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Widespread detection of N, N-diethyl-m-toluamide in U.S. streams: Comparison with concentrations of pesticides, personal care products, and other organic wastewater compounds

One of the most frequently detected organic chemicals in a nationwide study concerning the effects of wastewater on stream water quality conducted in the year 2000 was the widely used insect repellant N , N -diethyl- m -toluamide (DEET). It was detected at levels of 0.02 μg/L or greater in 73% of the stream sites sampled, with the selection of sampling sites being biased toward streams thought to be subject to wastewater contamination (i.e., downstream from intense urbanization and livestock production). Although DEET frequently was detected at all sites, the median concentration was low (0.05 μg/L). The highest concentrations of DEET were found in streams from the urban areas (maximum concentration, 1.1 μg/L). The results of the present study suggest that the movement of DEET to streams through wastewater-treatment systems is an important mechanism that might lead to the exposure of aquatic organisms to this chemical.

Environmental Toxicology and Chemistry↗

Multiple sublethal chemicals negatively affect tadpoles of the green frog, Rana clamitans

Many habitats may be exposed to multiple chemical contaminants, particularly in agricultural areas where fertilizer and pesticide use are common; however, the singular and interactive effects of contaminants are not well understood. The objective of our study was to examine how realistic, sublethal environmental levels of ammonium nitrate fertilizer (0, 10, 20 mg/L and ammonium chloride control) and the common insecticide carbaryl (0 or 2.5 mg/L) individually and interactively affect the development, size, and survival of green frog ( Rana clamitans ) tadpoles. We reared tadpoles for 95 d in outdoor 1,000-L polyethylene ponds. We found that the combination of carbaryl and nitrate had a negative effect on development and mass of tadpoles compared to the positive effect that either contaminant had alone. Presence of carbaryl was generally associated with short-term increases in algal resources, including ponds exposed to both carbaryl and nitrate. However, with exposure to nitrate and carbaryl, tadpole mass and development were not positively affected as with one chemical stressor alone. The combination of these sublethal contaminants may reduce the ability of amphibians to benefit from food-rich environments or have metabolic costs. Our study demonstrates the importance of considering multiple stressors when evaluating population-level responses.

Environmental Toxicology↗

Effects of selected polybrominated diphenyl ether flame retardants on lake trout (Salvelinus namaycush) thymocyte viability, apoptosis, and necrosis

Polybrominated diphenyl ether (PBDE) flame-retardants have been identified as an emergent contaminants issue in many parts of the world. In vitro analyses were conducted to test the hypothesis that selected PBDEs congeners affect viability, apoptosis, and necrosis of thymocytes from laboratory-reared lake trout ( Salvelinus namaycush ). At current environmental levels (<1 mg/L), effects of the tested PBDEs on thymocytes were negligible. However, at 100 mg/L, major effects were seen for congener brominated diphenyl ether 47 (BDE-47) and minor effects were seen for congener BDE-99.

Environmental Toxicology and Chemistry↗

Time trends (1983-1999) for organochlorines and polybrominated diphenyl ethers in rainbow smelt ( Osmerus mordax ) from Lakes Michigan, Huron and Superior, USA

The U.S. Geological Service Great Lakes Science Center has archived rainbow smelt ( Osmerus mordax ) collected from the early 1980s to the present. These fish were collected to provide time- and site-dependent contaminant residue data needed by researchers and managers to fill critical data gaps regarding trends and behavior of persistent organic contaminants in the Great Lakes ecosystem. In the present study, data are presented for concentrations of several organochlorine (OC) contaminants in the archived smelt, including DDT, polychlorinated biphenyls (PCBs), toxaphene, and chlordanes in Lakes Michigan and Huron (MI, USA) and in Lake Superior (MN, USA). The trends for all the OCs were declining as a first-order decay over the sampled time series (1983/1985&ndash;1993/1999) with the exception of toxaphene in Lake Superior and PCBs at the Charlevoix/Little Traverse Bay site in Lake Michigan. Concentration of the emerging contaminant, polybrominated diphenyl ethers (PBDEs), also was traced from its apparent entry into this ecosystem in approximately 1980 until 1999. Time trends for the PBDEs were increasing exponentially at all sites, with concentration-doubling times varying from 1.58 to 2.94 years.

