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USGS1993

Biomagnification of bioassay derived 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents

In recent years contamination of the Great Lakes ecosystem with planar chlorinated hydrocarbons (PCHs) has attracted considerable concern due to their known reproductive and teratogenic effects. The H4IIE bioassay has been standardized as a means of measuring the biological potency of a PCH mixture as 2,3,7,8-tetrachloro-p-dibenzodioxin equivalents (TCDD-EQ). Using this bioassay we have investigated the biomagnification of TCDD-EQ in a semi-closed ecosystem. The biomagnification of TCDD-EQ is demonstrated and results indicate that the food chain is the major pathway for TCDD-EQ through this ecosystem. The H4IIE assay system is demonstrated to be a viable integrative measure of the total concentration of TCDD-EQ in different trophic levels.

Chemosphere↗

USGS1993

Determination of mono- and non-o,o′-chlorine substituted polychlorinated biphenyls in Aroclors and environmental samples

High resolution capillary gas chromatography (GC) is the best known technique for the separation of complex mixtures; however, no single GC column has yet separated all 209 congeners of polychlorinated biphenyls (PCBs). A number of coeluting PCB congener pairs exist, and even under favorable separation conditions such as with multidimensional GC, assignment of peak identities to known PCB structures is tedious, subject to errors from other contaminants, and requires enrichment to achieve the necessary detection limits for the most toxic PCB congeners. Routine analysis of PCBs is also complicated by coelution with other halogenated hydrocarbons such as naphthalenes, terphenyls, dibenzofurans, and pesticides. Therefore, techniques for class separations of PCBs prior to gas chromatography must be developed. These techniques should separate PCB congeners along lines that have environmental or toxicological significance. The unique ability of activated carbon to separate halogenated aromatics on the basis of molecular planarity and degree of halogenation has been demonstrated. We present a method that uses dispersed carbon on glass fibers and commercially available instrumentation to fractionate and determine mono- and non-o,o′-chlorine substituted PCB congeners in Aroclors and environmental samples.

Chemosphere↗

USGS1995

A chemodynamic approach for estimating losses of target organic chemicals from water during sample holding time

Minimizing the loss of target organic chemicals from environmental water samples between the time of sample collection and isolation is important to the integrity of an investigation. During this sample holding time, there is a potential for analyte loss through volatilization from the water to the headspace, sorption to the walls and cap of the sample bottle; and transformation through biotic and/or abiotic reactions. This paper presents a chemodynamic-based, generalized approach to estimate the most probable loss processes for individual target organic chemicals. The basic premise is that the investigator must know which loss process(es) are important for a particular analyte, based on its chemodynamic properties, when choosing the appropriate method(s) to prevent loss.

Chemosphere↗

USGS1994

Separation of selenium species released from Se-exposed algae

We have assessed a fractionation scheme for selenium species that separates Se-containing amino acids and other organoselenium compounds in aqueous samples. We investigated the retention of standard solutions of selenate (Se +6 ), selenite (Se +4 ), and selenomethionine (Se −2 ) by fractionation media (Sephadex A-25 ion-exchange resin, copper-treated Chelex-100 ligand-exchange resin, and activated charcoal) and by several types of membrane filters. The fractionation method successfully isolated Se from the standard solutions into appropriate fractions for radiometric quantitation of 75 Se. However, some filter media retained unacceptably large amounts of selenate and selenite. Mass balance microcosms were inoculated with green algae ( Chlamydomonas "> Chlamydomonas reinhardtii "> reinhardtii ) previously exposed to inorganic 75 Se, and the fractionation scheme was used to examine the release of 75 Se species into water and air. The results of the microcosm exposure indicate that seasonal blooms and crashes of phytoplankton populations may produce increased concentrations of organoselenium species.

Chemosphere↗

USGS1995

Use of semipermeable membrane devices (SPMDS) to determine bioavailable organochlorine pesticide residues in streams receiving irrigation drainwater

The semipermeable membrane device (SPMD), consisting of a neutral lipid (triolein) enclosed in polyethylene layflat tubing, is very effective in sequestering bioavailable organochlorine (OC) pesticides in the environment. We used SPMDs to sequester OC pesticide residues in streams receiving irrigation drainwater and found toxaphene, the DDT complex, dieldrin, and endrin. Ambient water concentrations of the OC pesticides were calculated using an algorithm developed previously. Toxaphene residues were estimated to range from 300 to 7,000 ng/L.

