Further Evaluation of IDEQ 2019 Paired Fish and Surface Water Arsenic Data

April 21, 2021 Presenters

Dr. Paul Anderson Arcadis

1 Executive Dr #303, Chelmsford, MA 01824 978-322-4504 [email protected]

Dr. Emily Morrison Arcadis

550 Teague Rd, Suite 210, Hanover, MD 21076 410-295-1205 [email protected]

© Arcadis 2019 21 April 2021 2 Introduction

21 April 2021 3 Idaho 2019 Data - Summary of Previous Analyses • No statistically significant relationship between arsenic in fish tissue and surface water

Total As in Surface Water and Fish Tissue Inorganic As in Surface Water and Fish Tissue Total As in Surface Water and Inorganic As Fish Tissue ) 700 12 ) g g ) k k g / / 12 k g g 600 / u u g 10 ( (

u ( e e 10 u u 500 e s s u s s

s 8 i i s T T i 8

400 T h h s s h i 6 i s F F i

6

300 F n n y = 0.1802x + 1.5901 y = 0.0977x + 1.6812 i i

y = 2.0932x + 75.185 n i s R² = 0.0116 s 4 R² = 0.0038 s A R² = 0.0013 A 4 200 P=0.48 l P=0.69 A c

a P=0.81 i t c n i o a n 2 T 100 2 g a r g o r n o I

0 n 0 0 I 0.0 2.0 4.0 6.0 8.0 10.0 0.0 2.0 4.0 6.0 8.0 10.0 0.0 2.0 4.0 6.0 8.0 10.0 Total As in Surface Water (ug/l) Inorganic As in Surface Water (ug/l) Total As in Surface Water (ug/l)

© Arcadis 2019 21 April 2021 4 Additional Evaluations

• Literature Review – Do previously published studies help explain the 2019 Idaho paired tissue and water data? • Additional Analyses of 2019 Idaho Data – Multivariate analysis to identify the parameters, if any, that have a statistically significant effect on iAs concentrations in fish tissue – Effect of fish body weight on tissue iAs concentration – Effect of fish feeding guild on the relationship between iAs concentration in tissue and surface water – Relationship between fish weight and on ratio of iAs to tAs – Effect of Idaho river basin on iAs surface water and tissue concentrations

© Arcadis 2019 21 April 2021 5 Literature Review

21 April 2021 6 Literature Review – Water/Tissue Relationship

• No relationship between As in surface water and fish tissue • Williams et al. 2006 – compiled surface water and fish tissue total As concentrations from 8 field studies (lakes, ponds, rivers in US and Canada)

© Arcadis 2019 21 April 2021 7 Literature Review -

• iAs undergoes biodilution/biodiminution • iAs bioaccumulates at lower trophic levels, including aquatic plants (e.g., periphyton, , and ) • iAs concentrations decrease with increasing trophic level in the foodweb – Chen and Folt 2000; Chen et al., 2008; Cheng et al., 2013; Chetalat et al., 2019; Dovick et al., 2015, Lopez et al., 2016; Maeda et al., 1990; Rahman et al., 2012

© Arcadis 2019 21 April 2021 8 Literature Review – Biomagnification (cont.) • Studies using stable isotope analysis to quantify organism trophic level position demonstrate biodiminution (Revenga et al., 2012)

© Arcadis 2019 21 April 2021 9 Revenga et al. 2012 Literature Review – /Conversion • Fish exposed in laboratory settings absent a accumulate As in tissue • Majority of total Arsenic (tAs) is in organic forms (e.g. methylated forms of As and arsenobetaine) • tAs in fish tissue was primarily arsenobeteine (56% in carp; 89% in eel, 95% in mullet, rainbow trout, and chub; Ciardullo et al 2008 and 2010) • 90% of tAs in muscle, liver, gill tissues of tilapia exposed to iAs in laboratory was organic As; 30-80% of tAs in gastrointestinal tract was organic As (Pei et al 2019) • 70-80% of tAs in tissues of carp exposed to iAs in laboratory was organic (Cui et al 2021) • Internal bioregulation converts inorganic As to organic As

© Arcadis 2019 21 April 2021 10 Literature Review Summary • Arsenic concentrations in tissue are not related to arsenic concentrations in the water column of natural systems • Arsenic concentrations decrease with increasing trophic level • This appears to be due to bioregulation of arsenic in aquatic organisms – conversion of inorganic forms to organic forms • Bioaccumulation in the traditional sense does not appear to apply to arsenic

© Arcadis 2019 21 April 2021 11 Additional Analyses of IDEQ Data

21 April 2021 12 Additional Analysis of 2019 IDEQ Data

1. Multivariate analysis - identify which, if any, parameters have a statistically significant effect on iAs concentrations in fish tissue 2. Relationship between fish body weight and tissue iAs concentration 3. Effect of fish feeding guild (diet) on the relationship between iAs concentration in tissue and surface water 4. Relationship between fish weight and trophic level on ratio of iAs to tAs 5. Effect of Idaho river basin on the relationship between iAs concentrations in tissue and surface water.