Environmental Toxicology and Chemistry↗

A field assessment of long-term laboratory sediment toxicity tests with the amphipod Hyalella azteca

Response of the amphipod Hyalella azteca exposed to contaminated sediments for 10 to 42 d in laboratory toxicity tests was compared to responses observed in controlled three-month invertebrate colonization exposures conducted in a pond. Sediments evaluated included a sediment spiked with dichlorodiphenyldichloroethane (DDD) or dilutions of a field sediment collected from the Grand Calumet River (GCR) in Indiana (USA) (contaminated with organic compounds and metals). Consistent effects were observed at the highest exposure concentrations (400 ??g DDD/goc [DDD concentrations normalized to grams of organic carbon (goc) in sedimentl or 4% GCR sediment) on survival, length, and reproduction of amphipods in the laboratory and on abundance of invertebrates colonizing sediments in the field. Effect concentrations for DDD observed for 10-d length and 42-d reproduction of amphipods (e.g., chronic value [ChV] of 66 ??g DDD/goc and 25% inhibition concentration [IC25] of 68 ??g DDD/goc for reproduction) were similar to the lowest effect concentrations for DDD measured on invertebrates colonizing sediment the field. Effect concentrations for GCR sediment on 28-d survival and length and 42-d reproduction and length of amphipods (i.e., ChVs of 0.20-0.66% GCR sediment) provided more conservative effect concentrations compared to 10-d survival or length of amphipods in the laboratory or the response of invertebrates colonizing sediment in the field (e.g., ChVs of 2.2% GCR sediment). Results of this study indicate that use of chronic laboratory toxicity tests with H. azteca and benthic colonization studies should be used to provide conservative estimates of impacts on benthic communities exposed to contaminated sediments. Bioaccumulation of DDD by oligochaetes colonizing the DDD-spiked sediment was similar to results of laboratory sediment tests previously conducted with the oligochaete Lumbriculus variegates, confirming that laboratory exposures can be used to estimate bioaccumulation by oligochaetes exposed in the field. ?? 2005 SETAC.

Environmental Toxicology and Chemistry↗

Acute and chronic toxicity of lead in water and diet to the amphipod Hyalella azteca

We evaluated the influence of waterborne and dietary lead (Pb) exposure on the acute and chronic toxicity of Pb to the amphipod Hyalella azteca . Test solutions were generated by a modified diluter with an extended (24‐h) equilibration period. Acute (96‐h) toxicity of Pb varied with water hardness in the range of 71 to 275 mg/L as CaCO 3 , despite similar dissolved Pb concentrations. Acute toxicity was greatest in soft test water, with less than 50% survival at the lowest dissolved Pb concentration (151 μg/L). Survival also was significantly reduced in medium‐hardness water but not in hard test water. In chronic (42‐d) studies, amphipods were exposed to waterborne Pb and fed either a control diet or a diet equilibrated with waterborne Pb levels. For animals fed the control diet, the median lethal concentration (LC50) for Pb was 24 μg/L (as dissolved Pb), and significant reductions in survival occurred at 16 μg/L. Exposure to Pb‐treated diets significantly increased toxicity across a wide range of dissolved Pb concentrations, with a LC50 of 16 μg/L and significant reductions in growth and reproduction at 3.5 μg/L. Significant effects on growth and reproduction occurred at dissolved Pb concentrations close to the current U.S. chronic water‐quality criterion. Our results suggest that both aqueous‐ and dietary‐exposure pathways contribute significantly to chronic Pb exposure and toxic effects in aquatic biota.

Environmental Toxicology and Chemistry↗

Absorption of p,p'-dichlorodiphenyldichloroethylene and dieldrin in largemouth bass from a 60-D slow-release pellet and detection using a novel enzyme-linked immunosorbent assay method for blood plasma

This work describes the uptake of two organochlorine pesticides from slow-release pellets by largemouth bass and the utility of a blood plasma enzyme-linked immunosorbent assay (ELISA) method for exposure verification. We measured blood and tissue levels by gas chromatography/mass spectrometry and by a novel ELISA method, and present a critical comparison of the results.