Chemosphere↗

USGS1995

Postembryonic growth and development of Hyalella azteca in laboratory cultures and contaminated sediments

The environmental, biological, and ecological requirements of but a few species used in testing sediments are known and well understood. The present investigation was designed to provide fundamental information on the postembryonic growth and development of Hyalella azteca "> Hyalella azteca (Amphipoda) that can be used as sublethal indicators of contaminated sediments, and the influence growth characteristics may have on interpretation of sediment toxicity test results. The biological endpoints for measuring H. azteca "> H. azteca growth and development included sexual maturation, molt frequency, intermolt duration, body length, antennal segment addition, and the relation between total body length and antennal segment addition. To use growth and development of H. azteca "> H. azteca as sublethal indicators of contaminated sediments, tests of up to 28 days duration should begin with immature amphipods (less than two weeks old) that will begin the adult stage at the end of the test. Sexual maturation begins at the sixth instar (about 24 days at 20°C) and can be used as a sublethal indicator of development effects. The presence of an enlarged propodus is a reliable indicator of sexual maturation in H. azteca "> H. azteca which easily distinguishes the immature (first five instars) from the juvenile (instars 6 and 7) stage.

Chemosphere↗

USGS2004

Degradation of picric acid and 2,6-DNT in marine sediments and waters: The role of microbial activity and ultra-violet exposure

Bio- and photo-transformation of two munitions and explosives of concern, 2,6-dinitrotoluene (2,6-DNT) and 2,4,6-trinitrophenol (picric acid) were assessed in spiked marine sediments and water. A sandy and a fine-grained sediment, with 0.25% and 1.1% total organic carbon, respectively, were used for biotransformation assessments at 10 and 20 °C. Sterilized sediments were used as controls for biotic vs. abiotic transformation. Transformation products were analyzed by HPLC, GC/MS and LC/MS. Biotransformation in sediments started soon after the initial contact of the chemicals with the sediments and proceeded for several months, with rates in the following sequence: fine-grain at 20 °C > fine-grain at 10 °C > sand at 20 °C > sand at 10 °C. The biotransformation paths seemed to be similar for all conditions. The major biotransformation product of 2,6-DNT was 2-amino-6-nitrotoluene (2-A-6-NT). 2-Nitrotoluene (2-NT) and other minor components, including N , N -dimethyl-3-nitroaniline, benzene nitrile, methylamino-2-nitrosophenol and diaminophenol, were also identified. After more prolonged incubation these chemicals were replaced by high molecular weight polymers. Several breakdown products of picric acid were identified by GC/MS, including 2,4-dinitrophenol, amino dinitrophenols, 3,4-diamino phenol, amino nitrophenol and nitro diaminophenol. Photo-transformation of 2,6-DNT and picric acid in seawater was assessed under simulated solar radiation (SSR). No significant photolysis of picric acid in seawater was observed for up to 47 days, but photo-transformation of 2,6-DNT began soon after the initial exposure to SSR, with 89% being photo-transformed in 24 h and none remaining after 72 h. High molecular weight chemicals were generated, with mass spectra ranging from molecular weight 200–500 compared to 182 for DNT, and the color of the stock solution changed from clear to orange. Complexity of the mass spectra and mass differences among fragments suggest that multiple polymers were produced and were co-eluting during the LC/MS analyses.

Chemosphere↗

USGS2005

Influence of sediment on the fate and toxicity of a polyethoxylated tallowamine surfactant system (MON 0818) in aquatic microcosms

