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Effects of metal mining and milling on boundary waters of Yellowstone National Park, USA

Aquatic resources in Soda Butte Creek within Yellowstone National Park, USA, continue to be threatened by heavy metals from historical mining and milling activities that occurred upstream of the park's boundary. This includes the residue of gold, silver, and copper ore mining and processing in the early 1900s near Cooke City, Montana, just downstream of the creek's headwaters. Toxicity tests, using surrogate test species, and analyses of metals in water, sediments, and macroinvertebrate tissue were conducted from 1993 to 1995. Chronic toxicity to test species was greater in the spring than the fall and metal concentrations were elevated in the spring with copper exceeding water quality criteria in 1995. Tests with amphipods using pore water and whole sediment from the creek and copper concentrations in the tissue of macroinvertebrates and fish also suggest that copper is the metal of concern in the watershed. In order to understand current conditions in Soda Butte Creek, heavy metals, especially copper, must be considered important factors in the aquatic and riparian ecosystems within and along the creek extending into Yellowstone National Park.

Environmental Management↗

Geogenic organic contaminants in the low-rank coal-bearing Carrizo-Wilcox aquifer of East Texas, USA

The organic composition of groundwater along the Carrizo-Wilcox aquifer in East Texas (USA), sampled from rural wells in May and September 2015, was examined as part of a larger study of the potential health and environmental effects of organic compounds derived from low-rank coals. The quality of water from the low-rank coal-bearing Carrizo-Wilcox aquifer is a potential environmental concern and no detailed studies of the organic compounds in this aquifer have been published. Organic compounds identified in the water samples included: aliphatics and their fatty acid derivatives, phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, and phthalates. Many of the identified organic compounds (aliphatics, phenols, heterocyclic compounds, PAHs) are geogenic and originated from groundwater leaching of young and unmetamorphosed low-rank coals. Estimated concentrations of individual compounds ranged from about 3.9 to 0.01 μg/L. In many rural areas in East Texas, coal strata provide aquifers for drinking water wells. Organic compounds observed in groundwater are likely to be present in drinking water supplied from wells that penetrate the coal. Some of the organic compounds identified in the water samples are potentially toxic to humans, but at the estimated levels in these samples, the compounds are unlikely to cause acute health problems. The human health effects of low-level chronic exposure to coal-derived organic compounds in drinking water in East Texas are currently unknown, and continuing studies will evaluate possible toxicity.

Texas↗

Abandoned mine drainage in the Swatara Creek Basin, southern anthracite coalfield, Pennsylvania, USA: 1. stream quality trends coinciding with the return of fish

Acidic mine drainage (AMD) from legacy anthracite mines has contaminated Swatara Creek in eastern Pennsylvania. Intermittently collected base-flow data for 1959–1986 indicate that fish were absent immediately downstream from the mined area where pH ranged from 3.5 to 7.2 and concentrations of sulfate, dissolved iron, and dissolved aluminum were as high as 250, 2.0, and 4.7 mg/L, respectively. However, in the 1990s, fish returned to upper Swatara Creek, coinciding with the implementation of AMD treatment (limestone drains, limestone diversion wells, limestone sand, constructed wetlands) in the watershed. During 1996–2006, as many as 25 species of fish were identified in the reach downstream from the mined area, with base-flow pH from 5.8 to 7.6 and concentrations of sulfate, dissolved iron, and dissolved aluminum as high as 120, 1.2, and 0.43 mg/L, respectively. Several of the fish taxa are intolerant of pollution and low pH, such as river chub (Nocomis icropogon) and longnose dace (Rhinichthys cataractae). Cold-water species such as brook trout (Salvelinus fontinalis) and warm-water species such as rock bass (Ambloplites rupestris) varied in predominance depending on stream flow and stream temperature. Storm flow data for 1996–2007 indicated pH, alkalinity, and sulfate concentrations decreased as the stream flow and associated storm-runoff component increased, whereas iron and other metal concentrations were poorly correlated with stream flow because of hysteresis effects (greater metal concentrations during rising stage than falling stage). Prior to 1999, pH\5.0 was recorded during several storm events; however, since the implementation of AMD treatments, pH has been maintained near neutral. Flow-adjusted trends for1997–2006 indicated significant increases in calcium; decreases in hydrogen ion, dissolved aluminum, dissolved and total manganese, and total iron; and no change in sulfate or dissolved iron in Swatara Creek immediately downstream from the mined area. The increased pH and calcium from limestone in treatment systems can be important for mitigating toxic effects of dissolved metals. Thus, treatment of AMD during the 1990s improved pH buffering, reduced metals transport, and helped to decrease metals toxicity to fish.

