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1.
Environ Pollut ; 267: 115470, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-33254663

RESUMO

Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:0) and accessible (CAS:0) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:0 concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:0 variability. CAS:0 in sediment ranged from 10 to 90% of the total concentration in sediment. CW:0 was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:0 values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.

2.
Environ Pollut ; : 116121, 2020 Nov 24.
Artigo em Inglês | MEDLINE | ID: mdl-33272798

RESUMO

POCIS is the most widely applied passive sampler of polar organic substances, because it was one of the first commercially available samplers for that purpose on the market, but also for its applicability for a wide range of substances and conditions. Its main weakness is the variability of sampling performance with exposure conditions. In our study we took a pragmatic approach and performed in situ calibration for a set of 76 pharmaceuticals and their metabolites in five sampling campaigns in surface water, covering various temperature and flow conditions. In individual campaigns, RS were calculated for up to 47 compounds ranging from 0.01 to 0.63 L d-1, with the overall median value of 0.10 L d-1. No clear changes of RS with water temperature or discharge could be found for any of the investigated substances. The absence of correlation of experimental RS with physical-chemical properties in combination with the lack of mechanistic understanding of compound uptake to POCIS implies that practical estimation of aqueous concentrations from uptake in POCIS depends on compound-specific experimental calibration data. Performance of POCIS was compared with grab sampling of water in seven field campaigns comprising multiple sampling sites, where sampling by both methods was done in parallel. The comparison showed that for 25 of 36 tested compounds more than 50% of POCIS-derived aqueous concentrations did not differ from median of grab sampling values more than by a factor of 2. Further, for 30 of 36 compounds, more than 80% of POCIS data did not differ from grab sampling data more than by a factor of 5. When accepting this level of accuracy, in situ derived sampling rates are sufficiently robust for application of POCIS for identification of spatial and temporal contamination trends in surface waters.

3.
Environ Sci Technol ; 54(13): 7942-7951, 2020 07 07.
Artigo em Inglês | MEDLINE | ID: mdl-32551598

RESUMO

The concentrations of hydrophobic organic compounds (HOCs) in aquatic biota are used for compliance, as well as time and spatial trend monitoring in the aqueous environment (European Union water framework directive, OSPAR). Because of trophic magnification in the food chain, the thermodynamic levels of HOCs, for example, polychlorinated biphenyl congeners, dichlorodiphenyltrichloroethane, and brominated diphenyl ether congeners, in higher trophic level (TL) organisms are expected to be strongly elevated above those in water. This work compares lipid-based concentrations at equilibrium with the water phase derived from aqueous passive sampling (CL⇌water) with the lipid-based concentrations in fillet and liver of fish (CL) at different TLs for three water bodies in the Czech Republic and Slovakia. The CL values of HOCs in fish were near CL⇌water, only after trophic magnification up to TL = 4. For fish at lower TL, CL progressively decreased relative to CL⇌water as KOW of HOCs increased above 106. The CL value decreasing toward the bottom of the food chain suggests nonequilibrium for primary producers (algae), which is in agreement with modeling passive HOC uptake by algae. Because trophic magnification and the resulting CL in fish exhibit large natural variability, CL⇌water is a viable alternative for monitoring HOCs using fish, showing a twofold lower confidence range and requiring less samples.


Assuntos
Monitoramento Ambiental , Poluentes Químicos da Água , Animais , República Tcheca , Peixes , Cadeia Alimentar , Água Doce , Eslováquia , Água , Poluentes Químicos da Água/análise
4.
Environ Int ; 138: 105597, 2020 05.
Artigo em Inglês | MEDLINE | ID: mdl-32120059