© Arcadis 2019 21 April 2021 13 Feeding Guild Assignments Species Guild/Diet • Assumed adult diet when assigning Bridgelip sucker Herbivore guild Cutthroat trout Insectivore Dace sp. Insectivore

Mountain whitefish Insectivore

Reside shiner Insectivore

Sculpin sp. Insectivore

Catfish sp. Piscivore

Brook trout Piscivore

Brown trout Piscivore

Largemouth bass Piscivore

Northern pikeminnow Piscivore

Rainbow trout Piscivore

Smallmouth bass Piscivore

© Arcadis 2019 21 April 2021 14 1. Multivariate Analysis • Identify parameters with a statistically significant effect on iAs concentration in fish tissue • Only fish weight has a statistically significant effect on iAs tissue concentration

Parameter F-Ratio P-value

Basin 0.88 0.51 Species 1.66 0.14 Feeding Guild 0.09 0.77 Average Fish Sample Weight* 12.4 0.002 Tissue Total As 0.78 0.39 Surface Water Total As 1.74 0.20 Surface Water Inorganic As 3.09 0.09 Error *Average weight of composite sample fish

© Arcadis 2019 21 April 2021 15 2. Relationship Between Fish Weight and iAs in Tissue

Inorganic Arsenic and Fish Weight Inorganic Arsenic and Fish Weight Composite Sample Average Fish Weight Individual Fish Weights )

g 12 12 k / g u

( Bridgelip Suckers

Bridgelip Suckers

e 10 10 ) u g s k s / i g T

u

8 ( h 8 s i s F A

n c i i

6 n s 6 a A g

r c i o n n I a 4 4

g -0.28 e -0.241 r y = 2.6858x y = 2.4884x u o s n R² = 0.1157

s R² = 0.0982 I i

P=0.02 T 2 2 P<0.01 h s i F 0 0 0 500 1000 1500 2000 0 500 1000 1500 2000 2500 3000 3500 Composite Sample Average Fish Weight (g) Individual Fish Sample Weight (g)

• Fish <100 g have a large range of iAs tissue concentrations • Virtually all fish >100 g have iAs tissue concentration ≤1 µg/kg – Bridgelip sucker is the exception

© Arcadis 2019 21 April 2021 16 2. Relationship Between Weight and iAs in Tissue - Bridgelip Sucker Inorganic Arsenic and Fish Weight Bridgelip Sucker • iAs tissue concentrations increase 12 ) g

with increasing weight k / 10 g u (

s y = 0.7439x0.348 A

8

c R² = 0.6088

• Bridgelip sucker diet changes from i

n P<0.001 a g r

primarily aquatic insect larvae for o 6 In

e

small suckers (<150 mm in length) u s 4 s i T

to primarily herbivorous as suckers h s i 2 grow larger (Dauble 1980) F 0 0 100 200 300 400 500 600 700 800 Individual Fish Weight (g)

• As a result, suckers transition from a higher to a lower trophic level with increasing weight, likely explaining the increase in iAs tissue concentration with increasing weight

© Arcadis 2019 21 April 2021 17 2. Relationship Between Weight and iAs in Tissue - Trout and Bass Species • Brown trout, rainbow trout, brook trout, largemouth bass, and smallmouth bass are primarily piscivorous as adults

Inorganic Arsenic in Fish Tissue and Fish Weight • Young may have more Trout and Bass Species Only )

g 10

insectivorous diet (i.e. lower trophic k / g

u 9 (

level) e u

s 8 s i T 7 h

– Change in iAs concentration as s i

F -0.707 6 y = 22.072x n i fish grow and transition from R² = 0.3369 s

A 5

P<0.001 c i

lower to higher trophic levels n

a 4 g r o

n 3 • The decrease in iAs tissue I 2

concentration with increasing 1

weight is statistically significant 0 0 100 200 300 400 500 600 700 800 Individual Fish Weight (g) © Arcadis 2019 21 April 2021 18 3. Effect of Feeding Guild on the Relationship Between iAs in Tissue and Surface Water Inorganic As in Surface Water and Fish Tissue by Feeding Guild • Herbivorous fish – not 12 Piscivores statistically significant, Insectivores 10 Herbivores small sample size (n=3) ) g Herbivores /k

g y = 1.3566x + 1.4752 u 8 ( R² = 0.5052 s P=0.38 A

• Insectivorous and c i n a

piscivorous fish – g r 6 Insectivores o n

I y = 0.7694x + 0.9477

significant relationships e R² = 0.1428 u

s P=0.05 s i 4 T

between iAs in surface h s i

F Piscivores water and fish tissue y = -0.3752x + 2.0873 2 R² = 0.0897 • However, little of the P=0.04 0 variation in tissue iAs 0 1 2 3 4 5 6 7 8 9 concentrations is explained Surface Water Inorganic As (ug/l) by iAs in surface water