Environmental Toxicology and Chemistry↗

Influence of water temperature on acetylcholinesterase activity in the pacific tree frog ( Hyla regilla )

This investigation evaluated whether acetylcholinesterase (AChE) in Pacific tree frogs ( Hyla regilla ) from different geographical locations was influenced by different temperatures during early aquatic life stages, independent of pesticide exposure. Tadpoles were collected from both a California coastal pond and a Sierra Nevada mountain range pond, USA. Groups of frogs from each location were raised in temperatures representative of either the Sierra Nevada (8°C) or the coastal (19°C) location. Metamorphs from both locations raised as tadpoles at 19°C had AChE activities of 42.3 and 38.7 nm/min/mg protein, while those raised as tadpoles at 8°C had activities of 26.9 and 28.2 nm/min/mg protein. A two-way analysis of variance revealed temperature to be the significant factor in determining AChE activity ( F = 22.3, p < 0.001), although origin was not important ( F = 0.09, p = 0.75). Interpretations regarding the influence of pesticides upon AChE activity in Pacific tree frogs must consider the influence of environmental temperature to enable cross-population comparisons.

Environmental Toxicology and Chemistry↗

Metamorphosis of two amphibian species after chronic cadmium exposure in outdoor aquatic mesocosms

Amphibian larvae at contaminated sites may experience an alteration of metamorphic traits and survival compared to amphibians in uncontaminated conditions. Effects of chronic cadmium (Cd) exposure on the metamorphosis of American toads ( Bufo americanus ) and southern leopard frogs ( Rana sphenocephala ) were determined. The two species were reared separately from shortly after hatching through metamorphosis in outdoor mesocosms (1,325-L polyethylene cattle tanks) that simulated natural ponds and enhanced environmental realism relative to the laboratory. Both species exhibited a decrease in survival with increasing initial nominal aqueous Cd concentration. Cadmium treatment did not influence mass at metamorphosis for either species when survival was included as a covariate, but increased the age at metamorphosis for the American toads. The whole body Cd content of metamorphs increased with aqueous Cd treatment level for both species, and the American toads tended to possess more elevated residues. Cadmium quickly partitioned out of the water column and accumulated in and altered the abundance of the tadpoles' diet. Cadmium-contaminated sites may produce fewer metamorphs, and those that survive will metamorphose later and contain Cd. Interspecific differences in the response variables illustrate the importance of testing multiple species when assessing risk.

Environmental Toxicology and Chemistry↗

Subchronic effects of methylmercury on plasma and organ biochemistries in great egret nestlings

In recent years, high concentrations of mercury have been found in wading birds in Florida, USA. Great egret ( Ardea alba ) chicks (2 weeks old) were dosed orally daily with the equivalent of 0, 0.5, or 5 μg/g Hg as methylmercury chloride in the diet for up to 12 weeks. Weakness of the legs or paralysis occurred in all high-dosed birds. Geometric mean blood Hg concentrations were 0.17, 10.3, and 78.5 μg/g (wet wt), respectively. Mercury concentrations for organs (μg/g wet wt), including brain (0.22, 3.4, and 35, respectively), liver (0.34, 15.1, 138, respectively), and kidney (0.28, 8.1, and 120, respectively), increased in a dose-dependent manner. Total glutathione (GSH) peroxidase activity was significantly lower in the plasma, brain, liver, and kidney of the high-dosed group. Plasma aspartate aminotransferase activity increased with mercury treatment, whereas lactate dehydrogenase activity decreased. Four other plasma chemistries were decreased significantly in the high-dosed group and included uric acid, total protein, albumin, and inorganic phosphorus. Lipid peroxidation increased in liver (low and high dose) and brain (high dose). Tissue changes in concentrations of reduced thiols included decreased total thiols and protein-bound thiols in liver, decreased protein-bound thiols in kidney, and increased GSH in kidney and brain. Activities of GSH S -transferase and oxidized glutathione reductase increased in liver. In kidney, GSH S -transferase and glucose-6-phosphate dehydrogenase activities increased with mercury dose. These findings, including apparent compensatory changes, are compared to other Hg studies where oxidative stress was reported in egrets, herons, and diving ducks in the field and mallards in the laboratory.