RESUMO

The occurrence of chemical and biological contaminants of emerging concern (CECs) was investigated in treated wastewater intended for reuse in agriculture. An agarose hydrogel diffusion-based passive sampler was exposed to the outlet of a wastewater treatment plant (WWTP) located in Cyprus, which is equipped with membrane bioreactor (MBR). Passive samplers in triplicate were exposed according to a time-series exposure plan with maximum exposure duration of 28 days. Composite flow-proportional wastewater samples were collected in parallel with the passive sampling exposure plan and were processed by solid phase extraction using HORIZON SPE-DEX 4790 and the same sorbent material (Oasis HLB) as in the passive sampler. The analysis of passive samplers and wastewater samples enabled (i) the field-scale calibration of the passive sampler prototype by the calculation of in situ sampling rates of target substances, and (ii) the investigation of in silico predicted transformation products of the four most ecotoxicologically hazardous antibiotics (azithromycin, clarithromycin, erythromycin, ofloxacin). Additionally, the wastewater samples were subjected to the analysis of seven preselected antibiotic resistant genes (ARGs) and one mobile resistant element (int1). All extracts were analyzed for chemicals in a single batch using a highly sensitive method for pharmaceuticals, antibiotics and illicit drugs by liquid chromatography tandem MS/MS (LC-QQQ) and for various other target compounds (2316 compounds in total) by liquid chromatography high-resolution mass spectrometry (LC-HRMS). 279 CECs and all investigated ARGs (except for blaCTX-M-32) were detected, highlighting potential chemical and biological hazards related to wastewater reuse practices. 16 CECs were prioritized following ecotoxicological risk assessment, whereas sul1 and the mobile resistant element (int1) showed the highest abundance. Comprehensive monitoring efforts using novel sampling methods such as passive sampling, wide-scope target screening and molecular analysis are required to assure safe application of wastewater reuse and avoid spread and crop uptake of potentially hazardous chemicals.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Agricultura , Monitoramento Ambiental , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/análise
5.
Sci Total Environ ; 720: 137480, 2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32146393

RESUMO

Silicone (polydimethylsiloxane or PDMS) wristbands and cotton T-shirts were used to assess the exposure of e-waste recyclers in Dhaka, Bangladesh to polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), dechlorane plus (DPs), and organophosphate esters (OPEs). The median surface-normalized uptake rates of PBDEs, NBFRs, DPs, and OPEs were 170, 8.5, 4.8, and 270 ng/dm2/h for wristbands and 5.4, 2.0, 0.94, and 23 ng/dm2/h for T-shirts, respectively. Concentrations of Tris(2-chloroethyl) phosphate (TCEP), Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), Tri-m-cresyl phosphate (TmCP), Bis(2-ethlyhexyl) tetrabromophthalate (BEH-TEBP), and Dechlorane plus (DPs) in wristbands were significantly correlated with those in T-shirts. Wristbands accumulated ~7 times more mass than T-shirts, especially of compounds expected to be mainly in the gas phase. We introduce the silicone "sandwich" method to approximate the easily releasable fraction (ERF) from T-shirts, hypothesized to be related to dermal exposure. ERFs varied from 6 to 75% of total chemical accumulated by T-shirts and were significantly negatively correlated with compounds' octanol-air partition coefficient (log Koa). The median daily exposure doses via dermal transfer from the front of the T-shirt to the front body trunk were 0.32, 0.13, 0.11, and 9.1 ng/kg-BW/day for PBDEs, NBFRs, DPs, and OPEs, respectively. The evidence of e-waste recycler exposure to flame retardants in this low income country, lacking protective personal equipment, calls for measures to minimize their exposure and for chemical management regulations to consider exposures to chemicals in waste products.


Assuntos
Resíduo Eletrônico , Bangladesh , Monitoramento Ambiental , Ésteres , Retardadores de Chama , Éteres Difenil Halogenados , Organofosfatos , Silicones
6.
Chemosphere ; 249: 126183, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32088466