Pennsylvania↗

Effects of historical lead–zinc mining on riffle-dwelling benthic fish and crayfish in the Big River of southeastern Missouri, USA

The Big River (BGR) drains much of the Old Lead Belt mining district (OLB) in southeastern Missouri, USA, which was historically among the largest producers of lead–zinc (Pb–Zn) ore in the world. We sampled benthic fish and crayfish in riffle habitats at eight sites in the BGR and conducted 56-day in situ exposures to the woodland crayfish (Orconectes hylas) and golden crayfish (Orconectes luteus) in cages at four sites affected to differing degrees by mining. Densities of fish and crayfish, physical habitat and water quality, and the survival and growth of caged crayfish were examined at sites with no known upstream mining activities (i.e., reference sites) and at sites downstream of mining areas (i.e., mining and downstream sites). Lead, zinc, and cadmium were analyzed in surface and pore water, sediment, detritus, fish, crayfish, and other benthic macro-invertebrates. Metals concentrations in all materials analyzed were greater at mining and downstream sites than at reference sites. Ten species of fish and four species of crayfish were collected. Fish and crayfish densities were significantly greater at reference than mining or downstream sites, and densities were greater at downstream than mining sites. Survival of caged crayfish was significantly lower at mining sites than reference sites; downstream sites were not tested. Chronic toxic-unit scores and sediment probable effects quotients indicated significant risk of toxicity to fish and crayfish, and metals concentrations in crayfish were sufficiently high to represent a risk to wildlife at mining and downstream sites. Collectively, the results provided direct evidence that metals associated with historical mining activities in the OLB continue to affect aquatic life in the BGR.

Missouri↗

Evidence for exposure to selenium by breeding interior snowy plovers (Charadrius nivosus) in saline systems of the Southern Great Plains

Interior snowy plover ( Charadrius nivosus ) population declines and deteriorating conditions throughout the Southern Great Plains (SGP) of Texas, New Mexico, and Oklahoma may be linked to environmental contaminants. Concentrations of V, As, Cd, Pb, and Se were quantified in breeding snowy plover blood, feathers (5th primary; P5), and potential prey (tiger beetles [ Cicindela circumpicta and C. togata ]). Se was (a) most commonly detected relative to other quantified elements and (b) frequently quantified at levels exceeding background or toxicity thresholds. Of samples greater than instrumentation detection limits, 98% of snowy plover blood and 22% of feather samples were greater than Se toxicity thresholds of 1 ppm ww for blood and 5 ppm dw for feathers (blood quantifiable range: 0.83–15.12 ppm; feathers quantifiable range: 1.90–27.47 ppm). Almost all tiger beetle Se concentrations were below reported invertebrate thresholds of 30 ppm dw (quantifiable range: 0.54–45.84 ppm). Snowy plover blood Se concentrations were related to sex, individual body condition, and local tiger beetle Se concentrations, while plover P5 Se concentrations were related to state, sex, and presence of body molt. Tiger beetle Se concentrations were related to individual study sites in Texas. These results provide some of the first evidence of Se exposure risk for interior snowy plovers nesting in saline lake and alkali flat environments of the SGP. Future efforts should focus upon specific Se uptake pathways during breeding and nonbreeding seasons, as snowy plovers breeding in the SGP appear to be exposed to Se throughout their annual cycle.