© Arcadis 2019 21 April 2021 19 3. Effect of Feeding Guild on the Relationship Between iAs in Tissue and Surface Water • tAs highest in herbivorous fish, followed by piscivorous fish, and Median Sample Median Sample Median Inorganic Median Total lowest in insectivorous fish Guild Weight (grams) Length (mm) Arsenic (µg/kg) Arsenic (µg/kg) (Min – Max) (Min – Max) (Min – Max) (Min – Max) • iAs highest in herbivorous fish, then 380 340 4.4 87 Herbivororous insectivorous fish, and lowest in (20 - 740) (135 – 400) (2.3 – 10) (31 – 108)

piscivorous fish 20 110 0.6 41 Insectivorous (2 – 600) (60 – 400) (0.2 – 9.1) (11 – 278) • Herbivorous fish (bridgelip sucker) 240 240 0.4 53 Piscivorous • Longer and heavier than the (11 – 2,450) (110 – 540) (0.2 – 9.4) (0.9 – 583) insectivorous and piscivorous fish • But higher As concentrations because diet is primarily algae • Consistent with literature © Arcadis 2019 21 April 2021 20 4. Relationship Between Ratio of iAs to tAs and Fish Ratio of Inorganic to Total As and Average Fish Weight Weight Higher Trophic Level Species 1 o i t

a Brook Trout R

s A

l Brown Trout • Literature suggests larger, higher trophic 0.1 a t o

T Cutthroat Trout / c

level fish are likely to have lower of iAs to i n

a Largemouth Bass g

r 0.01

tAs ratios than lower trophic level species o n

I Rainbow Trout

e u

s Smallmouth Bass s i

T 0.001

• The ratio of iAs to tAs in most higher h 1 10 100 1000 s i trophic level species declined with F Average Weight (g) increasing body weight as these species Ratio of Inorganic to Total As and Average Fish Weight transitioned to a higher trophic level Lower Trophic Level Species o

i Bridgelip Sucker t 1 a R

Dace sp. s A

• The ratio of iAs to tAs in lower trophic l a

t Mountain Whitefish

o 0.1 T level fish did not change substantially with / c

i Northern n

a Pikeminnow g

r Redside Shiner increasing weight o 0.01 n I

e Sculpin sp. u s s i Catfish sp. T • 2019 IDEQ data consistent with literature

h 0.001 s i 1 10 100 1000 10000 F Average Weight (g)

© Arcadis 2019 21 April 2021 21 4. Ratio of iAs to tAs: Fish Weight and Trophic Level

• The iAs to tAs ratio tends to decrease with increasing weight and with increasing trophic level

Primary Diet Weight Range (g) Individual Species Components Species A = algae of Adult Fish Average I = insects 0-24 25-49 50-99 100-249 250-999 1000+ Bridgelip Sucker A 0.07 0.07 0.07 F = fish Common Carp A, I 0.02 0.02 Dace sp. A, F 0.03 0.03 Catfish A, I, F 0.02 0.02 Mountain Whitefish I 0.01 0.01 0.01 Sculpin sp. I 0.05 0.02 0.05 Redside Shiner I, F -0.03 0.03 Brook Trout I, F 0.003 0.003 Brown Trout I, F 0.02 0.06 0.009 0.009 Cutthroat Trout I, F 0.04 0.01 0.1 0.008 0.008 0.03 Rainbow Trout I, F 0.14 0.04 0.003 0.02 0.04 Northern Pike Minnow I, F 0.04 0.04 0.11 0.07 Smallmouth Bass F 0.004 0.004 Largemouth Bass F 0.009 0.003 Weight Class Average 0.05 0.03 0.07 0.01 0.02 (0.01)a 0.02 © Arcadis 2019 21 April 2021 22 a Weight class average if bridgelip sucker samples are excluded. 5. Effect of River Basin on the Relationship Between iAs in Tissue and Surface Water Average Inorganic As in Surface Water and Fish Tissue by River Basin • Overlap in fish tissue iAs 10 Clearwater River concentrations across river Basin Lower Bear River Basin

basins )

g Middle Snake River k / Basin g u (

Salmon River Basin

• Some river basins have no e u

s Spokane River Basin s i T overlap in surface water iAs

h 1

s Upper Snake River i F

Basin

concentrations n i

s A

c i n

• iAs concentrations in tissue a g r o n and water are independent I

0.1 0.01 0.1 1 10 Inorganic As in Surface Water (ug/l)