RESUMO

Diffusion coefficient (D) is an important parameter for prediction of micropollutant uptake kinetics in passive samplers. Passive samplers are nowadays commonly used for monitoring trace organic pollutants in different environmental matrices. Samplers utilising a hydrogel layer to control compound diffusion are gaining popularity. In this work we investigated diffusion of several perfluoroalkyl substances, currently used pesticides, pharmaceuticals and personal care products in 1.5% agarose hydrogel by measuring diffusion coefficients using two methods: a diffusion cell and a sheet stacking technique. Further, diffusion coefficients in water were measured using Taylor dispersion method. The sheet stacking method was used to measure D at 5, 12, 24, and 33 °C in order to investigate temperature effect on diffusion. Median D values ranged from 2.0 to 8.6 × 10-6 cm2 s-1 and from 2.1 to 8.5 × 10-6 cm2 s-1 for the diffusion cell and sheet stack methods respectively. For most compounds, the variability between replicates was higher than the difference between values obtained by the two methods. Rising temperature from 10 to 20 °C increases the diffusion rate by the factor of 1.41 ± 0.10 in average. In water, average D values ranged from 3.03 to 10.0 × 10-6 cm2 s-1 and were comparable to values in hydrogel, but some compounds including perfluoroalkyl substances with a long aliphatic chain could not be evaluated properly due to sorptive interactions with capillary walls in the Taylor dispersion method. Sampling rates estimated using the measured D values were systematically higher than values estimated from laboratory sampler calibration in our previously published study, by the factor of 2.2 ± 1.0 in average.


Assuntos
Monitoramento Ambiental/métodos , Sefarose/análise , Poluentes Químicos da Água/análise , Transporte Biológico , Cosméticos , Difusão , Monitoramento Ambiental/instrumentação , Hidrogéis , Cinética , Compostos Orgânicos , Praguicidas/análise , Temperatura , Água
7.
Crit Rev Anal Chem ; : 1-35, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31597440

RESUMO

We comprehensively review the current state-of-the-art of environmental monitoring for hydrophobic organic contaminants in aqueous matrices using passive sampling devices. Principles of the theory of passive sampling are presented. Strategies for passive sampler design and operation, limitations in performance and data quality-assurance and quality-control are reviewed. Advances in applications of available passive sampling devices are extensively critiqued. Future trends and current challenges facing practitioners and barriers to further adoption of the devices are discussed.

8.
Sci Total Environ ; 696: 133935, 2019 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-31442727

RESUMO

The Danube River is a large transboundary river with many tributaries. Pollution from industries, municipal wastewater and navigation is discharged into the river directly or via its tributaries. These discharges can adversely contribute to the water and sediment quality, posing a risk to aquatic life. Contaminants with low water solubility tend to accumulate in suspended solids, which deposit in riverbed sediments. Subsequently, their levels in sediment represent a time integrated sample indicating the pollution in the watercourse. However, total concentrations in sediment do not directly represent the exposure risk to aquatic life as accumulation in sediment heavily depends on its properties, i.e. the amount of organic material and its composition, which is difficult to characterize as any natural material. To provide contaminant concentrations on a defined basis, surface layer riverbed sediment samples collected at eleven locations along the Danube stretch in the territory of Serbia in 2012, were ex-situ (in the laboratory) equilibrated with silicone passive samplers of constant accumulative properties, using the multi-ratio equilibrium passive sampling approach. Contaminant's equilibrium concentrations in passive samplers are mutually comparable in time and space and are better measure for bioavailability than total sediment concentrations. Uptake in the passive sampler converted to equivalent freely dissolved (pore-) water concentrations agreed well with those obtained from surface water passive sampling carried out within the Joint Danube Survey 3 in 2013. Furthermore, equilibrium passive sampler PCB concentrations, converted to lipid-based concentrations, agreed well with concentrations measured in fish sampled in the Danube several years earlier. Out of eleven priority substances, only fluoranthene exceeded the EU EQS in water, while the EQS for biota was exceeded or approached for fluoranthene and benz[a]pyrene, and hexachlorobenzene.

9.
Environ Sci Pollut Res Int ; 26(15): 15273-15284, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30929173

RESUMO

Passive samplers based on diffusive gradients in thin hydrogel films (DGT) were recently modified for sampling of polar organic compounds in water. However, since the sampling rates of the commonly used DGT design with the surface area of 3.1 cm2 are low, we propose to increase them by applying a two-sided design with a larger sampling surface area of 22.7 cm2. The sampler design consists of two sorptive hydrogel disks compressed between two diffusive hydrogel disk layers strengthened by nylon netting and held together by two stainless steel rings. Sorbent/water distribution coefficients (KSW) were determined, and the sampler was calibrated for monitoring 11 perfluoroalkyl substances and 12 pharmaceuticals and personal care products in water at laboratory conditions using a closed system with artificial flow generated by submersible pumps. A field performance test was conducted at five locations in the Morava River basin in Czech Republic. The median value of laboratory-derived sampling rates was 43 mL day-1 with extreme values of 2 mL day-1 and 90 mL day-1 for perfluorotridecanoic and perfluoroheptanoic acids, respectively. The log KSW values of tested compounds ranged from 3.18 to 5.47 L kg-1, and the estimated halftime to attain sampler-water equilibrium ranged from 2 days to more than 28 days, which is the maximum recommended exposure period, considering potential issues with the stability of hydrogel. The sampler can be used for assessment of spatial trends as well as estimation of aqueous concentration of investigated polar compounds.