New Mexico, Oklahoma, Texas↗

Chronic effects of metal releases from historical mining on threatened crayfish in Madison County Missouri, USA

The Little St. Francis River and its tributaries drain metals-contaminated areas of the Madison County Mines National Priority List Superfund site (MCM) which was designated in 2003 to facilitate remediation of metals contamination within the MCM. One concern for natural resource trustees in the MCM is the potential effects of elevated metals concentrations on the federally threatened St. Francis River crayfish, Faxonius quadruncus , which has a geographic range that is limited to the St. Francis River watershed. A survey of riffle-dwelling crayfish, in-situ cage study, and laboratory toxicity tests were conducted to assess the effects of mining-derived metals on F. quadruncus and other crayfish species in the MCM. Crayfish densities were significantly greater at sites upstream of metals releases from historical mining (henceforth mining releases) compared to densities at sites downstream of mining releases, and metals concentrations in whole-body crayfish, surface water, sediments, macroinvertebrates, fish, and plant material were greater at sites downstream of mining releases compared to sites upstream of mining releases. Crayfish densities were also negatively correlated with consensus-based adverse effects indices, expressed as surface-water toxic units and sediment probable effects quotients. Decreased growth and increased mortality during cage and laboratory studies were likely due to exposure to, and subsequently uptake of, elevated concentrations of metals. Crayfish in all studies were found to bioaccumulate metals, which supports their utility as bioindicators of metals contamination. Study results show that elevated metals concentrations associated with mining releases in the MCM continue to adversely affect biota, including the federally threatened F. quadruncus .

Missouri↗

Changing agricultural practices: Potential consequences to aquatic organisms

Agricultural practices pose threats to biotic diversity in freshwater systems with increasing use of glyphosate-based herbicides for weed control and animal waste for soil amendment becoming common in many regions. Over the past two decades, these particular agricultural trends have corresponded with marked declines in populations of fish and mussel species in the Upper Conasauga River watershed in Georgia/Tennessee, USA. To investigate the potential role of agriculture in the population declines, surface waters and sediments throughout the basin were tested for toxicity and analyzed for glyphosate, metals, nutrients, and steroid hormones. Assessments of chronic toxicity with Ceriodaphnia dubia and Hyalella azteca indicated that few water or sediment samples were harmful and metal concentrations were generally below impairment levels. Glyphosate was not observed in surface waters, although its primary degradation product, aminomethyl phosphonic acid (AMPA), was detected in 77% of the samples (mean = 509 μg/L, n = 99) and one or both compounds were measured in most sediment samples. Waterborne AMPA concentrations supported an inference that surfactants associated with glyphosate may be present at levels sufficient to affect early life stages of mussels. Nutrient enrichment of surface waters was widespread with nitrate (mean = 0.7 mg NO 3 -N/L, n = 179) and phosphorus (mean = 275 μg/L, n = 179) exceeding levels associated with eutrophication. Hormone concentrations in sediments were often above those shown to cause endocrine disruption in fish and appear to reflect the widespread application of poultry litter and manure. Observed species declines may be at least partially due to hormones, although excess nutrients and herbicide surfactants may also be implicated.

Environmental Monitoring and Assessment↗

Pre-mining trace element and radiation exposure to biota from a breccia pipe uranium mine in the Grand Canyon (Arizona, USA) watershed

The risks to wildlife and humans from uranium (U) mining in the Grand Canyon watershed are largely unknown. In addition to U, other co-occurring ore constituents contribute to risks to biological receptors depending on their toxicological profiles. This study characterizes the pre-mining concentrations of total arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), mercury (Hg), nickel (Ni), selenium (Se), thallium (Tl), U, and zinc (Zn); radiation levels; and histopathology in biota (vegetation, invertebrates, amphibians, birds, and mammals) at the Canyon Mine. Gross alpha levels were below the reporting limit (4 pCi/g) in all samples, and gross beta levels were indicative of background in vegetation (<10–17 pCi/g) and rodents (<10–43.5 pCi/g). Concentrations of U, Tl, Pb, Ni, Cu, and As in vegetation downwind from the mine were likely the result of aeolian transport. Chemical concentrations in rodents and terrestrial invertebrates indicate that surface disturbance during mine construction has not resulted in statistically significant spatial differences in fauna concentrations adjacent to the mine. Chemical concentrations in egg contents and nestlings of non-aquatic birds were less than method quantification limits or did not exceed toxicity thresholds. Bioaccumulation of As, Pb, Se, Tl, and U was evident in Western spadefoot ( Spea multiplicata ) tadpoles from the mine containment pond; concentrations of As (28.9–31.4 μg/g) and Se (5.81–7.20 μg/g) exceeded toxicity values and were significantly greater than in tadpoles from a nearby water source. Continued evaluation of As and Se in biota inhabiting and forging in the mine containment pond is warranted as mining progresses.