Environmental Toxicology and Chemistry↗

Delineating copper accumulation pathways for the freshwater bivalve Corbicula using stable copper isotopes

Delineation of metal uptake routes in aquatic invertebrates is critical for characterizing bioaccumulation dynamics and assessing risks associated with metal exposure. Here we demonstrate that Cu stable isotopic ratios can be manipulated in both exposure media and algae to determine the efflux rate constant ( k e ) and to estimate Cu assimilation efficiency (AE) from ingested food in a freshwater bivalve ( Corbicula fluminea ). The Cu AE in Corbicula fed 65 Cu‐spiked Cryptomonas ozolini was 38%. Copper uptake routes had no significant influence on efflux; k e of 0.004 per day characterized the slowest component of efflux following short‐term exposures to 65 Cu in water or in both food and water. Incorporation of the physiological parameters for dietary and dissolved uptake as well as rate constants of loss into a bioaccumulation model allowed for assessing the relative contribution of water and food as Cu sources. At [ 65 Cu 2+ ] of 6.7 μg/L, Corbicula accumulated twice as much Cu from diet as from water. In most freshwater systems, the dietary pathway is likely to act as the major Cu uptake route for Corbicula . Extrapolation of our laboratory results to the San Francisco Bay—Delta (California, USA) indicated that our biodynamic model and the laboratory‐derived parameters for dietary 65 Cu uptake provided a realistic representation of the processes involved in Cu accumulation by the bivalve Corbicula .

Environmental Toxicology and Chemistry↗

Chlorfenapyr and mallard ducks: Overview, study design, macroscopic effects, and analytical chemistry

The first commercial pesticide derived from a class of compounds known as halogenated pyrroles was registered for use in the United States in 2001. Chlorfenapyr degrades slowly in soil, sediment, and water and is highly toxic to birds. Information on biochemical or histological endpoints in birds is lacking; therefore, a two‐year study was conducted to provide information needed to develop diagnostic criteria for chlorfenapyr toxicosis. In the first year, male mallard ducks were fed concentrations of 0, 2, 5, or 10 ppm technical chlorfenapyr or 5 ppm of a formulated product in their diet during a 10‐week chronic exposure study. Survival, body weight, feed consumption (removal), behavior, and molt progression were monitored. Feed and liver were analyzed for chlorfenapyr and two metabolites. Five of 10 ducks in the 10‐ppm group died, and neurotoxic effects were observed in the 5‐and 10‐ppm groups. Feed removal increased for ducks receiving chlorfenapyr and body weights of 5‐ and 10‐ppm ducks were reduced. Loss of body fat, muscle atrophy, and bile retention were suggestive of metabolic disruption or a decreased ability to digest and absorb nutrients. Liver and kidney weights and liver and kidney weight/body weight ratios exhibited a positive response to concentrations of chlorfenapyr in the diet. Emaciation and elevated organ weight/body weight ratios are candidates for a suite of indicators of chronic chlorfenapyr exposure. Liver is the preferred tissue for chemical confirmation of exposure.

Environmental Toxicology and Chemistry↗

Interlaboratory evaluation of Hyalella azteca and Chironomus tentans short-term and long-term sediment toxicity tests

Methods for assessing the long-term toxicity of sediments to Hyalella azteca and Chironomus tentans can significantly enhance the capacity to assess sublethal effects of contaminated sediments through multiple endpoints. Sublethal tests allow us to begin to understand the relationship between short-term and long-term effects for toxic sediments. We present an interlaboratory evaluation with long-term and 10-d tests using control and contaminated sediments in which we assess whether proposed and existing performance criteria (test acceptability criteria [TAC]) could be achieved. Laboratories became familiar with newly developed, long-term protocols by testing two control sediments in phase 1. In phase 2, the 10-d and long-term tests were examined with several sediments. Laboratories met the TACs, but results varied depending on the test organism, test duration, and endpoints. For the long-term tests in phase 1, 66 to 100% of the laboratories consistently met the TACs for survival, growth, or reproduction using H. azteca , and 70 to 100% of the laboratories met the TACs for survival and growth, emergence, reproduction, and hatchability using C. tentans . In phase 2, fewer laboratories participated in long-term tests: 71 to 88% of the laboratories met the TAC for H. azteca , whereas 50 to 67% met the TAC for C. tentans . In the 10-d tests with H. azteca , and C. tentans , 82 and 88% of the laboratories met the TAC for survival, respectively, and 80% met the TAC for C. tentans growth. For the 10-d and long-term tests, laboratories predicted similar toxicity. Overall, the interlaboratory evaluation showed good precision of the methods, appropriate endpoints were incorporated into the test protocols, and tests effectively predicted the toxicity of sediments.

