawns.jpg Graphical depiction of fish sampling results Fisheries Queensland Nov 30 Sampling – banana prawns 32 FH – Fisheries FQ_Fish-sampling-data-update-Nov11.pdf Fish sampling update – 11 November 2011 Fisheries Queensland Nov 24 Sampling FH – Fisheries FQ_Map-of-Gladstone-fish-sampling- Fish sampling map – 8 November 2011 Fisheries Queensland Nov 09 Sampling 8Nov11.pdf FH – Fisheries FQ_Fish-sampling-data-updated8Nov11.pdf Fish sampling update – 8 November 2011 Fisheries Queensland Nov 09 Sampling FH – Fisheries FQ_Map-of-Gladstone-fish-sampling- Fish sampling map – 17 October 2011 Fisheries Queensland Oct 24 Sampling 20Oct11.pdf FH – Fisheries FQ_Fish-sampling-data-update- Fish sampling update – 17 October 2011 Fisheries Queensland Oct 24 Sampling 17Oct11.pdf FH – Fisheries FQ_Gladstone fish sampling protocol.doc Details of fish sampling protocol. Fisheries Queensland Oct 24 Sampling FH – Fish Pathology BQ Gladstone Fish Health Report- Biosecurity Queensland report including Biosecurity Queensland Dec 08 Testing 8Dec2011.pdf toxicology results FH – Fish Pathology BQ lab report_P11-75654.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 17 Testing testing FH – Fish Pathology BQ lab report_P11-75573.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 17 Testing testing FH – Fish Pathology BQ lab report_P11-75569.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 17 Testing testing FH – Fish Pathology BQ lab report_P11-75566.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 17 Testing testing FH – Fish Pathology BQ lab report_P11-75531.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 17 Testing testing FH – Fish Pathology BQ lab report_P11-75529.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 16 Testing testing 33 FH – Fish Pathology BQ lab report_P11-75528.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 16 Testing testing FH – Fish Pathology BQ lab report_P11-75468.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 16 Testing testing FH – Fish Pathology BQ lab report_P11-75467.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 16 Testing testing FH – Fish Pathology BQ lab report_P11-75466.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 16 Testing testing FH – Fish Pathology BQ lab report_P11-75412.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 16 Testing testing FH – Fish Pathology BQ-Gladstone-Fish-Report-November- Fish Health Sampling Reports Biosecurity Queensland Nov 08 Testing 2011.pdf Gladstone Harbour As at 3 November 2011 FH – Fish Pathology BQ Lab Report P11-75286.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-75194.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-75124.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-75123.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-75085.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-75082.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing 34 FH – Fish Pathology BQ Lab Report P11-75082 SAS.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-74922.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-74903.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-74868.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-74796.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-74663.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing FH – Fish Pathology BQ Lab Report P11-74622.pdf Biosecurity Queensland lab report for fish Biosecurity Queensland Nov 07 Testing testing. FH – Fish Pathology BQ_Clarification-of-Interim-Biosecurity- Clarification of details within fish testing Biosecurity Queensland Oct 24 Testing Report-6Oct-2011.pdf report provided by Biosecurity Queensland. FH – Fish Pathology BQ_gladstone-fish_health-BQ-report-2.pdf Fish testing report provided by Biosecurity Biosecurity Queensland Oct 24 Testing Queensland. FH – Fish Pathology Biosecurity Qld_Interim Vet Diagnostic_30 Briefing to Chief Veterinary Officer Biosecurity Queensland Oct 05 Testing Sept 11.doc Biosecurity Queensland - Gladstone Fish Health Interim Veterinary Diagnostic Assessment (IVDA) FH – Fish Catch FQ_catch graphs_Barramunid_Gladstone