The fate and toxicity of a polyethoxylated tallowamine (POEA) surfactant system, MON 0818, was evaluated in water–sediment microcosms during a 4-d laboratory study. A surfactant solution of 8 mg l −1 nominal concentration was added to each of nine 72-l aquaria with or without a 3-cm layer of one of two natural sediments (total organic carbon (TOC) 1.5% or 3.0%). Control well water was added to each of nine additional 72-l aquaria with or without sediment. Water samples were collected from the microcosms after 2, 6, 24, 48, 72, and 96 h of aging to conduct 48-h toxicity tests with Daphnia magna and to determine surfactant concentrations. Elevated mortality of D. magna (43–83%) was observed in overlying water sampled from water-only microcosms throughout the 96-h aging period, whereas elevated mortality (23–97%) was only observed in overlying water sampled from water–sediment microcosms during the first 24 h of aging. Measured concentrations of MON 0818 in water-only microcosms remained relatively constant (4–6 mg l −1 ) during the 96-h period, whereas the concentrations in overlying water from microcosms containing either of the two types of sediment dissipated rapidly, with half-lives of 13 h in the 3.0% TOC sediment and 18 h in the 1.5% TOC sediment. Both toxicity and the concentration of MON 0818 in overlying water decreased more rapidly in microcosms containing sediment with the higher percent TOC and clay and with a higher microbial biomass. Mortality of D. magna was significantly correlated with surfactant concentrations in the overlying water. These results indicate that the toxicity of the POEA surfactant in water rapidly declines in the presence of sediment due to a reduction in the surfactant concentration in the overlying water above the sediment.

Chemosphere↗

USGS2005

Toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine to larval zebrafish (Danio rerio)

Hexahydro-1,3,5-trinitro-1,3,5-triazine, a cyclonitramine commonly known as RDX, is used in the production of military munitions. Contamination of soil, sediment, and ground and surface waters with RDX has been reported in different places around the world. Acute and subacute toxicities of RDX have been relatively well documented in terrestrial vertebrates, but among aquatic vertebrates the information available is limited. The objective of this study was to characterize the acute toxicity of RDX to larval zebrafish. Mortality (LC50) and incidence of vertebral column deformities (EC50) were two of the end points measured in this study. The 96-h LC50 was estimated at 22.98 and 25.64 mg l-1 in two different tests. The estimated no-observed-effective- concentration (NOEC) values of RDX on lethality were 13.27 ?? 0.05 and 15.32 ?? 0.30 mg l-1; and the lowest-observed-effective- concentration (LOEC) values were 16.52 ?? 0.05 and 19.09 ?? 0.23 mg l-1 in these two tests, respectively. The 96-h EC50 for vertebral deformities on survivors from one of the acute lethality tests was estimated at 20.84 mg l-1, with NOEC and LOEC of 9.75 ?? 0.34 and 12.84 ?? 0.34 mg l-1, respectively. Behavioral aberrations were also noted in this acute toxicity study, including the occurrence of whirling movement and lethargic behavior. The acute effects of RDX on survival, incidence of deformities, and behavior of larval zebrafish occurred at the high end of the most frequently reported concentrations of RDX in aquatic environments. The chronic effects of RDX in aquatic vertebrates need to be determined for an adequate assessment of the ecological risk of environmental RDX. ?? 2005 Elsevier Ltd. All rights reserved.

Chemosphere↗

USGS2005

Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream

Four water samples collected using standard depth and width water-column sampling methodology were compared to an innovative passive, in situ, sampler (the polar organic chemical integrative sampler or POCIS) for the detection of 96 organic wastewater-related contaminants (OWCs) in a stream that receives agricultural, municipal, and industrial wastewaters. Thirty-two OWCs were identified in POCIS extracts whereas 9-24 were identified in individual water-column samples demonstrating the utility of POCIS for identifying contaminants whose occurrence are transient or whose concentrations are below routine analytical detection limits. Overall, 10 OWCs were identified exclusively in the POCIS extracts and only six solely identified in the water-column samples, however, repetitive water samples taken using the standard method during the POCIS deployment period required multiple trips to the sampling site and an increased number of samples to store, process, and analyze. Due to the greater number of OWCs detected in the POCIS extracts as compared to individual water-column samples, the ease of performing a single deployment as compared to collecting and processing multiple water samples, the greater mass of chemical residues sequestered, and the ability to detect chemicals which dissipate quickly, the passive sampling technique offers an efficient and effective alternative for detecting OWCs in our waterways for wastewater contaminants.