Environmental Toxicology and Chemistry↗

Presence and distribution of wastewater-derived pharmaceuticals in soil irrigated with reclaimed water

Three sites in the Front Range of Colorado, USA, were monitored from May through September 2003 to assess the presence and distribution of pharmaceuticals in soil irrigated with reclaimed water derived from urban wastewater. Soil cores were collected monthly, and 19 pharmaceuticals, all of which were detected during the present study, were measured in 5‐cm increments of the 30‐cm cores. Samples of reclaimed water were analyzed three times during the study to assess the input of pharmaceuticals. Samples collected before the onset of irrigation in 2003 contained numerous pharmaceuticals, likely resulting from the previous year's irrigation. Several of the selected pharmaceuticals increased in total soil concentration at one or more of the sites. The four most commonly detected pharmaceuticals were erythromycin, carbamazepine, fluoxetine, and diphenhydramine. Typical concentrations of the individual pharmaceuticals observed were low (0.02–15 μg/kg dry soil). The existence of subsurface maximum concentrations and detectable concentrations at the lowest sampled soil depth might indicate interactions of soil components with pharmaceuticals during leaching through the vadose zone. Nevertheless, the present study demonstrates that reclaimed‐water irrigation results in soil pharmaceutical concentrations that vary through the irrigation season and that some compounds persist for months after irrigation.

Environmental Toxicology and Chemistry↗

Source apportionment modeling of volatile organic compounds in streams

It often is of interest to understand the relative importance of the different sources contributing to the concentration cw of a contaminant in a stream; the portions related to sources 1, 2, 3, etc. are denoted cw,1, cw,2, cw,3, etc. Like c w, 'he fractions ??1, = cw,1/c w, ??2 = cw,2/cw, ??3 = cw,3/cw, etc. depend on location and time. Volatile organic compounds (VOCs) can undergo absorption from the atmosphere into stream water or loss from stream water to the atmosphere, causing complexities affecting the source apportionment (SA) of VOCs in streams. Two SA rules are elaborated. Rule 1: VOC entering a stream across the air/water interface exclusively is assigned to the atmospheric portion of cw. Rule 2: VOC loss by volatilization, flow loss to groundwater, in-stream degradation, etc. is distributed over cw,1 cw,2, c w,3, etc. in proportion to their corresponding ?? values. How the two SA rules are applied, as well as the nature of the SA output for a given case, will depend on whether transport across the air/water interface is handled using the net flux F convention or using the individual fluxes J convention. Four hypothetical stream cases involving acetone, methyl-tert-butyl ether (MTBE), benzene, chloroform, and perchloroethylene (PCE) are considered. Acetone and MTBE are sufficiently water soluble from air for a domestic atmospheric source to be capable of yielding cw values approaching the common water quality guideline range of 1 to 10 ??g/L. For most other VOCs, such levels cause net outgassing (F > 0). When F > 0 in a given section of stream, in the net flux convention, all of the ??j, for the compound remain unchanged over that section while cw decreases. A characteristic time ??d can be calculated to predict when there will be differences between SA results obtained by the net flux convention versus the individual fluxes convention. Source apportionment modeling provides the framework necessary for comparing different strategies for mitigating contamination at points of interest along a stream. ?? 2006 SETAC.

Environmental Toxicology and Chemistry↗

Influence of metal exposure history on the bioaccumulation and subcellular distribution of aqueous cadmium in the insect Hydropsyche californica

The influence of metal exposure history on rates of aqueous Cd accumulation, elimination, and subcellular distribution was examined in the aquatic insect Hydropsyche californica . Specimens were obtained from a reference site and a metal‐contaminated site and returned to the laboratory where they were continuously exposed to aqueous Cd (518 ng/L, nominal) for 6 d, followed by 9 d of depuration. Rates of Cd accumulation and elimination were similar in insects from the two sites. Efflux rate constants, k e , ranged from 0.20 to 0.24/d ( t 1/2 ≈ 3 d). Immediately following exposure, the cytosol accounted for 40% of the body burden in insects from both sites; however, 89 ± 2% of the cytosolic Cd was associated with metallothionein‐like proteins (MTLP) in insects from the contaminated site, compared to 60 ± 0% in insects from the reference site. The concentration of Cd bound to non‐MTLPs (representing potentially Cd‐sensitive proteins) was significantly greater in the insects from the reference site (134 ± 7 ng/g) than in those from the contaminated site (42 ± 2 ng/g). At the end of the depuration period, 90% of the accumulated Cd body burden had been eliminated, and Cd concentrations in MTLPs and non‐MTLPs were similar between the sites. Results suggested that differences in exposure history had no influence on the bioaccumulation of Cd, but did affect the concentrations of Cd bound to MTLP during Cd exposure in these insects.