Arizona↗

Incubating rainbow trout in soft water increased their later sensitivity to cadmium and zinc

Water hardness is well known to affect the toxicity of some metals; however, reports on the influence of hardness during incubation or acclimation on later toxicity to metals have been conflicting. We incubated rainbow trout ( Oncorhynchus mykiss ) near the confluence of two streams, one with soft water and one with very-soft water (average incubation hardnesses of about 21 and 11 mg/L as CaCO 3 , respectively). After developing to the swim-up stage, the fish were exposed for 96-h to a mixture of cadmium (Cd) and zinc (Zn) in water with a hardness of 27 mg/L as CaCO 3 . The fish incubated in the higher hardness water were about two times more resistant than the fish incubated in the extremely soft water. This difference was similar or greater than the difference that would have been predicted by criteria hardness equations had the fish been tested in the different acclimation waters. We think it is plausible that the energy demands for fish to maintain homeostasis in the lower hardness water make the fish more sensitive to metals that inhibit ionoregulation such as Cd and Zn. We suggest that if important decisions were to be based upon test results, assumptions of adequate hardness acclimation should be carefully considered and short acclimation periods avoided. If practical, incubating rainbow trout in the control waters to be tested may reduce uncertainties in the possible influences of differing rearing water hardness on the test results.

Water, Air, & Soil Pollution↗

Geological considerations in hazardous waste disposal

Present regulations assume that long-term isolation of hazardous wastes - including toxic chemical, biological, radioactive, flammable and explosive wastes - may be effected by disposal in landfills that have liners of very low hydraulic conductivity. In reality, total isolation of wastes in humid areas is not possible; some migration of leachate from wastes buried in the gound will always occur. Regulations should provide performance standards applicable on a site-by-site basis rather than rigid criteria for site selection and design. The performance standards should take into account several factors: (1) the categories, segregation, degradation and toxicity of the wastes; (2) the site hydrogeology, which governs the direction and rate of contaminant transport; (3) the attenuation of contaminants by geochemical interactions with geologic materials; and (4) the release rate of unattenuated pollutants to surface or groundwater. An adequate monitoring system is essential. The system should both test the extent to which the operation of the site meets performance standards and provide sufficient warning of pollution problems to allow implementation of remedial measures. In recent years there has been a trend away from numerous, small disposal sites toward fewer and larger sites. The size of a disposal site should be based on the attenuation capacity of the geologic material, which has a finite, though generally not well-defined, limit. For slowly degradable wastes, engineered sites with leachate-collection systems appear to be only a temporary solution since the leachate collected will also require final disposal.

Journal of Hydrology↗

Role of intestinal microflora in the degradation of DDT by rainbow trout ( Salmo gairdneri )

Though liver homogenates show apparent microsomal enzyme DDT-dehydrochlorinase activity, in the intact fish the intestinal microflora play a major role in DDT detoxication. Since the presence of this microflora in fish depends on the recent intake of food (12), the rate of detoxication and hence the toxicity of ingested DDT to the rainbow trout will probably depend somewhat on the available food supply.

Life Sciences↗

An egg injection method for assessing early life stage mortality of polychlorinated dibenzo- p -dioxins, dibenzofurans, and biphenyls in rainbow trout, (Oncorhynchus mykiss)

