Research

Impact of Abandoned Mining Facility Wastes on the Aquatic Ecosystem of the Mogpog River, ,

Catherine B. Gigantone,1 Background. Mine waste from abandoned mining sites can cause environmental degradation Marisa J. Sobremisana,1 and ecological imbalance to receiving water bodies. Heavy metal pollution affects local Lorele C. Trinidad,2 communities and may pose health risks to the general public. An abandoned mining facility Veronica P. Migo3 in Marinduque, Philippines, situated on the of Mogpog River, continuously deposits mine wastes, which may affect the river and the health of local communities. 1 School of Environmental Sciences and Objectives. The aim of the present study was to examine the presence and extent of heavy Management, University of the Philippines metal contamination from mine wastes in the aquatic ecosystem of the Mogpog River by Los Baños, College, Laguna, Philippines determining the level of heavy metal concentration in the water, sediments and biota. 2 National Institute of Molecular Biology Methods. Four sampling sites were monitored for heavy metals (copper (Cu), arsenic (As), and Biotechnology, University of the chromium (Cr) and sulfur (S)) pollution. Several analyses were conducted to determine the Philippines Los Baños, College, Laguna, heavy metals present in the water, sediment and biota. Atomic absorption spectrophotometry Philippines was used for the analysis of Cu concentrations in water. X-ray fluorescence was used for the 3 Department of Chemical Engineering, analysis of total heavy metals in the sediments and biota. College of Engineering and Agro Industrial Results. An inverse relationship with water and sediment from upstream to downstream of Technology, University of the Philippines the river were observed. This trend shows deposition of Cu in the sediments as factored by Los Baños, College, Laguna, Philippines pH. Flora gathered from the riverbanks recorded concentrations of Cu in their leaves and fruits. Corresponding author: Conclusions. It has been difficult for the Mogpog River to regain water quality after years of Catherine B. Gigantone mine waste deposition. Acid mine drainage occurred upstream of the river which affects the [email protected] speciation of heavy metals. The potential risk of heavy metal exposure to local communities was observed due to the communities’ river utilization. Participant Consent. Obtained Ethics Approval. The Office of Vice Chancellor for Research and Extension of University of the Philippines Los Baños approved the study Competing Interests. The authors declare no competing financial interests. Introduction Keywords. mine waste pollution, heavy metals contamination, Marinduque, acid mine drainage. A previous study has been conducted Received December 1, 2019. Accepted March 26, 2020. to determine toxicities of heavy metals J Health Pollution 26 (200611) 2020 to humans and their harmful effects on © Pure Earth the environment.1 The most significant industries which introduce heavy metals into the environment are mining, coal fired power plants and waste disposal.1 Extraction of ore deposits during of heavy metals may exhibit acute in the country.6 Marinduque, an mining creates large volumes of rock or chronic illnesses such as Itai-itai island in the center of the country, wastes or mine tailings which contain (cadmium poisoning), Minamata has vast resources of gold containing high levels of heavy metals. These disease (mercury poisoning) and copper ores. Two mining companies waste materials, when released into keratosis (arsenic poisoning).5 previously operated on the island: the environment, are highly toxic and Consolidated Mining Inc. and cause adverse effects to the ecosystem The Philippines is very rich in natural Marcopper Mining Corporation. Both and human health.2,3 Heavy metals and mineral resources; exploration have had incidents of mine tailings cause histological and morphological of mineral resources began as early disposal in Marinduque’s aquatic changes in tissues, physiology, behavior, as the 1900’s during American ecosystems. reproduction and biochemistry of colonization.6 Gold and copper are blood and enzymes.4 Human exposure the most abundant mineral resources In 1993, the Maguila-guila earthen

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dam collapsed due to heavy rains, Abbreviations depositing large volumes of mine wastes into the Mogpog River, causing LOD Limit of detection adverse environmental impacts to terrestrial and aquatic ecosystems. Health impacts of heavy metal intoxication to nearby communities were reported and the river was declared to be biologically dead.7 The present study evaluates the mined in Marinduque. Copper to the center of the Philippines (Figure presence and extent of heavy metals, speciation in water and sediments 1). Mogpog is one of six municipalities specifically copper (Cu), chromium spatially distributed in Mogpog River within Marinduque. (Cr), arsenic (As) and sulfur (S) is highlighted. The area is innately rich contamination from mine wastes in in Cu, hence it is expected to have high The Mogpog River is a shallow river the aquatic ecosystem of the Mogpog Cu concentrations relative to other with a depth ranging from 2-3 feet. It River by determining the levels of trace metals. was declared biologically dead due to heavy metal concentrations in the mine tailings spillage in 1993.8 Prior water, sediments and biota of the Methods to the disaster, the river was used for river system. Marcopper porphyry laundering clothes, planting water copper, a high-grade copper, was Marinduque is an island province close spinach (locally known as kangkong),

