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1.
Environ Pollut ; 295: 118687, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-34920043

RESUMO

Remediation of hydrophobic organic contaminants using activated carbon is an effective means by which to clean up contaminated areas. Predicting remediation success using laboratory experimentation with soil, however, is unclear. Current remediation efforts involving activated carbon addition to floodplain soils downstream of the Velsicol Chemical Corporation Superfund Site (VCCSS) have offered the opportunity to directly compare in situ activated carbon remediation with laboratory experimentation. The objective of the current study was to compare bioaccumulation of DDT, DDD, and DDE (DDX) residues by earthworms (Eisenia fetida) exposed to laboratory-aged (LA) or field-aged (FA) soils from four locations. Samples were evaluated at 0-, 3-, and 9-months post-remediation to determine the ability of laboratory studies to predict in situ remediation. Floodplain soils downstream from the VCCSS were amended with 2% by weight activated carbon in the field and the laboratory, and then aged for 3- or 9-months. At 0-, 3-, and 9-months bioaccumulation assays were conducted with LA and FA soils and tissue concentrations were compared within study sites. In both LA and FA soils, activated carbon caused significant reductions (37.01-92.94%) in bioaccumulated DDX in earthworms. Field-collected worms showed a similar trend in reduction of bioaccumulated DDX, suggesting activated carbon remediation was successful in reducing bioavailable DDX for native organisms within the floodplain soils. The rate of reduction in bioavailable DDX, however, was significantly faster in LA soils (ß = -0.189, p < 0.0001) compared to FA soils (ß = -0.054, p < 0.0038). Differences in temperature and methods of activated carbon incorporation between LA and FA soils may account for the differences in remediation rate, suggesting laboratory experiments may overpredict the extent or speed in which remediation occurs in the field. Therefore, use of laboratory studies in predicting success of activated carbon remediation may be most effective when conditions mimic field remediation as closely as possible.


Assuntos
Oligoquetos , Poluentes do Solo , Animais , Carvão Vegetal , DDT/análise , Solo , Poluentes do Solo/análise
2.
Chemosphere ; 261: 127811, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32750622

RESUMO

Bioaccessibility-based extraction tools, such as single-point Tenax extractions (SPTEs), provide cost-effective and accurate estimates of bioaccumulation and toxicity of hydrophobic organic contaminants during environmental sampling. Use of SPTEs as a screening tool in risk assessment is hindered by the requirement for normalization of extractable concentrations for organic carbon (OC). Normalizing SPTE concentrations for the volume of Tenax used during the extraction could improve the applicability of this methodology by removing the system dependence when applying SPTE concentrations to estimates of bioaccumulation. The objective of this study was to examine the utility of Tenax phase volume normalization in place of OC normalization when using SPTEs to estimate bioaccumulation. No significant differences were observed between the slope of regression lines generated between SPTE concentrations normalized for either Tenax phase volume or OC (p = 0.410), but slight improvement of the regression was noted when using phase volume normalization (R2 = 0.829) compared to OC normalization (R2 = 0.740). Replacing OC normalization with phase volume normalization in use of SPTEs more accurately represents the partition of the chemical to the Tenax during the SPTE, improves estimates of bioaccumulation, and expands the use of SPTEs as a rapid assessment tool for determining bioaccumulation during screening of contaminated environments.


Assuntos
Monitoramento Ambiental/métodos , Polímeros/química , Animais , Sedimentos Geológicos/química , Interações Hidrofóbicas e Hidrofílicas , Medição de Risco
3.
Environ Monit Assess ; 192(4): 216, 2020 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-32140849

RESUMO

The Pine River, in the central, Lower Peninsula region of Michigan, has a long history of contamination. Livestock facilities and manure application sites along the Pine River and its tributaries have led to elevated nutrient levels. In addition to nutrient loading and associated low levels of dissolved oxygen, the presence Escherichia coli bacteria have caused environmental and human health concerns. According to the Michigan Department of Health and Human Services, and the Michigan Department of Environment, Great Lakes, and Energy, E. coli counts in summer months consistently have exceeded safe levels for human contact since 2005. Though it is recommended that residents do not swim in the Pine River, there are no specific restrictions on recreational fishing which is prevalent. Few studies have evaluated whether or not E. coli accumulates in the mucus of fish and, if so, whether that provides a viable route of E. coli exposure for anglers. This study first evaluated the presence of fecal coliform and E. coli bacteria on hatchery-raised caged fish placed in the river as well as resident fish. Results showed that fecal coliform and E. coli bacteria accumulated both on caged and resident fish. This result led to further testing showing E. coli to be found on anglers' hands whether or not they handled or interacted with resident fish. This study suggests that fishing in rivers with heavy bacterial loading from agricultural runoff may expose anglers to potentially harmful E. coli.