Assuntos
Fluorcarbonetos/química , Ácidos Heptanoicos/química , Hidrogéis/química , Compostos Orgânicos/química , Sefarose/química , Poluentes Químicos da Água/análise , República Tcheca , Difusão , Rios/química , Água
10.
Sci Total Environ ; 664: 424-435, 2019 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-30754010

RESUMO

We investigated a combination of approaches to extend the attainment of partition equilibria between silicone passive samplers (samplers) and surface or treated waste water towards more hydrophobic organic compounds (HOC). The aim was to identify the HOC hydrophobicity range for which silicone sampler equilibration in water is feasible within a reasonable sampler deployment period. Equilibrium partitioning of HOC between sampler and water is desirable for a simpler application as a "chemometer", aiming to compare chemical activity gradients across environmental media (e.g. water, sediment, biota). The tested approaches included a) long sampler exposure periods and high water flow to maximize mass transfer from water to sampler; b) the use of samplers with reduced sheet thicknesses; and c) pre-equilibration of samplers with local bottom sediment, followed by their exposure in surface water at the same sampling site. These approaches were tested at three sites including a fish pond with a low level of pollution, a river impacted by an urban agglomeration and an effluent of municipal wastewater treatment plant. Tested compounds included polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), DDT, its metabolites and their isomers, hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDE). The study shows that samplers with a surface area of 400-800 cm2 consisting of thin (100-500 µm) silicone sheets exposed at sampling rates of 10-40 L d-1 for a time period of up to four months reach partition equilibrium with water for compounds with log Kow ≤ 5.5. Nevertheless, for compounds beyond this limit it is challenging, within a reasonable time period, to reach equilibrium between sampler and water in an open system where water boundary layer resistance controls the mass transfer. For more hydrophobic HOC (log Kow > 6), the kinetic method using performance reference compounds is recommended instead.

11.
Sci Total Environ ; 650(Pt 1): 1599-1612, 2019 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-30308846

RESUMO

Complex mixtures of contaminants from multiple sources, including agriculture, industry or wastewater enter aquatic environments and might pose hazards or risks to humans or wildlife. Targeted analyses of a few priority substances provide limited information about water quality. In this study, a combined chemical and effect screening of water quality in the River Bosna, in Bosnia and Herzegovina was carried out, with focus on occurrence and effects of contaminants of emerging concern. Chemicals in water were sampled at 10 sites along the Bosna River by use of passive sampling. The combination of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS) enabled sampling of a broad range of contaminants from hydrophobic (PAHs, PCBs, OCPs) to hydrophilic compounds (pesticides, pharmaceuticals and hormones), which were determined by use of GC-MS and LC-MS (MS). In vitro, cell-based bioassays were applied to assess (anti)androgenic, estrogenic and dioxin-like potencies of extracts of the samplers. Of a total of 168 targeted compounds, 107 were detected at least once. Cumulative pollutant concentrations decreased downstream from the city of Sarajevo, which was identified as the major source of organic pollutants in the area. Responses in all bioassays were observed for samples from all sites. In general, estrogenicity could be well explained by analysis of target estrogens, while the drivers of the other observed effects remained largely unknown. Profiling of hazard quotients identified two sites downstream of Sarajevo as hotspots of biological potency. Risk assessment of detected compounds revealed, that 7 compounds (diazinon, diclofenac, 17ß-estradiol, estrone, benzo[k]fluoranthene, fluoranthene and benzo[k]fluoranthene) might pose risks to aquatic biota in the Bosna River. The study brings unique results of a complex water quality assessment in a region with an insufficient water treatment infrastructure.