New Jersey↗

USGS2006

Accumulation of As, Cd and selected trace elements in tubers of Scirpus aritimus L. from Doñana marshes (South Spain)

The collapse of a pyrite-mining, tailing dam on 1998 contaminated an area of 4286 ha along the Agrio and Guadiamar river valleys in southern Spain. Over 2700 ha of the Doñana marshes, an important wintering area for wetland European birds, were contaminated. This study reports analyses of the tubers of Scirpus maritimus (an important food for greylag geese, Anser anser ) collected in 2000 in the “Entremuros” (spill-affected area) and in nearby unaffected Doñana marshes (control areas). In the spill-affected area mean tuber tissue concentrations of Cd (0.25 mg kg −1 ) and Zn (61 mg kg −1 ) were greater than in those tubers from the control area (0.02 mg kg −1 for Cd, and 22 mg kg −1 for Zn); values of Cd and Zn in “Entremuros” (samples collected two years after the mine spill) were much smaller than those reported only a few months after the accident. Trace elements (As, Fe, Mn and Tl, and to a lesser extent Cd and Pb) showed a preferential accumulation in the outer skin of tubers. Surprisingly, concentrations of As and Fe were greater in tubers from some marsh sites not affected by the mine-spill than in tubers from the “Entremuros”. We suggest that relic river channels within the Doñana marshes may be contaminated by trace elements from historic mining activities. An exhaustive study of macrophytes and other plant species in this area is recommended to identify potential risks to wildlife.

Chemosphere↗

USGS2006

Assessment of pesticide residues in army cutworm moths (Euxoa auxiliaris) from the Greater Yellowstone Ecosystem and their potential consequences to foraging grizzly bears (Ursus arctos horribilis)

During summer, a grizzly bear ( Ursus arctos horribilis ) in the Greater Yellowstone Ecosystem (GYE) (USA) can excavate and consume millions of army cutworm moths ( Euxoa auxiliaris ) (ACMs) that aggregate in high elevation talus. Grizzly bears in the GYE were listed as threatened by the US Fish and Wildlife Service in 1975 and were proposed for delisting in 2005. However, questions remain about key bear foods. For example, ACMs are agricultural pests and concern exists about whether they contain pesticides that could be toxic to bears. Consequently, we investigated whether ACMs contain and transport pesticides to bear foraging sites and, if so, whether these levels could be toxic to bears. In 1999 we collected and analyzed ACMs from six bear foraging sites. ACMs were screened for 32 pesticides with gas chromatography with electron capture detection (GC–ECD). Because gas chromatography with tandem mass spectrometry (GC–MS/MS) can be more sensitive than GC–ECD for certain pesticides, we revisited one site in 2001 and analyzed these ACMs with GC–MS/MS. ACMs contained trace or undetectable levels of pesticides in 1999 and 2001, respectively. Based on chemical levels in ACMs and numbers of ACMs a bear can consume, we calculated the potential of chemicals to reach physiological toxicity. These calculations indicate bears do not consume physiologically toxic levels of pesticides and allay concerns they are at risk from pesticides transported by ACMs. If chemical control of ACMs changes in the future, screening new ACM samples taken from bear foraging sites may be warranted.

Wyoming↗

USGS2006

A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment

Veterinary antibiotics (VAs) are widely used in many countries worldwide to treat disease and protect the health of animals. They are also incorporated into animal feed to improve growth rate and feed efficiency. As antibiotics are poorly adsorbed in the gut of the animals, the majority is excreted unchanged in faeces and urine. Given that land application of animal waste as a supplement to fertilizer is often a common practice in many countries, there is a growing international concern about the potential impact of antibiotic residues on the environment. Frequent use of antibiotics has also raised concerns about increased antibiotic resistance of microorganisms. We have attempted in this paper to summarize the latest information available in the literature on the use, sales, exposure pathways, environmental occurrence, fate and effects of veterinary antibiotics in animal agriculture. The review has focused on four important groups of antibiotics (tylosin, tetracycline, sulfonamides and, to a lesser extent, bacitracin) giving a background on their chemical nature, fate processes, occurrence, and effects on plants, soil organisms and bacterial community. Recognising the importance and the growing debate, the issue of antibiotic resistance due to the frequent use of antibiotics in food-producing animals is also briefly covered. The final section highlights some unresolved questions and presents a way forward on issues requiring urgent attention.