Assuntos
Agricultura , Exposição Ambiental , Escherichia coli , Peixes , Microbiologia da Água , Animais , Monitoramento Ambiental , Humanos , Michigan , Rios , Estações do Ano
4.
Environ Monit Assess ; 191(11): 665, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31650258

RESUMO

The Pine River downstream of the Velsicol Superfund site has been contaminated with various hydrophobic organic pollutants for more than 50 years. Remediation and sediment dredging near the site began in spring of 1999, and was completed in 2006. In 2011, the Michigan Department of Environmental Quality completed a baseline assessment report long-term monitoring plan for the Pine River. However, there has been limited assessment of the benthic community since this evaluation. The objective of this research was to evaluate the risk of Pine River sediment to aquatic macroinvertebrates downstream from the Superfund site after decades of degradation and dredging using the Triad approach. Three sites were selected downstream from the Superfund site, and an upstream reference site was used. At each site, macroinvertebrates surveys were conducted and sediments were collected for chemical analysis of DDT (1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane) and its degradation products and for laboratory toxicity testing for mortality and sublethal effects using Hyalella azteca and Chironomus dilutus. Sediment concentrations of DDT, DDD, and DDE were below levels expected to cause toxicity, and there was no observed toxicity in laboratory tests. Additionally, there were no statistically significant differences in richness, richness of Ephemeroptera, Plecoptera, and Trichoptera (EPT) species, total EPT abundance, percent EPT, or percent dominant taxa between the reference site and the downstream sites. There was an observed decrease in abundance of macroinvertebrate taxa at all downstream sites and a shift in macroinvertebrate structure when comparing the reference with most impaired sites. Although the sites downstream of the Superfund site remain different than the upstream control, there are improvements in species composition and abundance. However, more research is needed to evaluate the potential effects on ecosystem function.


Assuntos
DDT/análise , Diclorodifenil Dicloroetileno/análise , Diclorodifenildicloroetano/análise , Monitoramento Ambiental/métodos , Sedimentos Geológicos/química , Locais de Resíduos Perigosos , Poluentes Químicos da Água/análise , Anfípodes/efeitos dos fármacos , Animais , Chironomidae/efeitos dos fármacos , DDT/metabolismo , Ecossistema , Michigan , Rios/química , Testes de Toxicidade
5.
Arch Environ Contam Toxicol ; 74(3): 361-371, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-28601932

RESUMO

Current methods for evaluating exposure in ecosystems contaminated with hydrophobic organic contaminants typically focus on sediment exposure. However, a comprehensive environmental assessment requires a more holistic approach that not only estimates sediment concentrations, but also accounts for exposure by quantifying other pathways, such as bioavailability, bioaccumulation, trophic transfer potential, and transport of hydrophobic organic contaminants within and outside of the aquatic system. The current study evaluated the ability of multiple metrics to estimate exposure in an aquatic ecosystem. This study utilized a small lake contaminated with polychlorinated biphenyls (PCBs) to evaluate exposure to multiple trophic levels as well as the transport of these contaminants within and outside of the lake. The PCBs were localized to sediments in one area of the lake, yet this area served as the source of PCBs to aquatic invertebrates, emerging insects, and fish and terrestrial spiders in the riparian ecosystem. The Tenax extractable and biota PCB concentrations indicated tissue concentrations were localized to benthic invertebrates and riparian spiders in a specific cove. Fish data, however, demonstrated that fish throughout the lake had PCB tissue concentrations, leading to wider exposure risk. The inclusion of PCB exposure measures at several trophic levels provided multiple lines of evidence to the scope of exposure through the aquatic and riparian food web, which aids in assessing risk and developing potential future remediation strategies.