Figure 1 — Study sampling sites

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fishing and other recreational activities species at the time of sampling which site (0.06 ppm) and other sampling by local communities. Marcopper resulted in a small sampling size of sites along the whole stretch of Mining Company is situated in a each species. Only 1 g dried sample Mogpog River (Butansapa 0.69 ppm; watershed drainage of the Mogpog per species were yielded from dried Mangyan Mababad 0.06 ppm; and River. Four sampling points within composite samples. For example, ~10 Nangka II 0.09 ppm). the Mogpog River were selected based guppies yielded ~1 g of dried samples; on their proximity to the mining area 3 individual ferns yielded ~1 g dried Figure 3 shows the Cu concentration (Figure 1). Bocboc, the first village sample. levels in the sediments from 4 posterior to the mining site was sampling sites along the Mogpog River selected as an upstream sampling site, Social survey and the amount of Cu in the control followed by Butansapa (midstream), site Paadjao Falls. Mangyan Mababad Mangyan Mababad (midstream) and A survey on local residents’ had the highest concentration of Cu Nangka II (downstream). A control knowledge, perceptions and attitude compared to the other three sites. site (Paadjao Falls) was also selected was conducted to determine possible based on its proximity to the sampling exposures of nearby communities Further comparison of Cu adsorbed sites, without being affected by mining along the riverbanks to heavy metals in sediments and dissociated in water activities. Sediments, water and biota in the river as factored by their current using polynomial regression (4th order samples were collected and analyzed river usage. The total population of and 3rd order consecutively) showed for total heavy metals (Cu, As and S) the four villages surveyed is 2794 an inverse relationship. Most of the Cu content. based on 2015 population census coming from the effluents accumulates data.10 Total number of households in the sediments as shown in Figure 4. Water quality analysis was estimated at 559. Using Slovin’s formula,11 one respondent from each Heavy metals in biota Temperature, pH, and copper of 61 households were considered at content were analyzed in the four 90% confidence level and 10% margin Table 1 shows the Cu levels in various sampling sites. Atomic absorption of error. Purposive sampling was fauna available along the Mogpog spectrophotometry was used in the used in selecting the respondents of River in comparison to fauna collected determination of Cu concentration in the study. Women aged between 18 at the control site (Paadjao Falls). the riverine water. to 60 were considered as respondents Fish collected from Bocboc migrated for the study. Women were chosen from Paadjao Falls. The sampling area Sediment and biota heavy metal as respondents because in general is near the merging of water from analysis they are more knowledgeable upstream of Bocboc and Paadjao about domestic use of river water Falls. Guppy (Poecilia sphenops) An X-ray fluorescence for activities such as bathing and collected from Bocboc had higher spectrophotometer (Niton) was used laundering. Informed consent was levels of Cu (121.19 ppm) compared in the analysis of the sediment and obtained from each participant. Prior to guppy samples collected at Paadjao biota’s total heavy metal concentration. to the conduct of the study, approval Falls (116.37 ppm). High levels of The Canadian Sediment Quality from the Office of Vice Chancellor for Cu dissociate in water and changes Guidelines and Standards were used Research and Extension of University in pH are some of the externalities in the analysis of threshold effect of the Philippines Los Baños was (from 8.23 to 3.81), which cause the levels and probable effect levels in obtained. non-survival of living biota in the the organisms present in the river.9 Mogpog River situated at Bocboc. The Mogpog River remains heavily Results Copper concentrations of Poecilia affected by mine waste leaking from sphenops (guppy) collected from abandoned facilities causing most Figure 2 shows the Cu concentration Bocboc station showed 4% more parts of the river to be biologically and pH levels in water from 4 Cu compared to those collected in dead. It has been difficult for the sampling sites along the Mogpog Paadjao Falls (control station). Only Mogpog River to regain water quality, River and a control site, Paadjao Falls. a few fauna species were collected in which affects the diversity of its flora High levels of Cu were present in the sampling sites due to the inability and fauna. Collated samples were the riverine water situated at Bocboc of the organisms to proliferate in the limited to the available flora and fauna (11.936 ppm) compared to the control riverine water.