Chemosphere↗

USGS2006

Fabricating data: How substituting values for nondetects can ruin results, and what can be done about it

The most commonly used method in environmental chemistry to deal with values below detection limits is to substitute a fraction of the detection limit for each nondetect. Two decades of research has shown that this fabrication of values produces poor estimates of statistics, and commonly obscures patterns and trends in the data. Papers using substitution may conclude that significant differences, correlations, and regression relationships do not exist, when in fact they do. The reverse may also be true. Fortunately, good alternative methods for dealing with nondetects already exist, and are summarized here with references to original sources. Substituting values for nondetects should be used rarely, and should generally be considered unacceptable in scientific research. There are better ways.

Chemosphere↗

USGS2007

Histological alternation and vitellogenin induction in adult rare minnow ( Gobiocypris rarus ) after exposure to ethynylestradiol and nonylphenol

Adult rare minnow ( Gobiocypris rarus ) were exposed to 0, 1, 5, and 25 ng/l (nominal concentrations) of 17α-ethynylestradiol (EE 2 ) and 3, 10, and 30 μg/l (nominal concentrations) of 4-nonylphenol (NP) under flow-through conditions for a period of 28 d. Low mortality was observed at 5 and 25 ng/l EE 2 and the growth of fish reduced significantly at 25 ng/l EE 2 compared to controls. However, the gonadosomatic indices (GSI) of male fish were significantly higher in 1 ng/l EE 2 treatments and in 10 and 30 μg/l NP treatments ( p < 0.05). Renal somatic indices (RSI) of male fish in EE 2 treatments were significantly higher than those in controls ( p < 0.05). In contrast, significantly decreased GSI and RSI of female fish could only be observed in 5 and 25 ng/l EE 2 treatments ( p < 0.05). Hepatosomatic indices (HSI) of male fish were significantly higher in 25 ng/l EE 2 treatments. However, significantly increased of HSI of female fish could only be observed in 1 ng/l EE 2 treatments. Plasma vitellogenin (VTG) induction could be observed in males after exposed to different concentrations of EE 2 and NP, and plasma VTG concentrations in females exposed to 5 and 25 ng/l EE 2 were also significantly higher than in controls ( p < 0.05). At level higher than 5 ng/l EE 2 or 30 μg/l NP, hepatic tissue and renal tissue impairment of males could be observed. The pathological male liver was associated with a hypertrophy of hepatocytes and damages to cellar structure and accumulated eosinophilic material. Renal tissue showed different pathological effects which was reflected by accumulated eosinophilic material, hemorrhages within the kidney tubules and hypertrophy of the tubular epithelia. Also at these levels of exposure, feminization of male fish could be noticed and parts of males manifested the testis-ova phenomenon. Ovaries of female rare minnow in 25 ng/l EE 2 treatment group were degenerated. Therefore when exposed to EE 2 and NP even at environmental observed concentrations, adverse effects could occur in the reproductive system of adult fishes. The observed hepatic tissue and renal tissue impairment should be due to the induction and accumulation of VTG in organs, especially in males.

Chemosphere↗

USGS2007

Chemical contamination of the Rybinsk Reservoir, northwest Russia: Relationship between liver polychlorinated biphenyls (PCB) content and health indicators in bream (Abramis brama)

The Rybinsk Reservoir (Russia) is the largest artificial waterbody in Europe (4550 km 2 ) and provides drinking water for population of the cities located along the coast line. Industrialization in Cherepovets at the northeastern portion of the reservoir, including one of the largest metallurgical facilities in Europe, has resulted in chemical contamination of the reservoir. The extent of polychlorinated biphenyls (PCB) contamination in bream liver, a common fish species, taken from six locations in the Rybinsk Reservoir and Volga River, and biochemical and morphometric biomarkers of fish health were investigated. Liver PCB concentrations ranged from non-detected to 3.4 μg/g wet wt of liver, with the greatest concentrations found in fish taken near the industrialized area in Sheksna Reach of Rybinsk Reservoir. The source of the bream contamination is the PCB pollution of bottom organisms and sediments conditioned with industrialization facilities of Cherepovets. The patterns of the PCB congeners in the livers of bream taken near Cherepovets were similar at all of the stations that were sampled around the reservoir and Volga River. Among the common fish health biomarkers used only liver total ChE activity and liver-somatic index in bream near Cherepovets can reflect environmental pollution. Other morphometric (FCF, Clark’s condition factors, and spleen-somatic index) and biochemical (protein content and acetylcholinesterase activity in the brain) biomarkers related with fish health varied among locations, but were not correlated to the concentrations of PCBs in the bream livers.