Assuntos
Ecotoxicologia/métodos , Exposição Ambiental/análise , Bifenilos Policlorados/análise , Poluentes Químicos da Água/análise , Animais , Biota , Ecossistema , Peixes , Cadeia Alimentar , Sedimentos Geológicos/química , Illinois , Insetos , Invertebrados , Lagos , Bifenilos Policlorados/farmacocinética , Bifenilos Policlorados/toxicidade , Aranhas , Poluentes Químicos da Água/farmacocinética , Poluentes Químicos da Água/toxicidade
6.
Arch Environ Contam Toxicol ; 72(4): 612-621, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28365790

RESUMO

Single-point Tenax extractions (SPTEs) of hydrophobic organic contaminants provide estimates of bioaccessibility through consistent measures of the chemical concentration initially in the rapidly desorbing fraction in sediment (C rapT0), such that a constant ratio is expected between SPTE and C rapT0 (C T /C rapT0, where T is the duration of the SPTE). As environmental factors (i.e., aging time and organic carbon content) and contaminant hydrophobicity can affect the C rapT0, the utility of the SPTEs as exposure estimates hinges on the consistency of the C T /C rapT0 ratio. Individually these factors have little impact on the ability of SPTEs to represent bioaccumulation, but the effect of these factors in combination, as well as SPTE methodological variation on the C T /C rapT0 ratio is poorly understood. The current study evaluated how environmental and methodological variation-expressed as varying Tenax to organic carbon mass (Tenax:OC) ratios-impacts the C 24h/C rapT0 ratio of pyrethroids in laboratory-spiked sediments. A multiple regression analysis was used to examine the impact of organic carbon, pyrethroid hydrophobicity, Tenax mass, and aging time on the C 24h/C rapT0 ratio. Only aging time of the pyrethroids in sediment significantly affected the C 24h/C rapT0 ratio with a slight decline of -0.0027/d in the C 24h/C rapT0 ratio, and this decline was considered negligible as a consistent C 24h/C rapT0 ratio of 1.46 ± 0.03 was observed across all experimental treatments. This result further demonstrates the consistency of SPTEs to estimate bioaccessibility of hydrophobic contaminants in sediment and subsequent exposure.


Assuntos
Polímeros/análise , Poluentes Químicos da Água/análise , Meio Ambiente , Sedimentos Geológicos/química
7.
Environ Toxicol Chem ; 36(5): 1301-1310, 2017 05.
Artigo em Inglês | MEDLINE | ID: mdl-27779324

RESUMO

The present study evaluated the risk associated with the application and co-occurrence of 2 herbicides, atrazine and sulfentrazone, applied to a 32-ha corn and soybean rotational field. Field concentrations of the compounds were measured in soil, runoff water, and groundwater, with peak mean atrazine and sulfentrazone concentrations found in the soil (144 ng/g dry wt, and 318 ng/g dry wt, respectively). Individual and mixture laboratory bioassays were conducted to determine the effects of atrazine and sulfentrazone on the survival of Daphnia magna and Pimephales promelas, the germination of Lactuca sativa, and the growth of Pseudokirchneriella subcapita and Lemna minor. Pseudokirchneriella subcapita and L. minor were the most susceptible species tested, and the effects on growth of the herbicides in mixtures best fit an independent action model. Risk quotients and margin of safety of 10% (MOS10) values were used to estimate risk and were calculated using runoff water concentrations. The MOS10 values were more sensitive than risk quotients in estimating risk. The MOS10 value for sulfentrazone runoff water concentration effects on P. subcapita was 7.8, and for L. minor was 1.1, with MOS10 values < 1 indicating potential risk. Overall, the environmentally relevant concentrations fell below the effect concentrations; therefore, atrazine and sulfentrazone posed little to no risk to the nontarget species tested. Environ Toxicol Chem 2017;36:1301-1310. © 2016 SETAC.


Assuntos
Atrazina/análise , Herbicidas/análise , Poluentes do Solo/análise , Sulfonamidas/análise , Triazóis/análise , Agricultura , Animais , Araceae/efeitos dos fármacos , Araceae/crescimento & desenvolvimento , Atrazina/toxicidade , Cyprinidae/crescimento & desenvolvimento , Daphnia/efeitos dos fármacos , Germinação/efeitos dos fármacos , Água Subterrânea/análise , Herbicidas/toxicidade , Alface/efeitos dos fármacos , Alface/crescimento & desenvolvimento , Risco , Poluentes do Solo/toxicidade , Sulfonamidas/toxicidade , Triazóis/toxicidade , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade
8.
Chemosphere ; 171: 308-317, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-28027475