Graphs representing cumulative catch of Fisheries Queensland Dec 2 Records and Fitzroy.doc barramundi, number of fishing days where barramundi was caught and catch of barramundi (kg) caught per fishing day for the Gladstone harbour (S30) and the Fitzroy 35 Area (R30; R29 & S29) FH – Fish Catch FQ_cumulative catch graphs_fitzroy and Graphs of cumulative catch of key fish Fisheries Queensland Dec 1 Records Gladstone.doc caught in Gladstone harbour (S30) and the Fitzroy Area (R30; R29 & S29) FH – Fish Catch FQ_Awoonga Barra spillover.pdf Details of Awoonga dam overflow Fisheries Queensland Oct 14 Records FH – Fish Catch Gladstone barra catch graphs.doc Details of catch of Barramundi in Gladstone Fisheries Queensland Oct 12 Records Harbour provided by Fisheries Queensland FH – Incident FQ_Gladstone Incident response to mid- Timeline and details of response from Fisheries Queensland Nov 11 Background nov2011.doc Queensland Government in relation to the Gladstone Fish Health issue FH – Incident Gladstone SITREP #16 6oct11.doc Daily SITREP prepared by Fisheries Fisheries Queensland Oct 07 Background Queensland FH – Incident Gladstone SITREP #15 5oct11.doc Daily SITREP prepared by Fisheries Fisheries Queensland Oct 06 Background Queensland FH – Incident Gladstone SITREP #14 4oct11.doc Daily SITREP prepared by Fisheries Fisheries Queensland Oct 06 Background Queensland FH – Incident GFHSP Chronology of Events.doc Chronology of events surrounding the Fisheries Queensland Oct 04 Background discovery and investigation of sick fish in Gladstone Harbour. FH – Incident Gladstone SITREP #13 3oct11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #12 30sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #11 29sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #10 28sep11.doc Daily SITREP Fisheries Queensland Oct 04 36 Background FH – Incident Gladstone SITREP #9 27sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #8 26sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #7 23sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #6 22sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #5 21sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #4 20sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #3 19sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #2 16sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Incident Gladstone SITREP #1 15sep11.doc Daily SITREP Fisheries Queensland Oct 04 Background FH – Scientific Collation of research projects.doc List of research projects Fisheries Queensland Dec 07 References FH – Scientific Net damage injuries.pdf Journal article – additional literature Brian Jones Nov 28 References provided by Panel member Net damage injuries to New Zealand hoki, Macruronus novaezelandia (Brian Jones) 37 (New Zealand Journal of Marine and Freshwater Research, 1993: Vol. 27: 23-30) FH – Scientific SAP journal article_dogger bank itch.pdf Journal article – additional literature Brian Jones Oct 13 References provided by Panel member FH – Scientific SAP journal article_EUS menhaden.pdf Journal article – additional literature Brian Jones Oct 13 References provided by Panel member FH – Scientific EUS review.pdf Journal article – additional literature Brian Jones Oct 07 References provided by Panel member Human Health HH Queensland Health_HHRA Final 7 Oct.doc Human health risks associated with Queensland Health Oct 13 diseased fish in the Gladstone region Assessment Report and Recommendations 7 October 2011 Water Quality WQ – Water Quality DERM_Comparison of Auckland Ck Analysis of water quality tests from DERM Dec 08 Sampling hatchery data.doc Gladstone Area Water Board WQ – Water Quality FQ_explanatory notes_hatchery sampling Water quality test results at the Gladstone Gladstone Area Dec 1 Sampling results.doc Area Water Hatchery intake Waterboard WQ – Water Quality FQ_Hatchery_Additional_Monitoring_Sep_ Water quality test results at the Gladstone Gladstone Area Dec 1 Sampling Oct_Nov_2011 (1).xls Area Water Hatchery intake Waterboard WQ – Water Quality FQ_WQ_Hatchery_results_(2).xls Water quality test results at the