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Figure 2 — Copper concentrations and pH of riverine water in various sampling sites of the Mogpog River

Figure 3 — Copper concentration of sediments collected from various sampling sites along the Mogpog River

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Figure 4 — Polynomial regression of copper in sediments and water of the Mogpog River

Table 1 — Copper Levels in Available Fauna in Paadjao Falls, Bocboc and Nangka II

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Table 2 — Copper Concentrations in Various Flora Species Gathered from Designated Sampling Sites along the Mogpog River

Table 2 shows the flora samples conducted by Dutta and Ghosh, Cassia compared to samples from Butansapa. gathered from various sampling alata is a hyperaccumulator plant No literature is available for cross- stations along the riverbanks of the species.14 Generally, the results of the referencing the level of Cu in these Mogpog River. Available flora with present study suggest that the streams flora species. direct contact to sediment and riverine of the Mogpog has high bioavailable water were collected and analyzed Cu in its sediments and water; and Among all the collected flora, only using X-ray fluorescence analysis. species found along the riverbanks are Pityrogramma calomelanos, commonly Based on the available data presented tolerant of high concentrations of Cu. known as silver back fern, recorded in Table 2, very high Cu content was As concentrations, amounting to recorded in the flora species situated Collected flora species were selected 36.32 ppm. All sediments tested along the Mogpog riverbanks. This is based on availability at the sampling for As yielded lower than the limit observed in Nephrolepis biserrata, a stations. No indicator species were of detection (LOD) of the X-ray fern species, which is found in Paadjao present across all sampling stations. fluorescence, a limitation of the

Falls and Bocboc with values of 34.06 This is due to the altered landscape instrument used for analysis. ppm and 225.76 ppm, respectively. and toxicity of sediments and water Another species found to have high to the biota. Percent differences in Cu Other relevant heavy metal in levels of Cu was Albizia saman (rain concentrations of some species were sediments tree) found in Butansapa (49.12 ppm) determined. Nephrolepis biserrata and Mangyan Mababad (49.59 ppm). collected from Bocboc station had Very high levels of Cr were recorded in Cassia alata gathered from the Nangka 85% more Cu compared to those Bocboc, compared to Paadjao Falls and II estuary had the highest Cu content collected in Paadjao Falls (controlled other sampling sites which recorded (334.58 ppm) recorded among all station). Albizia saman collected from

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Figure 5 — Chromium concentrations of sediments collected from various sampling sites along the Mogpog River

Figure 6 shows S levels in sediments River for laundering and bathing. The Butansapa (0.68682 ppm at pH 6.56) along the Mogpog River. Very high children in villages upstream of the and Mangyan Mababad (0.05605 S concentrations were recorded in Mogpog River do not bathe in the ppm at pH 6.79) shows changes in Bocboc and Butansapa at 10828.68 river. All of the children across all sites the state of Cu. The neutral (6.5-7.55) ppm and 8027.77 ppm, respectively. were observed to cross the river more pH of water caused the formation of

High concentrations of S in sediments frequently compared to adults. Cu(OH)2(s). Comparing the values for indicate occurrence of acid mine dissolved Cu and pH to standards set drainage upstream of the Mogpog River. Discussion by Department of Environment and Natural Resources, Administrative Community exposure to heavy In general, cupric ion (Cu2+) was the Order 34 and 2016-08, the riverine metals dominant copper species in conditions water of the Mogpog River from with pH 3.81, while precipitates of Bocboc to Nangka II exceeded the

Figures 7 a-e present the respondents’ copper hydroxide (Cu(OH)2(s)) and acceptable level of dissolved Cu (Class self reported exposures in several Cu2+ were present at pH 6.5 - 7.55.15 AA-C 0.02 ppm; Class D 0.04 ppm) communities along the Mogpog It can be inferred that in the river, and Bocboc (pH 3.81) exceeded the River. Respondents from upstream the dominant Cu species present was acceptable pH level for Class AA-B and midstream villages of Mogpog in the form of dissociated Cu2+, as (6.5-8.5) and Class C-D (6.0-9.0).16,17 do not use the river for laundering observed by the high Cu concentration and bathing, but frequently cross the in Bocboc (11.9360 ppm at pH 3.81) The control site Paadjao Falls had Cu Mogpog River, while respondents riverine water. Similarly, the decline levels exceeding the Administrative from Nangka II still use the Mogpog in Cu concentration observed in Order 2016-08 standard for water