RESUMO

Use of Tenax extractable concentrations to estimate biological exposure to hydrophobic organic contaminants is well documented, yet method variation exists between studies, specifically in the ratio of Tenax mass to organic carbon mass in the sediment (Tenax:OC ratio) being extracted. The effects of this variation on exposure estimates are not well understood. As Tenax is theoretically in direct competition with organic carbon for freely dissolved chemical in sediment interstitial water, varying the Tenax:OC ratio could impact single-point Tenax extraction (SPTE) exposure estimates. Therefore, the effects of varying Tenax:OC ratios on SPTE pyrethroid concentrations from field-contaminated and laboratory-spiked sediments were compared to bioaccumulation by Lumbriculus variegatus. The Tenax:OC ratio had minimal effect on SPTE pyrethroid concentrations. The SPTE pyrethroid concentrations obtained using the highest and lowest Tenax:OC ratios ranged from 0.85- to 3.91-fold different, which is unlikely to contribute substantial error to bioaccessibility estimates. Comparisons to Tenax exposure endpoints from previous research reveal the variation in these endpoints is likely due to toxicokinetic and toxicodynamic differences; processes common to exposure estimates provided by any chemical extraction technique. As the pyrethroid concentrations in the experimental sediments caused toxicity to L. variegatus, thus affecting bioaccumulation, the SPTE concentrations overestimated bioaccumulation. However, SPTE concentrations strongly correlated with growth inhibition regardless of the Tenax:OC ratio, providing accurate estimates of the correct exposure endpoint. Tenax masses of 0.500-0.800 g should provide sufficient Tenax to achieve Tenax:OC ratios of at least 5:1, which will provide accurate exposure estimates while retaining the ease of conducting SPTEs.


Assuntos
Carbono/química , Sedimentos Geológicos/química , Oligoquetos/efeitos dos fármacos , Polímeros/química , Piretrinas/isolamento & purificação , Poluentes Químicos da Água/isolamento & purificação , Animais , Recuperação e Remediação Ambiental , Interações Hidrofóbicas e Hidrofílicas , Oligoquetos/crescimento & desenvolvimento , Piretrinas/química , Poluentes Químicos da Água/química
9.
Environ Pollut ; 220(Pt A): 375-382, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27756597

RESUMO

The recent discovery of pyrethroid-resistant Hyalella azteca populations in California, USA suggests there has been significant exposure of aquatic organisms to these terrestrially-applied insecticides. Since resistant organisms are able to survive in relatively contaminated habitats they may experience greater pyrethroid bioaccumulation, subsequently increasing the risk of those compounds transferring to predators. These issues were evaluated in the current study following toxicity tests in water with permethrin which showed the 96-h LC50 of resistant H. azteca (1670 ng L-1) was 53 times higher than that of non-resistant H. azteca (31.2 ng L-1). Bioaccumulation was compared between resistant and non-resistant H. azteca by exposing both populations to permethrin in water and then measuring the tissue concentrations attained. Our results indicate that resistant and non-resistant H. azteca have similar potential to bioaccumulate pyrethroids at the same exposure concentration. However, significantly greater bioaccumulation occurs in resistant H. azteca at exposure concentrations non-resistant organisms cannot survive. To assess the risk of pyrethroid trophic transfer, permethrin-dosed resistant H. azteca were fed to fathead minnows (Pimephales promelas) for four days, after which bioaccumulation of permethrin and its biotransformation products in fish tissues were measured. There were detectable concentrations of permethrin in fish tissues after they consumed dosed resistant H. azteca. These results show that bioaccumulation potential is greater in organisms with pyrethroid resistance and this increases the risk of trophic transfer when consumed by a predator. The implications of this study extend to individual fitness, populations and food webs.