To characterize the risk that polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) pose to salmonid early life stage survival, we developed a method to expose rainbow trout (Oncorhynchus mykiss) eggs to graded doses of PCDD, PCDF, and PCB congeners, using 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as a prototype. Rainbow trout eggs were injected 24&ndash;50 h post-fertilization with 0.2 &mu;l of 50 mM phosphatidylcholine (PC) liposomes (control) or 0.2 &mu;l of 5&ndash;7 graded doses of TCDD incorporated into 50 mM PC liposomes. Injection volume never exceeded 0.6% egg volume. Immediately following injection, the injection site was sealed with Super glue&reg;, resulting in 92&ndash;97% of TCDD dose retained by the egg. Following both egg injection and waterborne egg exposure. TCDD toxicity in rainbow trout was manifested by half-hatching mortality but predominantly by sac fry mortality associated with hemorrhages, pericardial edema, and yolk sac edema. TCDD LD 50 s, following injection and waterborne exposure of rainbow trout eggs, were 421 (331&ndash;489) and 439 (346&ndash;519) pg TCDD/g egg (LD 50 , 95% fiducial limits), respectively. As in rainbow trout, TCDD toxicity in lake trout (Salvelinus namaycush) following the same two routes of exposure was manifested by half-hatching mortality but predominantly by sac fry mortality preceded by hemorrhages and yolk sac edema. LD 50 s, based on the dose of TCDD in lake trout eggs, were 47 (21&ndash;65) and 65 (60&ndash;71) pg/g following injection and waterborne exposure, respectively. The egg injection method is ideal for assessing the relationship between early life stage mortality in rainbow trout and graded egg doses of individual PCDD, PCDF, or PCB congeners.

Aquatic Toxicology↗

Effects of industrial effluents, heavy metals, and organic solvents on mallard embryo development

Mallard eggs were externally exposed at 3 and 8 days of incubation to 7 different industrial effluents and to 7 different heavy metal, organic solvent, and petroleum solutions to screen for potential embryo-toxic effects. This route of exposure was chosen in order to simulate the transfer of pollutant from the plumage of aquatic birds to their eggs. Five of the effluents including mineral pigment, scouring effluent, sludge, and tannery effluent resulted in small but significant reductions in embryonic growth. Treatment with methyl mercury chloride solution of 50 ppm (Hg) impaired embryonic growth but much higher concentrations were required to affect survival and cause teratogenic effects. Oil used to suppress road dust was the most toxic of the pollutants tested and only 0.5 microliter/egg caused 60% mortality by 18 days of development. These findings, in combination with other studies suggest that petroleum pollutants, or effluents in combination with petroleum, may pose a hazard to birds' eggs when exposure is by this route.

Toxicology Letters↗

The geochemistry of continental hydrothermal systems

Hydrothermal systems on the continents are of great significance because they are primary sources of economically important metals and geothermal energy, they are tourist attractions, they support bathing and health resorts, and they host extreme life forms. Research on hot springs and their deposits provide clues to early life on Earth and possibly on Mars and have led to major breakthroughs in biotechnology. Aqueous and gas-rich hydrothermal fluids also contribute to a range of volcanic hazards including the destabilization of volcanic edifices, acting as propellant in steam-driven hydrothermal explosions, reducing effective stresses in mudflows (lahars), emitting toxic and potentially lethal gases, and transporting toxic metals to watersheds. The main goals of this review are to summarize the state of knowledge on the chemistry of continental hydrothermal systems and highlight the myriad processes that operate under a wide range of temperatures, pressures, chemical compositions, and oxidation states.

Book chapter↗

Nonsteroidal anti-inflammatory drugs in raptors

The use of analgesia has become standard, and appropriate, practice in avian medicine. As in mammals, pain control in avian patients is usually accomplished with opioids and nonsteroidal anti-inflammatory drugs (NSAIDs) used singly or in combination for a multimodal approach. Despite their usefulness, widespread use, and relative safety in clinical use, few controlled studies in birds have been conducted on efficacy, safety, and dosing. The guidelines for the use of NSAIDs in raptors and other birds have mainly been empirical. More recently, NSAIDs in free-living raptors have emerged as a major conservation issue with the discovery that diclofenac sodium was responsible for the population crash of three species of Gyps vultures in southern Asia. In this context, residues of veterinary NSAIDs in domestic animals are now considered environmental contaminants that can be significantly toxic to vultures and possibly other avian scavengers. Ironically, the disaster with Asian vultures has led to a considerable body of research on NSAIDs in raptors to the benefit of clinicians who now have scientific information available to help assess dosing, safety, toxicity, and pharmacokinetics of NSAIDs in their raptor patients.