Gladstone Gladstone Area Dec 1 Sampling Area Water Hatchery intake Waterboard WQ – Water Quality DERM_phys-chem-port-curtis-october DERM water testing results October 2011 – DERM Nov 24 Sampling 2011.pdf phys/chem WQ – Water Quality DERM_nutrients-port-curtis-october DERM water testing results October 2011 – DERM Nov 24 38 Sampling 2011.pdf nutrients WQ – Water Quality DERM_metals-port-curtis-october 2011.pdf DERM water testing results October 2011 - DERM Nov 24 Sampling metals WQ – Water Quality PCIMP Report 2008-2010.pdf Port Curtis Integrated Monitoring Program Port Curtis Integrated Nov 22 Sampling Monitoring Program Port Curtis cosystem health report 2008- (provided by Leigh 2010 Gray) WQ – Water Quality Port Curtis Ecosystem Health Report Card Port Curtis Integrated Monitoring Program Port Curtis Integrated Nov 22 2011_Summary.pdf Monitoring Program Sampling Port Curtis cosystem health report 2008- (provided by Leigh 2010 Gray) Summary WQ – Water Quality Home Website link to: Western Basin Dredging Gladstone Ports Nov 18 Sampling Sediment Quality report and EIS (report too Corporation (provided large to upload to Govdex) by Leigh Gray) WQ – Water Quality DERM_supplementary water data_port- Water Quality of Port Curtis and Tributaries DERM Nov 08 Sampling curtis.pdf Supplementary Report Based on Data Collected in the week of 26th September 2011 November 2011 WQ – Water Quality 7-cm_port_curtis_modelling.pdf Hydrodynamic Modelling of the Port Curtis CSIRO (provided by Oct 24 Sampling Region DERM) CSIRO WQ – Water Quality Port Curtis monitoring summary.xls Details of monitoring program summary for DERM Oct 13 Sampling Port Curtis. WQ – Water Quality GPC_WBPD_Stage1_Water_Quality_Mana Water quality reports from Gladstone Ports Gladstone Ports Oct 05 Sampling gement_Plan.pdf Corporation website. Corporation WQ – Water Quality GPC_Report_Towards_a_light- Water quality reports from Gladstone Ports Gladstone Ports Oct 05 Sampling based_monitoring_program_Environmetrics Corporation website. Corporation 39 .pdf WQ – Water Quality GPC_Briefing_Western_Basin_Dredging_a Water quality reports from Gladstone Ports Gladstone Ports Oct 05 Sampling nd_Disposal_Project_Environmental_Impac Corporation website. Corporation ts.pdf WQ – Water Quality DERM-port-curtis-water-quality.pdf Port Curtis and Tributaries Comparison of DERM Oct 05 Sampling Current and Historical Water Quality October 2011 WQ – Scientific Chesapeake Bay Front Page.mht Journal article – additional literature Brian Jones Oct 13 References provided by Panel member WQ – Scientific SAP journal article_aerosolized toxins.pdf Journal article – additional literature Brian Jones Oct 13 References provided by Panel member WQ – Scientific SAP journal article_brevetoxins.pdf Journal article – additional literature Brian Jones Oct 13 References provided by Panel member Ecosystem Health EH – Seagrass FQ_Seagrass report_October 2011.pdf Gladstone Permanent Transect Seagrass Fisheries Queensland Nov 10 Monitoring Monitoring - October 2011 Interim Update Report EH – Seagrass FQ_Seagrass report_September 2011.pdf Gladstone Permanent Transect Seagrass Fisheries Queensland Nov 10 Monitoring Monitoring - Additional September 2011 assessment Update Report EH – Seagrass FQ_Seagrass report_July 2011.pdf Gladstone Permanent Transect Seagrass Fisheries Queensland Nov 10 Monitoring Monitoring - July 2011 Update EH – Seagrass FQ_Seagrass report_March 2011.pdf Gladstone Permanent Transects Seagrass Fisheries Queensland Nov 10 Monitoring Monitoring Sites - February and March 2011 Update Industry Representation Industry QSIA_1_letter from Law Essentials.doc Documents received from Law Essentials QSIA Dec 23 Representation with information specific to the fish and QSIA_2_Gladstone Harbour Chronolgy of 40 events.doc crustacean health issues in Gladstone. QSIA_3_details.doc The first attachment is the letter from Michael Garrahy summarising these QSIA_4_McMullen.pdf documents. QSIA_5_Appo.pdf The other documents are a chronolgy of QSIA_6_Pershouse.pdf dredging and development in the Harbour and Statuary Declarations from fishers