Assuntos
Anfípodes/metabolismo , Cyprinidae/metabolismo , Inseticidas/metabolismo , Permetrina/metabolismo , Poluentes Químicos da Água/metabolismo , Anfípodes/efeitos dos fármacos , Animais , California , Cadeia Alimentar , Resistência a Inseticidas , Inseticidas/análise , Inseticidas/toxicidade , Permetrina/análise , Permetrina/toxicidade , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade
10.
Environ Toxicol Chem ; 34(7): 1445-53, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-26118373

RESUMO

It is well documented that using exhaustive chemical extractions is not an effective means of assessing exposure of hydrophobic organic compounds in sediments and that bioavailability-based techniques are an improvement over traditional methods. One technique that has shown special promise as a method for assessing the bioavailability of hydrophobic organic compounds in sediment is the use of Tenax-extractable concentrations. A 6-h or 24-h single-point Tenax-extractable concentration correlates to both bioaccumulation and toxicity. This method has demonstrated effectiveness for several hydrophobic organic compounds in various organisms under both field and laboratory conditions. In addition, a Tenax bioaccumulation model was developed for multiple compounds relating 24-h Tenax-extractable concentrations to oligochaete tissue concentrations exposed in both the laboratory and field. This model has demonstrated predictive capacity for additional compounds and species. Use of Tenax-extractable concentrations to estimate exposure is rapid, simple, straightforward, and relatively inexpensive, as well as accurate. Therefore, this method would be an invaluable tool if implemented in risk assessments.


Assuntos
Recuperação e Remediação Ambiental , Sedimentos Geológicos/química , Polímeros/química , Anfípodes/efeitos dos fármacos , Animais , Disponibilidade Biológica , Inseticidas/química , Inseticidas/toxicidade , Modelos Teóricos , Piretrinas/química , Piretrinas/toxicidade , Medição de Risco , Poluentes do Solo/química , Poluentes do Solo/toxicidade
12.
Integr Environ Assess Manag ; 11(2): 208-20, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-25377271

RESUMO

Characterizing sediment-associated hydrophobic contaminants is problematic, because assessing the total amount of a compound available for chemical exchange with an organism is difficult. To address this, contaminant concentrations have been normalized for specific sediment characteristics (including organic C content) or the chemical activity has been estimated using passive samplers. Another approach to assess compound availability is to determine the extent of readily desorbed compound using resin extractions of sediment slurries. The present paper reviews the literature that uses Tenax® TA, a 2,6-diphenylene-oxide polymer as an extraction tool to measure bioavailability of hydrophobic organic contaminants in sediment. Some work has assessed the extent of desorption with sequential extractions to characterize the maximum rate and pool sizes for different desorbing fractions of bound contaminant. As such, the rapidly desorbing fraction has been well correlated with the extent of degradation, bioaccumulation, and toxicity of hydrophobic contaminants. A shortcut to measuring the full desorption curve to determine the rapidly desorbing compound is to use a single-point extraction, with 6 h or 24 h extractions being the most common. The Tenax extraction has been shown to be effective with laboratory-spiked sediments, field-collected sediments, laboratory-exposed organisms, field-collected organisms, and studies among laboratories. Furthermore, a literature-based model has described the bioaccumulation of polychlorinated biphenyls from independently measured field-collected sediments. Despite the success of this approach, applying the Tenax method to manage contaminated sediments is limited by the absence of a standard set of conditions to perform the extractions, as well as standard methods for using field sediments.


Assuntos
Organismos Aquáticos/efeitos dos fármacos , Recuperação e Remediação Ambiental , Sedimentos Geológicos/análise , Polímeros/química , Poluentes Químicos da Água/toxicidade , Adsorção , Organismos Aquáticos/metabolismo , Disponibilidade Biológica , Interações Hidrofóbicas e Hidrofílicas , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/metabolismo
13.
Environ Toxicol Chem ; 33(2): 286-92, 2014 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-24127319

RESUMO

Recent literature has shown that bioavailability-based techniques, such as Tenax extraction, can estimate sediment exposure to benthos. In a previous study by the authors, Tenax extraction was used to create and validate a literature-based Tenax model to predict oligochaete bioaccumulation of polychlorinated biphenyls (PCBs) from sediment; however, its ability to assess sediment remediation was unknown. The present study further tested the Tenax model by examining the impacts of remediation on surface sediment concentrations, Tenax extractable concentrations, and tissue concentrations of laboratory-exposed Lumbriculus variegatus. Tenax extractable concentration was an effective exposure metric to evaluate changes in Lumbriculus exposure preremediation and postremediation, with 75% of the postremediation data corresponding to the Tenax model. At nondredged sites, bioaccumulation was better predicted by the Tenax model, with 86% of the data falling within the 95% confidence intervals, than at dredged sites, for which only 64% of the data fit the Tenax model. In both pre- and postdredge conditions, when the model failed, it was conservative, predicting higher PCB concentrations than observed in the oligochaetes, particularly for the postdredge data. The present study advances understanding of the applicability of the Tenax model for use when examining systems that may have undergone significant disturbances. The Tenax model provides a unique tool for quickly quantifying potential exposure to benthic organisms.