Book chapter↗

Organic compounds in produced waters from coalbed natural gas wells in the Powder River Basin, Wyoming, USA

The organic composition of produced water samples from coalbed natural gas (CBNG) wells in the Powder River Basin, WY, sampled in 2001 and 2002 are reported as part of a larger study of the potential health and environmental effects of organic compounds derived from coal. The quality of CBNG produced waters is a potential environmental concern and disposal problem for CBNG producers, and no previous studies of organic compounds in CBNG produced water have been published. Organic compounds identified in the produced water samples included: phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, various non-aromatic compounds, and phthalates. Many of the identified organic compounds (phenols, heterocyclic compounds, PAHs) are probably coal-derived. PAHs represented the group of organic compounds most commonly observed. Concentrations of total PAHs ranged up to 23 ??g/L. Concentrations of individual compounds ranged from about 18 to <0.01 ??g/L. Temporal variability of organic compound concentrations was documented, as two wells with relatively high organic compound contents in produced water in 2001 had much lower concentrations in 2002. In many areas, including the PRB, coal strata provide aquifers for drinking water wells. Organic compounds observed in produced water are also likely present in drinking water supplied from wells in the coal. Some of the organic compounds identified in the produced water samples are potentially toxic, but at the levels measured in these samples are unlikely to have acute health effects. The human health effects of low-level, chronic exposure to coal-derived organic compounds in drinking water are currently unknown. Continuing studies will evaluate possible toxic effects from low level, chronic exposure to coal-derived organic compounds in drinking water supplies.

Applied Geochemistry↗

Priority pollutants and associated constituents in untreated and treated discharges from coal mining or processing facilities in Pennsylvania, USA

Clean sampling and analysis procedures were used to quantify more than 70 inorganic constituents, including 35 potentially toxic or hazardous constituents, organic carbon, and other characteristics of untreated (influent) and treated (effluent) coal-mine discharges (CMD) at 38 permitted coal-mining or coal-processing facilities in the bituminous coalfield and 4 facilities in the anthracite coalfield of Pennsylvania. Of the 42 facilities sampled during 2011, 26 were surface mines, 11 were underground mines, and 5 were coal refuse disposal operations. Treatment of CMD with caustic soda (NaOH), lime (CaO or Ca(OH) 2 ), flocculent, or limestone was ongoing at 21%, 40%, 6%, and 4% of the facilities, respectively; no chemicals were added at the remaining facilities. All facilities with CMD treatment incorporated structures for active or passive aeration and settling of metal-rich precipitate. The untreated influent samples had wide ranges of pH (2.8&ndash;7.6), hot acidity (&minus;600 to 8000 mg/L as CaCO 3 ), specific conductance (SC; 253&ndash;13,000 &mu;S/cm), total dissolved solids (TDS; 168&ndash;18,100 mg/L), and associated dissolved (<0.45-&mu;m pore-size filter) constituents, including SO 4 (14.7&ndash;10,700 mg/L), Fe (<0.01 to 4100 mg/L), Mn (0.02&ndash;136 mg/L), Al (<0.01 to 128 mg/L), and Zn (<0.003 to 18.8 mg/L). Concentrations of Ag (<1 &mu;g/L), Hg (<1 &mu;g/L), Sn (<0.5 &mu;g/L), and CN (<0.01 mg/L) were below detection limits. Only one influent sample met permitted mine effluent (PME) limits plus dissolved-constituent criteria maximum concentration (CMC) thresholds for the protection of freshwater aquatic organisms. The pH of the treated effluent samples ranged from 5.5 to 11.9 and was greater than or equal to the pH of the corresponding influent at all sites. All the effluent samples met CMC levels for dissolved concentrations of Ag, As, Ba, Cd, Cl, Cr, Pb, Ni, Sb, Se, Tl, V, NH 3 , NO 2 , NO 3 , and CN; however, nine violated one or more of the PME limits for pH (<6, n = 1), net acidity (>0, n = 3), Fe (>7 mg/L, n = 1), or Mn (>5 mg/L, n = 8), plus one or more exceeded CMC levels for Al (>0.75 mg/L, n = 2), Co (>95 &mu;g/L, n = 5), Zn (>307 &mu;g/L, n = 1), Cu (>7.4 &mu;g/L, n = 1), or Se (>12.8 &mu;g/L, n = 3). Although CMC exceedances for Co and Zn were attributed to samples also violating the PME limit for pH or Mn, the samples that exceeded the CMC for Al, Cu, or Se met applicable PME limits for pH, Fe, and Mn. Furthermore, many of the pH-compliant effluents did not meet reference criteria for SO 4 and related measures of ionic strength, including TDS, SC, and osmotic pressure. The Wilcoxon matched-pair signed-ranks statistic was used to test if the overall difference between the effluent and influent pairs was equal to zero. Constituents that statistically were the same for effluent and influent ( p > 0.05) included flow rate, SC, osmotic pressure, hardness, alkalinity, total organic carbon (TOC), K, Cl, NO 3 , PO 4 , Sb, Sr, Br, Se, Mo, and V. Although temperature, dissolved oxygen, pH, Ca, and Na were greater in the effluent than the influent, most constituents decreased as a result of treatment, including TDS, acidity, SO 4 , Al, Fe, Mn, Mg, As, Ba, Be, Cd, Cr, Co, Cu, F, Pb, Ni, NH 3 , Tl, Ti, U, Zn, Zr, total phenols, total inorganic carbon (TIC), biological oxygen demand (BOD), and chemical oxygen demand (COD). Nevertheless, some constituents that decreased, such as SO 4 , still did not meet reference criteria. Findings from this study suggest that typical chemical or aerobic treatment of CMD to pH > 6 with removal of Fe to <7 mg/L and Mn to <5 mg/L may provide a reasonable measure of protection for aquatic life from priority pollutant metals and other toxic or hazardous constituents in effluent but may not be effective for achieving permissible or background levels for TDS, SC, osmotic pressure, or concentrations of SO 4 and some other pollutants, including Se, Br, and Cl, if present.