Environmental Toxicology and Chemistry↗

Dietary exposure of mink ( Mustela vison ) to fish from the Housatonic River, Berkshire County, Massachusetts, USA: Effects on reproduction, kit growth, and survival

We evaluated the effects of feeding farm-raised mink (Mustela vison) diets containing polychlorinated biphenyl (PCB)-contaminated fish from the Housatonic River (HR; Berkshire County, MA, USA) on adult reproductive performance and kit growth and survival. Diets contained 0.22-3.54% HR fish, providing 0.34-3.7 ??g total PCBs (TPCB)/g feed wet wt (3.5-68.5 pg toxic equivalence [TEQ]/g). Female mink were fed diets before breeding through weaning of kits. Twelve kits from each treatment were maintained on their respective diets for an additional 180 d. Dietary PCBs had no effect on the number of offspring produced, gestation period, or other measures of adult reproductive performance. Mink kits exposed to 3.7 ??g TPCB/g feed (68.5 pg TEQ/g) in utero and during lactation had reduced survivability between three and six weeks of age. The lethal concentrations to 10 and 20% of the population (LC10 and LC20, respectively) were estimated to be 0.231 and 0.984 ??g TPCB/g feed, respectively. Because inclusion of PCB-contaminated fish that composed approximately 1% of the diet would reduce mink kit survival by 20% or more, it is likely that consumption of up to 30-fold that quantity of HR fish, as could be expected for wild mink, would have an adverse effect on wild mink populations. ?? 2006 SETAC.

Environmental Toxicology and Chemistry↗

Dietary exposure of mink (Mustela vison) to fish from the Housatonic River, Berkshire County, Massachusetts, USA: Effects on organ weights and histology and hepatic concentrations of polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalence

The effects of feeding ranch mink ( Mustela vison ) diets containing polychlorinated biphenyl (PCB)-contaminated fish (88 gold fish [ Carassius auratus ] weighing a total of 70.3 kg and 16 carp [ Cyprinus carpio ] weighing a total of 77.3 kg) collected from the Housatonic River (HR; Berkshire County, MA, USA) in October 1999 on organ weights and histology and hepatic concentrations of total PCBs (&Sigma;PCBs) and 2,3,7,8-tetrachlorodibenzo- p -dioxin toxic equivalence (TEQ) were evaluated. Diets contained 0.22 to 3.54% HR fish, which provided 0.34 to 3.7 &mu;g &Sigma;PCBs/g feed (3.5-69 pg TEQ/g feed). Female mink were fed the diets eight weeks before breeding through weaning of kits at six weeks of age. Offspring were maintained on their respective diets for an additional 180 d. The dietary concentration of PCBs that caused a decrease in kit survival (3.7 &mu;g &Sigma;PCBs/g feed [69 pg TEQ/g]) resulted in a maternal hepatic concentration of 3.1 &mu;g &Sigma;PCBs/g wet weight (218 pg TEQ/g). Organ weights were not consistently affected. Mandibular and maxillary squamous cell proliferation was apparent in 31-week-old juveniles exposed to as low as 0.96 (xg &Sigma;PCBs/g feed (9.2 pg TEQ/g). Juveniles in this treatment group had a liver concentration of 1.7 &mu;g &Sigma;PCBs/g wet weight (40 pg TEQ/g). Because inclusion of PCB-contaminated fish, which comprised approximately 1% of the diet, resulted in mandibular and maxillary squamous cell proliferation, it is possible that consumption of up to 30-fold that quantity of HR fish, as could be expected for wild mink, would result in more severe lesions characterized by loss of teeth, thus impacting survivability.

Environmental Toxicology and Chemistry↗