QSIA_7_auction statement.pdf particularly relative to the crab disease. QSIA_8_Dale.pdf QSIA_9_Zink.tif QSIA_10_Samuels.tif Industry QSIA REPORT TO THE SCIENTIFIC QSIA comments and report to the GFHSAP QSIA Dec 19 Representation PANEL.pdf Industry QSIA_fisher statement.pdf Comments provided by commercial fisher in QSIA Dec 19 Representation relation to the Gladstone fish health issue Industry QSIA_Gladstone Fishboard Baseline Independent Testing undertaken by QSIA Dec 14 Representation Steven Nearhos Ref 86508 Dec 8 2011 Baseline - Inspection of fish and possible draft.pdf attribution of RSD initiation at Gladstone. Industry QSIA_sunni ,fish 029.JPG Photos from catch from Turkey beach week QSIA Dec 14 Representation beginning 5 December 2011 showing the QSIA_sunni ,fish 028.JPG sorts of lesions and rashes seen on other species. Fish caught by Chris Putman. QSIA_sunni ,fish 027.JPG QSIA_sunni ,fish 026.JPG QSIA_sunni ,fish 025.JPG QSIA_sunni ,fish 024.JPG QSIA_sunni ,fish 021.JPG QSIA_sunni ,fish 020.JPG QSIA_sunni ,fish 018.JPG 41 QSIA_sunni ,fish 017.JPG QSIA_sunni ,fish 015.JPG QSIA_sunni ,fish 014.JPG Industry QSIA_Law Essentials letter including video Letter from Law Essential to QSIA QSIA Dec 5 Representation links.doc Industry QSIA_email comments 20 november QSIA comments QSIA Nov 24 Representation 2011.doc Industry Timeline barra with pics 2.pdf Timeline barra – statement provided by Johnny Mitchell Nov 22 Representation Johnny Mitchell in relation to Awoonga dam (provided by Fisheries overflow and Barramundi catch Queensland) Industry BHart_response to DERM water quality Response provided by Barry Hart in relation Barry Hart (provided by Nov 08 Representation report.pdf to DERM water quality report. Fisheries Queensland) Industry QSIA Response to the Explanatory note to QSIA comment on Biosecurity Queensland QSIA Oct 31 Representation the Interim Biosecurity Report of the 6th report. October 2011.doc Industry QSIA_meeting with Gladstone fishing Details of meeting held by QSIA with the QSIA Oct 28 Representation community_19102001.doc Gladstone fishing community. Panel Documents Panel documents GFHSAP details of document provided - List of documents provided to the panel up Fisheries Queensland Dec 08 sorted.doc to 7 December 2011 Panel documents Gladstone Harbour SAP ToR 29Sep11.doc Terms of Reference for the GFHSAP Fisheries Queensland Oct 03 Panel documents Gladstone Fish Health Scientific Advisory Govdex site established created by Govdex Sep 30 Panel Robot 42 Appendix 2 - Terms of Reference and a list of Panel members and invited participants and their areas of expertise GLADSTONE HARBOUR AND SURROUNDING WATERS Scientific Advisory Panel – Terms of Reference Context/Background Following reports of diseased finfish, notably barramundi, from commercial catches in the Gladstone region, the Queensland Seafood Industry Association (QSIA) advised the Government that a number of commercial fishers or people associated with commercial fishers had reported health issues. Pending the outcome of laboratory testing of samples of diseased fish and in view of community concerns regarding food safety and human health, the Fisheries Gladstone (Gladstone Harbour and Surrounding Waters) Emergency Disease and Quarantine Declaration 2011 was put in place on Friday 16 September 2011. This prohibits all fishing, the use of all forms of fishing apparatus and the landing of any live fish (excluding crab) within the prescribed area that were caught outside the prescribed area. The interim closure is intended to be for no more than 21 days. Biosecurity Queensland has to date provided interim test results for samples of barramundi, and advised that eye lesions are due to a parasite ( Neobenedenia sp, a fluke) and skin lesions in one fish are due to red spot disease. Work on pathology and toxicology is continuing in relation to identification of causes of lesions in a variety of seafood species taken from the area. Queensland Health is continuing to follow up on any individuals reporting health issues. The Department of Environment and Resource Management is collating