Pennsylvania↗

Individual variability in esterase activity and CYP1A levels in Chinook salmon (Oncorhynchus tshawytscha) exposed to esfenvalerate and chlorpyrifos

Acetylcholinesterase (AChE) activity has traditionally been monitored as a biomarker of organophosphate (OP) and/or carbamate exposure. However, AChE activity may not be the most sensitive endpoint for these agrochemicals, because OPs can cause adverse physiological effects at concentrations that do not affect AChE activity. Carboxylesterases are a related family of enzymes that have higher affinity than AChE for some OPs and carbamates and may be more sensitive indicators of environmental exposure to these pesticides. In this study, carboxylesterase and AChE activity, cytochrome P4501A (CYP1A) protein levels, and mortality were measured in individual juvenile Chinook salmon (Oncorhynchus tshawytscha) following exposure to an OP (chlorpyrifos) and a pyrethroid (esfenvalerate). As expected, high doses of chlorpyrifos and esfenvalerate were acutely toxic, with nominal concentrations (100 and 1 ??g/l, respectively) causing 100% mortality within 96 h. Exposure to chlorpyrifos at a high dose (7.3 ??g/l), but not a low dose (1.2 ??g/l), significantly inhibited AChE activity in both brain and muscle tissue (85% and 92% inhibition, respectively), while esfenvalerate exposure had no effect. In contrast, liver carboxylesterase activity was significantly inhibited at both the low and high chlorpyrifos dose exposure (56% and 79% inhibition, respectively), while esfenvalerate exposure still had little effect. The inhibition of carboxylesterase activity at levels of chlorpyrifos that did not affect AChE activity suggests that some salmon carboxylesterase isozymes may be more sensitive than AChE to inhibition by OPs. CYP1A protein levels were ???30% suppressed by chlorpyrifos exposure at the high dose, but esfenvalerate had no effect. Three teleost species, Chinook salmon, medaka (Oryzias latipes) and Sacramento splittail (Pogonichthys macrolepidotus), were examined for their ability to hydrolyze a series of pyrethroid surrogate substrates and in all cases hydrolysis activity was undetectable. Together these data suggest that (1) carboxylesterase activity inhibition may be a more sensitive biomarker for OP exposure than AChE activity, (2) neither AChE nor carboxylesterase activity are biomarkers for pyrethroid exposure, (3) CYP1A protein is not a sensitive marker for these agrochemicals and (4) slow hydrolysis rates may be partly responsible for acute pyrethroid toxicity in fish. ?? 2005 Elsevier B.V. All rights reserved.

Aquatic Toxicology↗