Assuntos
Modelos Teóricos , Oligoquetos/metabolismo , Bifenilos Policlorados/metabolismo , Polímeros/química , Poluentes Químicos da Água/metabolismo , Adsorção , Animais , Disponibilidade Biológica , Recuperação e Remediação Ambiental , Sedimentos Geológicos/química , Bifenilos Policlorados/química , Poluentes Químicos da Água/química
14.
Environ Toxicol Chem ; 33(4): 868-74, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24375636

RESUMO

The majority of sediment toxicity and aquatic bioaccumulation assessments are conducted using standardized species, such as Hyalella azteca, Chironomus dilutus, and Lumbriculus variegatus. The burrowing mayfly, Hexagenia sp., may serve as an ideal supplemental organism for both toxicity and bioaccumulation studies for several reasons. Hexagenia are recognized as sensitive species, have a long aquatic life stage (up to 2 yr), and have large bodies, which aid in retrieval from sediments and for residue analysis. The present study outlines the authors' established method for collecting and hatching eggs, raising nymphs, and using these animals for toxicity testing. Furthermore, the relative sensitivity of 3 size classes of Hexagenia to a representative contaminant (bifenthrin) was examined and compared with laboratory-derived median lethal concentrations for the more traditionally used Hyalella and Chironomus. Finally, sublethal end points, including immobilization and suspended solids, were defined for this species. This provides guidance for the use of this species in toxicological bioassays.


Assuntos
Insetos/efeitos dos fármacos , Inseticidas/toxicidade , Piretrinas/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Bioensaio , Tamanho Corporal/efeitos dos fármacos , Sedimentos Geológicos , Insetos/fisiologia , Dose Letal Mediana , Atividade Motora/efeitos dos fármacos , Testes de Toxicidade
15.
Integr Environ Assess Manag ; 10(2): 167-78, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24307344

RESUMO

This manuscript surveys the literature on passive sampler methods (PSMs) used in contaminated sediments to assess the chemical activity of organic contaminants. The chemical activity in turn dictates the reactivity and bioavailability of contaminants in sediment. Approaches to measure specific binding of compounds to sediment components, for example, amorphous carbon or specific types of reduced carbon, and the associated partition coefficients are difficult to determine, particularly for native sediment. Thus, the development of PSMs that represent the chemical activity of complex compound-sediment interactions, expressed as the freely dissolved contaminant concentration in porewater (Cfree ), offer a better proxy for endpoints of concern, such as reactivity, bioaccumulation, and toxicity. Passive sampling methods have estimated Cfree using both kinetic and equilibrium operating modes and used various polymers as the sorbing phase, for example, polydimethylsiloxane, polyethylene, and polyoxymethylene in various configurations, such as sheets, coated fibers, or vials containing thin films. These PSMs have been applied in laboratory exposures and field deployments covering a variety of spatial and temporal scales. A wide range of calibration conditions exist in the literature to estimate Cfree , but consensus values have not been established. The most critical criteria are the partition coefficient between water and the polymer phase and the equilibrium status of the sampler. In addition, the PSM must not appreciably deplete Cfree in the porewater. Some of the future challenges include establishing a standard approach for PSM measurements, correcting for nonequilibrium conditions, establishing guidance for selection and implementation of PSMs, and translating and applying data collected by PSMs.


Assuntos
Monitoramento Ambiental/métodos , Sedimentos Geológicos/química , Compostos Orgânicos/análise , Poluentes Químicos da Água/análise , Compostos Orgânicos/metabolismo , Poluentes Químicos da Água/metabolismo
16.
Chemosphere ; 90(3): 1117-22, 2013 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-23084260