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Figure 6 — Sulfur concentrations of sediments collected from various sampling sites along the Mogpog River

quality.17 This data suggests that of Cu from 0.05605 ppm (Mangyan of water during wave movement and Marinduque is naturally rich in Cu. Mababad) to 0.09145 ppm (Nangka tide influx. As pH increases under Comparison of Cu content in Bocboc II) may be brought about by salinity saline conditions, Cu precipitates

(11.94 ppm), Butansapa (0.69 ppm) of the estuary wherein dissolution of (Cu2O(s)) dissolve forming Cu-chloride 19 and Nangka II (0.09 ppm) to Paadjao Cu precipitates (Cu2O(s)) to aqueous (Cl) complexes. This is evident in

Falls (0.06 ppm) shows that Cu content forms of copper chloride (CuCl(x)(aq)) is the sudden drop of Cu concentration in the river stream is relatively high. It facilitated.19 from 4617.2 ppm (Mangyan Mababad) can be inferred that there is continuous to 503.59 ppm (Nangka II), although leakage of wastewater and sediments Copper in sediments relatively high compared to 75.35 ppm coming from the Marcopper Mining recorded in Paadjao Falls. Comparing Corporation into the Mogpog River, There was an increasing trend in heavy the natural Cu present in soil, confirming the observation of local metals concentration in sediments represented by sediments in Paadjao residents, as shown in Figure 8. The moving further downstream. This Falls, there is a significant increase Bocboc site had an acidic pH that may trend can be attributed to the pH of in the Cu concentration of sediment be an indication of acid mine drainage the riverine water, which influences along the Mogpog River. in the area due to mine wastewater and the fate of Cu: either it can be sediments from abandoned mining dissociated in water in ionic form Copper in sediment-water facilities. This is brought about by the (acidic); or it forms precipitates and interaction reaction of mined sulfide rocks with adheres to sediments (neutral to dissolved and/or atmospheric oxygen. basic).15 In this case, Cu precipitated As observed in Figure 2 (Cu in water) The pH levels affect the speciation from water and adhered to sediments and Figure 3 (Cu in sediments), there of heavy metals in water causing the due to its pH value (6.56 to 6.79). was an increasing level of heavy metals decreasing trend of Cu in water as A decline in Cu concentration in present in the sediments downstream observed downstream.18 On the other sediments gathered in Nangka II, an of the river, but decreasing levels of hand, increases in the concentration estuary, may be attributed to mixing heavy metals dissociated in the water.

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Figure 7 — Exposure to Mogpog River through the following activities: (a) bathing; (b) children bathing; (c) river crossing; (d) children’s river crossing; and (e) laundry

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This relationship is illustrated in Figure 4. It can be inferred that the dominant species of Cu was Cu2+ in Bocboc brought about by low pH value (3.81). On the other hand, dominant Cu speciation at Butansapa and

Mangyan Mababad was solid Cu(OH)2 due to its neutral pH (6.56 and 6.79, respectively).15

The earthen dam (Maguila-guila dam) drains to the Mogpog River. Bocboc is the nearest sampling station in the upstream part of the river. Sedimentation was observed in the area which caused shallowing of the river (2-3 feet depth).

Other heavy metal in biota

Silver back fern (Pityrogramma calomelanos) is a metallotolerant species specific to As and is an As hyperaccumulator.20 Ferns are observed to thrive in Cu enriched substrates.20 Other fern species (Nephrolepis biserrata and Amphineuron sp.) gathered from Paadjao Falls, Butansapa and Bocboc recorded values of As less than LOD (9 ppm). This can be attributed to the specificity of plants to accumulate or hyperaccumulate certain heavy metals. Extremophiles are important in ecological assessments as they can be used for monitoring the extent of pollution in the environment.21