Rybinsk Reservoir↗

USGS2007

Trends of brominated diphenyl ethers in fresh and archived Great Lakes fish (1979-2005)

While few environmental measurements of brominated diphenyl ethers (BDEs) were completed prior to the mid-1990s, analysis of appropriately archived samples might enable the determination of contaminant trends back to the introduction of these chemicals. In this paper, we first investigate the stability of BDEs in archived frozen and extracted fish samples, and then characterize trends of these chemicals in rainbow smelt ( Osmerus mordax ) and lake trout ( Salvelinus namaycush ) in each of the Great Lakes between 1979 and 2005. We focus on the four most common congeners (BDE-47, 100, 99 and 153) and use a change-point analysis to detect shifts in trends. Analyses of archived fish samples yielded precise BDE concentration measurements with only small losses (0.8% per year in frozen fish tissues, 2.2% per year in refrigerated extracts). Trends in fish from all Great Lakes showed large increases in BDE concentrations that started in the early to mid-1980s with fairly consistent doubling times (generally 2–4 years except in Lake Erie smelt where levels increased very slowly), though concentrations and trends show differences by congener, fish species and lake. The most recent data show that accumulation rates are slowing, and concentrations of penta- and hexa-congeners in trout from Lakes Ontario and Michigan and smelt from Lake Ontario started to decrease in the mid-1990s. Trends in smelt and trout are evolving somewhat differently, and trout concentrations in the five lakes are now ranked as Michigan > Superior = Ontario > Huron = Erie, and smelt concentrations as Michigan > Ontario > Huron > Superior > Erie. The analysis of properly archived samples permits the reconstruction of historical trends, congener distributions, biomagnification and other information that can aid the understanding and management of these contaminants.

Chemosphere↗

USGS2008

Concentrations and time trends of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in aquatic bird eggs from San Francisco Bay, CA 2000-2003

Concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in 169 avian eggs. We analyzed randomly collected eggs of two species of piscivorous birds: Caspian tern (Sterna caspia) (n = 78) and Forster's tern (Sterna forsteri) (n = 76). We also analyzed fail-to-hatch eggs from two species protected under the Federal Endangered Species Act of 1973, that breed in the San Francisco Bay region: the piscivorous California Least tern (Sterna antillarum brownii) (n = 11) and the omnivorous California Clapper rail (Rallus longirostris obsoletus) (n = 4). San Francisco Bay eggs were collected annually for four years (2000-2003), and additional 20 eggs were collected and analyzed from Gray's Harbor, Washington in 2001. Geometric mean PBDE concentrations did not significantly differ in the three tern species, but concentrations in eggs from the fail to hatch California Clapper rail eggs were significantly lower than those found in the randomly collected tern eggs. Median concentrations of ???PBDEs in Caspian tern eggs for 2000-2003 were 2410, 4730, 3720 and 2880 ng/g lipid weight (lw), respectively, in Forster's terns 1820, 4380, 5460 and 3600 ng/g lw, respectively, and in California Least terns for 2001 and 2002 were 5060 and 5170 ng/g lw, respectively. In contrast, median ???PBDEs concentration in California Clapper rail eggs for 2001 was 379 ng/g lw. Five PBDEs were the major congeners found and decreased in the order BDE-47, -99, -100, -153, and -154. BDE-32, -28, -71, -66, -85, -183 were less prevalent, minor congeners, as was BDE-209, which was measured in a subset of samples. PBDE concentrations in bird eggs from San Francisco Bay were site related. There was no significant difference in PBDE concentrations in Caspian tern eggs from San Francisco Bay and Gray's Harbor, WA. Average PBDE concentrations in eggs did not significantly increase over the period 2000-2003. ?? 2008 Elsevier Ltd. All rights reserved.

Chemosphere↗