RESUMO

Recent studies have determined that techniques, such as solid phase microextraction (SPME) fibers and Tenax beads, can predict bioaccumulation and potentially could predict toxicity for several compounds and species. Toxicity of bifenthrin was determined using two standard sediment toxicity tests with the benthic species Hyalella azteca and Chironomus dilutus in three reference sediments with different characteristics. The objectives of the current study were to establish bioavailability-based median lethal concentrations (LC50) and median effect concentrations (EC50) of the pyrethroid insecticide bifenthrin, compare their ability to assess toxicity to the use of whole sediment concentrations, as well as to make comparisons of the concentrations derived using each method in order to make assessments of accuracy and extrapolation potential. Four metrics were compared including SPME fiber concentration, pore water concentration derived using SPMEs, 6 h Tenax extractable concentration, and 24 h Tenax extractable concentration. The variation among the LC50s and EC50s in each sediment derived using bioavailability-based methods was comparable to variation among organic carbon normalized sediment concentrations, but improved over whole sediment concentrations. There was a significant linear relationship between SPME or Tenax and organic carbon normalized sediment concentrations. Additionally, there was a significant relationship between the SPME and Tenax concentrations across sediments. The significant linear relationship between SPME and Tenax concentrations further demonstrates that these bioavailability-based endpoints are interrelated. This study derived bioavailability-based benchmarks that may prove to be more accurate than sediment-based ones in predicting toxicity across sediment types.


Assuntos
Anfípodes/efeitos dos fármacos , Chironomidae/efeitos dos fármacos , Sedimentos Geológicos/análise , Inseticidas/toxicidade , Piretrinas/toxicidade , Animais , Inseticidas/isolamento & purificação , Dose Letal Mediana , Polímeros/química , Piretrinas/isolamento & purificação , Microextração em Fase Sólida/métodos
17.
Environ Pollut ; 173: 47-51, 2013 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-23202281

RESUMO

The presence of pyrethroids in both urban and agricultural sediments at levels lethal to invertebrates has been well documented. However, variations in bioavailability among sediments make accurate predictions of toxicity based on whole sediment concentrations difficult. A proposed solution to this problem is the use of bioavailability-based estimates, such as solid phase microextraction (SPME) fibers and Tenax beads. This study compared three methods to assess the bioavailability and ultimately toxicity of pyrethroid pesticides including field-deployed SPME fibers, laboratory-exposed SPME fibers, and a 24-h Tenax extraction. The objective of the current study was to compare the ability of these methods to quantify the bioavailable fraction of pyrethroids in contaminated field sediments that were toxic to benthic invertebrates. In general, Tenax proved a more sensitive method than SPME fibers and a correlation between Tenax extractable concentrations and mortality was observed.


Assuntos
Clorpirifos/análise , Monitoramento Ambiental/métodos , Sedimentos Geológicos/química , Polímeros/química , Piretrinas/análise , Poluentes do Solo/análise , Microextração em Fase Sólida , Animais , Clorpirifos/química , Piretrinas/química , Poluentes do Solo/química
18.
Environ Toxicol Chem ; 31(9): 2168-74, 2012 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22786796

RESUMO

In the companion paper, solid phase microextraction (SPME) fiber concentrations were used as a dose metric to evaluate the toxicity of hydrophobic pesticides, and concentration-response relationships were found for the hydrophobic pesticides tested in the two test species. The present study extends the use of fiber concentrations to organism body residues to specifically address biotransformation and provide the link to toxic response. Test compounds included the organochlorines p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), p,p'-dichlorodiphenyldichloroethane (p,p'-DDD), and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE); two pyrethroids, permethrin and bifenthrin; and an organophosphate, chlorpyrifos. Toxicity, body residues, and biotransformation of the target compounds were determined for the midge Chironomus dilutus and the amphipod Hyalella azteca. Significant regression relationships were found without regard to chemical, extent of biotransformation, or whether the chemical reached steady state in the organisms. The equilibrium SPME fiber concentrations correlated with the parent compound concentration in the biota; however, the regressions were duration specific. Furthermore, the SPME fiber-based toxicity values yielded species-specific regressions with the parent compound-based toxicity values linking the use of SPME fiber as a dose metric with tissue residues to estimate toxic response.


Assuntos
Praguicidas/toxicidade , Poluentes Químicos da Água/toxicidade , Anfípodes/efeitos dos fármacos , Anfípodes/metabolismo , Animais , Biotransformação , Chironomidae/efeitos dos fármacos , Chironomidae/metabolismo , Clorpirifos/química , Clorpirifos/metabolismo , Clorpirifos/toxicidade , DDT/química , DDT/metabolismo , DDT/toxicidade , Diclorodifenil Dicloroetileno/química , Diclorodifenil Dicloroetileno/metabolismo , Diclorodifenil Dicloroetileno/toxicidade , Diclorodifenildicloroetano/química , Diclorodifenildicloroetano/metabolismo , Diclorodifenildicloroetano/toxicidade , Interações Hidrofóbicas e Hidrofílicas , Permetrina/química , Permetrina/metabolismo , Permetrina/toxicidade , Resíduos de Praguicidas/metabolismo , Praguicidas/química , Praguicidas/metabolismo , Piretrinas/química , Piretrinas/metabolismo , Piretrinas/toxicidade , Microextração em Fase Sólida , Poluentes Químicos da Água/química , Poluentes Químicos da Água/metabolismo
19.
Environ Toxicol Chem ; 31(9): 2159-67, 2012 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22767390