and reporting on available water quality monitoring and sediment metals information for the area. Objectives and Roles The Queensland Government is convening an expert Scientific Advisory Panel to provide independent advice to the Minister for Main Roads, Fisheries and Marine Infrastructure via the Department of Employment, Economic Development and Innovation. The role of the Scientific Advisory Panel is to review the Queensland Government's monitoring regimes, results and analysis primarily focusing on fish health in Gladstone Harbour and surrounds but also including consideration of water quality monitoring and human health issues where relevant and appropriate. This may include: • The water quality monitoring regime currently in place in Gladstone Harbour; • The investigation of recent fish and other diseased marine species in Gladstone Harbour; • Whether there is evidence of a link between the water quality and health of seafood species in Gladstone Harbour and surrounding areas; and • Whether there is any risk to human health in relation to water quality or seafood taken in these waters and recommendations for improvements in safe work practices in the fishing industry. Specifically, the Scientific Advisory Panel is requested to: 1. Review • the available test results, and assess previous water quality data and the current water quality and sediment monitoring regime; • the pathology and toxicology testing of seafood; and 43 • the investigation of potential impacts, if any, on human health. 2. Advise Government as to whether there is a need for additional testing or investigations. 3. Advise Government whether there are any identifiable reasons, based on the information supplied to the Panel and the expertise of its members, for the health issues affecting seafood species (finfish and crustaceans) in the Gladstone area and the evidence for links to human health issues. It is expected that the Panel will provide a preliminary assessment of existing information and reports within two weeks (by 13 October 2011), and will advise within six weeks as to what additional monitoring and analysis may be required. A final report from the Panel will be completed by mid December. Membership The membership of the Panel comprises eminent scientists, from the government and academic sectors, with recognised expertise and research publications concerning: aquatic environmental science including water quality; fish health and toxicology; and human health especially in relation to potential for transmission of diseases from marine species to humans. Panel Members Dr Ian Poiner (Chair) Chief Executive Officer, Australian Institute of Marine Science (Tropical marine ecology and fisheries) Professor Beate Escher University of Queensland, and Deputy Director, Entox (Environmental toxicology) Prof Rick Speare Anton Breinl Centre, James Cook University (Human health; tropical and zoonotic diseases) Professor David Parry Science Leader, Australian Institute of Marine Science, Northern Territory (Estuarine habitat and health, ecotoxicology) Dr Brian Jones Adjunct Professor, Murdoch University and Principal Fish Pathologist, Department of Fisheries Western Australia Prof Rod Connolly Griffith University, Australian Rivers Institute (Water quality and ecosystem health) Dr John Robertson General Manager, Fisheries Habitat and Assessment, Fisheries Queensland Julia Playford - (Invitee) Director, Water Quality and Aquatic Ecosystem Health, DERM Paul Florian - (Invitee) Director, Environmental Health, Queensland Health, Rockhampton Michael Gardner - (Invitee) President, Queensland Seafood Industry Association Leigh Gray – (Invitee) Manager, Water Quality Operations, Great Barrier Reef Marine Park Authority Secretariat will be provided by Fisheries Queensland, a service of the Department of Employment, Economic Development and Innovation. 44 Appendix 3 – Concept maps developed by the Queensland Government summarising the available information on the Gladstone fish health issue. 45 46 47 QLD gov feedback to fishermen Black Ooze Coal Ooze Dredging turbidity Leaking bund wall 2