Notes: •Horizontal bars represent the min and max of the surface water iAs concentrations at each basin •Vertical bars represent the min and max of the fish tissue iAs concentrations at each basin

© Arcadis 2019 21 April 2021 23 Conclusions

21 April 2021 24 Conclusions

• 2019 Idaho data are consistent with trends reported in the literature across a wide variety of study locations and freshwater aquatic foodwebs • Further evaluation of the 2019 data indicates: • iAs undergoes biodilution/biodiminuition (decrease in concentration with increasing trophic level) in Idaho aquatic food webs • iAs tissue concentrations decrease with increasing fish size and trophic level, regardless of iAs concentration in surface water for most fish species • Organic As is the primary form of As in fish tissue, especially in larger and upper trophic level fish likely because of metabolic transformation of iAs to organic As • As a result, iAs in surface water is not predictive of iAs in fish tissue

© Arcadis 2019 21 April 2021 25 Thank you! Questions/Discussion

© Arcadis 2019 21 April 2021 26 References

• Chen, C.Y., and C.L. Folt. 2000. Bioaccumulation and diminution of arsenic and lead in a freshwater food web. Environ. Sci. Technol. 34:3878-3884. • Chen C.Y., P.C. Pickhardt, M.Q. Xu, C.L. Folt. 2008. and arsenic bioaccumulation and in Baiyangdian Lake, China. Water, Air, and Soil Pollution 190:115–27. • Cheng, Z., K-C. Chen, K-B. Li, X-P. Nie, S.C. Wu, C. K-C. Wong, M-H. Wong. 2013. Arsenic contamination in the freshwater fish ponds of Pearl River Delta: bioaccumulation and health risk assessment. Environmetnal Science and Pollution Research 20: 4484-4495. • Chetalat, J., P.A. Cott, M. Rosabal, A. Houben, C. McClelland, E.B. Rose, M. Amyot. 2019. Arsenic bioaccumulation in subarctic fishes of a mineimpacted bay on Great Slave Lake, Northwest Territories, Canada. PLoS ONE 14(8): e0221361. • Ciardullo, S. F. Aureli, A. Raggi, F. Cubadda. 2010. Arsenic speciation in freshwater fish: Focus on extraction and mass balance. Talanta 81: 213-221. • Ciardullo, S. F. Aureli, E. Coni, E. Guandalini, F. Iosi, A. Raggi, G. Rufo, F. Cubadda. 2008. Bioaccumulation potential of dietary arsenic, cadmium, lead, mercury, and selenium in organs and tissues of rainbow trout (Oncorhynchus mykiss) as a function of fish growth. Journal of Agriculture and Food Chemistry 56: 2442-2451. • Cui, D., P. Zhang, H. Liu, Z. Zhang, Y. Song, Z. Yang. 2021. The dynamic changes of arsenic biotransformation and bioaccumulation in muscle of freshwater food fish crucian carp during chronic diet-borne exposure. Journal of Environmental Sciences 100: 74-81. • Dovick, M.A., T.R. Kulp, R.S. Arkle, D.S. Pilliod. 2015. Bioaccumulation trends of arsenic and antimony in a freshwater ecosystem affected by mine drainage. Environmental Chemistry 13: 149-159. • Lopez, A.R., D.R. Hesterberg, D.H. Funk, D.B. Buchwalter. 2016. Bioaccumulation Dynamics of Arsenate at the Base of Aquatic Food Webs. Environmental Science and Technology 50: 6556-6564. • Maeda, S., A. Ohki, T. Tokuda and M. Ohmine. 1990. Transformation of arsenic compounds in a freshwater food chain. Appl. Organom. Chem. 4:251-254. • Pei, J.J., Zuo, X. Wang, J. Yu, L. Liu, W. Fan. 2019. The Bioaccumulation and Tissue Distribution of Arsenic Species in Tilapia. International Journal of Environmental Research and Public Health 16: 757-768. • Rahman, M.A., H. Hasegawa, R. Peter Lim. 2012. Bioaccumulation, biotransformation and trophic transfer of arsenic in the aquatic food chain. Environmental Research 116:118–35. • Revenga, J.E., L.M. Campbell, M.A. Arribere, S.R. Guevara. 2012. Arsenic, cobalt and chromium food web biodilution in a Patagonia mountain lake. Ecotoxicology and Environmental Safety 81: 1-10. • Williams, L., R.A. Schoof, J.W. Yager, J.W. Goodrich-Mahoney. 2006. Arsenic bioaccumulation in freshwater fishes. Human and Ecological Risk Assessment 12:

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