RESUMO

Use of solid-phase microextraction (SPME) fibers as a dose metric for toxicity testing was evaluated for hydrophobic pesticides to the midge Chironomus dilutus and the amphipod Hyalella azteca. Test compounds included p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), p,p'-dichlorodiphenyldichloroethane (p,p'-DDD), p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), permethrin, bifenthrin, tefluthrin, and chlorpyrifos. Acute water toxicity tests were determined for 4- and 10-d exposures in both species. Median lethal and sublethal concentrations were expressed both on a water concentration (LC50 and EC50) and on an equilibrium SPME fiber concentration (LC50(fiber) and EC50(fiber)) basis. A significant log dose-response relationship was found between log fiber concentration and organism mortality. It has been shown in the literature that equilibrium SPME fiber concentrations reflect the bioavailable concentrations of hydrophobic contaminants, so these fiber concentrations should be a useful metric for assessing toxic effects from the bioavailable contaminant providing a framework to expand the use of SPME fibers beyond estimation of bioaccumulation.


Assuntos
Praguicidas/química , Poluentes Químicos da Água/química , Anfípodes/efeitos dos fármacos , Animais , Chironomidae/efeitos dos fármacos , Clorpirifos/química , Clorpirifos/toxicidade , Ciclopropanos/química , Ciclopropanos/toxicidade , DDT/química , DDT/toxicidade , Diclorodifenil Dicloroetileno/química , Diclorodifenil Dicloroetileno/toxicidade , Diclorodifenildicloroetano/química , Diclorodifenildicloroetano/toxicidade , Hidrocarbonetos Fluorados/química , Hidrocarbonetos Fluorados/toxicidade , Interações Hidrofóbicas e Hidrofílicas , Dose Letal Mediana , Permetrina/química , Permetrina/toxicidade , Praguicidas/toxicidade , Piretrinas/química , Piretrinas/toxicidade , Microextração em Fase Sólida , Testes de Toxicidade Aguda , Poluentes Químicos da Água/toxicidade
20.
Environ Sci Technol ; 46(4): 2413-9, 2012 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-22316215

RESUMO

Recent studies recognize the ability of chemical techniques such as solid phase microextraction (SPME) fibers and Tenax extraction to predict bioavailability more effectively than exhaustive chemical extractions for sediment-associated organic contaminants. While the majority of research using these techniques studied legacy compounds such as PCBs and PAHs, there is great potential for these methods to work well for highly toxic, rapidly biotransformed compounds such as pyrethroid insecticides. The current study compared the ability of the two techniques to predict the bioavailability of permethrin and bifenthrin to two benthic invertebrates (Lumbriculus variegatus and Hexagenia sp.). In addition, variations in the application of the two techniques, specifically duration and conditions of exposure of the SPME fibers and duration of extraction with Tenax, were explored. The SPME fiber concentrations correlated strongly to both 6 and 24 h Tenax concentrations. The SPME fiber concentrations and 6 h and 24 h Tenax extractable concentrations correlated with both the parent permethrin and bifenthrin concentrations in the tissues of both species at steady state. Parent compound tissue concentrations for both species could be predicted with a single relationship for individual pyrethroids. This demonstrated the potential value of these methods to predict the bioavailability of compounds subject to biotransformation and application to multiple species.


Assuntos
Insetos/metabolismo , Inseticidas/metabolismo , Oligoquetos/metabolismo , Permetrina/metabolismo , Piretrinas/metabolismo , Poluentes Químicos da Água/metabolismo , Animais , Disponibilidade Biológica , Biotransformação , Monitoramento Ambiental/métodos , Inseticidas/química , Permetrina/química , Polímeros/química , Piretrinas/química , Microextração em Fase Sólida , Poluentes Químicos da Água/química
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