Heavy metals in sediment

High concentrations of detected Cr indicate that the mine wastewater and sediments contain Cr, thus contaminating Bocboc sediments. Low readings of Cr in other sampling sites may imply that Cr from upstream may Figure 8 — Documentation of mine waste pollution in Bocboc, have been accumulated in the biota or Mogpog River sediments (a & b) suspended milky-white colloids; and changed its speciation. The Cr present (c) rust deposits along the riverbank in the sediments may be present as organic salts, which is bioavailable for organism uptake. Various flora gathered across sampling sites had

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2020 Apr 27]. 35 p. Report No.: CCME EPC-98E. 19. Ahonen L. Effect of saline water on metallic Available from: http://ceqg-rcqe.ccme.ca/download/ copper [Internet]. Helsinki, Finland: Posiva Oy; 1999 en/226/ Oct [cited 2020 Mar 31]. 34 p. Available from: http:// 10. Philippine Statistics Authority. 2015 Census www.posiva.fi/files/2581/POSIVA-99-58_Working- of Population Report No. 1 – G report_web.pdf REGION. Population by Province, City, Municipality, 20. Kachenko AG, Singh B, Bhatia NP. Heavy and . [Internet] 2016 [cited 2020 May 6] metal tolerance in common fern species. Aust J Bot Available from: http://www.psa.gov.ph/sites/default/ [Internet]. 2007 Jan 18 [cited 2020 Mar 31];55(1):63- files/17_MIMAROPA%204B.pdf 73. Available from: https://doi.org/10.1071/BT06063 11. Cochran, William G. Sampling Techniques. Third Subscription required to view. edition. New York, USA. Wiley, 1977. 21. Arora NK, Panosyan H. Extremophiles: 12. Daly HR, Hart BT, Campbell IC. Copper toxicity applications and roles in environmental sustainability. to Paratya australiensis. IV. Relationship with ecdysis. Environ Sustain [Internet]. 2019 [cited 2020 Mar Environ Toxicol Chem [Internet]. 1992 Jun [cited 31];2:217-8. Available from: https://doi.org/10.1007/ 2020 Apr 27];11(6):881-3. Available from: https://doi. s42398-019-00082-0 org/10.1002/etc.5620110616 Subscription required 22. Loudon AG. Marcopper porphyry copper deposit, to view. Philippines. Econ Geol [Internet]. 1976 Jul 1 [cited 13. Ambient water quality criteria for copper 2020 Mar 31];71(4):721-32. Available from: https:// [Internet]. Washington, DC: United States doi.org/10.2113/gsecongeo.71.4.721 Environmental Protection Agency; 1980 [cited 2020 23. Bigham JM, Cravotta CA III. Acid mine drainage. Apr 27]. 169 p. Report No.: EPA 440/5-80-036. In: Lal R, editor. Encyclopedia of soil science. 3rd ed. Available from: https://www.epa.gov/wqc/ambient- Boca Raton, FL: CRC Press; 2016. 5 p. water-quality-criteria-copper 14. Dutta K, Ghosh AR. Comparative study on bioaccumulation and translocation of heavy metals in some native plant species along the bank of chromite contaminated Damsal Nala of Sukinda Valley, Odisha, India. Int Res J Biol Sci. 2016 Jul;5(7):32-52. 15. Albrecht TW, Addai-Mensah J, Fornasiero D. Effect of pH, concentration and temperature on copper and zinc hydroxide formation/precipitation in solution. Chemeca 2011: Engineering a Better World; 2011 Sep 18-21; Sydney Hilton Hotel, Australia. Barton, Australia: Engineers Australia; 2011. p. 2100-10. 16. DENR administrative order no. 34: revised water usage and classification [Internet]. Quezon City, Philippines: Department of Environment and Natural Resources; 1990 Mar 20 [cited 2020 Mar 31]. 17 p. Available from: https://emb.gov.ph/wp-content/ uploads/2016/04/DAO-1990-34.pdf 17. DENR administrative order no. 2016-08: water quality guidelines and general effluent standards of 2016 [Internet]. Quezon City, Philippines: Department of Environment and Natural Resources; 2016 May 24 [cited 2020 Mar 31]. 25 p. Available from: https://pab.emb.gov.ph/wp-content/ uploads/2017/07/DAO-2016-08-WQG-and-GES.pdf 18. Jennings SR, Neuman DR, Blicker PS. Acid mine drainage and effects on fish health and ecology: a review. Bozeman, MT: Reclamation Research Group Publication; 2008 Jun. 29 p.

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