Assuntos
Monitoramento Ambiental , Rios/química , Poluentes Químicos da Água/análise , Bioensaio , Bósnia e Herzegóvina , Dioxinas/análise , Disruptores Endócrinos/análise , Estrogênios/análise , Compostos Orgânicos/análise , Praguicidas/análise , Bifenilos Policlorados/análise , Dibenzodioxinas Policloradas/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Águas Residuárias
12.
Chemosphere ; 211: 1193-1202, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30223335

RESUMO

The aim of the present study was to investigate the presence and bioaccumulation of new flame retardants (nBFRs), polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DDC-CO) in the marine environment close to an Arctic community. Passive sampling of air and water and grab sampling of sediment and amphipods was used to obtain samples to study long-range transport versus local contributions for regulated and emerging flame retardants in Longyearbyen, Svalbard. BDE-47 and -99, α- and ß-tetrabromoethylcyclohexane (DBE-DBCH), syn- and anti-dechlorane plus (DDC-CO) were detected in all investigated matrices and the DDC-COss at higher concentrations in the air than reported from other remote Arctic areas. Water concentrations of ΣDDC-COSs were low (3 pg/L) and comparable to recent Arctic studies. ΣnBFR was 37 pg/L in the water samples while ΣPBDE was 3 pg/L. In biota, ΣDDC-COSs dominated (218 pg/g ww) followed by ΣnBFR (95 pg/g ww) and ΣPBDEs (45 pg/g ww). When compared with other areas and their relative distribution patterns, contributions from local sources of the analysed compounds cannot be ruled out. This should be taken into account when assessing long-range transport of nBFRs and DDC-COs to the Arctic. High concentrations of PBDEs in the sediment indicate that they might originate from a small, local source, while the results for some of the more volatile compounds such as hexabromobenzene (HBBz) suggest long-range transport to be more important than local sources. We recommend that local sources of flame retardants in remote areas receive more attention in the future.


Assuntos
Retardadores de Chama/análise , Éteres Difenil Halogenados/análise , Hidrocarbonetos Clorados/análise , Compostos Policíclicos/análise , Anfípodes , Animais , Regiões Árticas , Bromobenzenos/análise , Monitoramento Ambiental/métodos , Svalbard
13.
Sci Total Environ ; 636: 1597-1607, 2018 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-29606316

RESUMO

A "dynamic" passive sampling (DPS) device, consisting of an electrically driven large volume water pumping device coupled to a passive sampler exposure cell, was designed to enhance the sampling rate of trace organic compounds. The purpose of enhancing the sampling rate was to achieve sufficient method sensitivity, when the period available for sampling is limited to a few days. Because the uptake principle in the DPS remains the same as for conventionally-deployed passive samplers, free dissolved concentrations can be derived from the compound uptake using available passive sampler calibration parameters. This was confirmed by good agreement between aqueous concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) derived from DPS and conventional caged passive sampler. The DPS device enhanced sampling rates of compounds that are accumulated in samplers under water boundary layer control (WBL) more than five times compared with the conventionally deployed samplers. The DPS device was deployed from a ship cruising downstream the Danube River to provide temporally and spatially integrated concentrations. A DPS-deployed sampler with surface area of 400cm2 can reach sampling rates up to 83Ld-1. The comparison of three passive samplers made of different sorbents and co-deployed in the DPS device, namely silicone rubber (SR), low density polyethylene (LDPE) and SDB-RPS Empore™ disks showed a good correlation of surface specific uptake for compounds that were sampled integratively during the entire exposure period. This provided a good basis for a cross-calibration between the samplers. The good correlation of free dissolved PAHs, PCBs and HCB concentration estimates obtained using SR and LDPE confirmed that both samplers are suitable for the identification of concentration gradients and trends in the water column. We showed that the differences in calculated aqueous concentrations between sampler types are mainly associated with different applied uptake models.


Assuntos
Monitoramento Ambiental/instrumentação , Poluentes Químicos da Água/análise , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Rios/química
14.
Sci Total Environ ; 636: 1608-1619, 2018 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-29530537

RESUMO

Many aquatic pollutants can be present at low concentrations, but their mixtures can still affect health or behavior of exposed organisms. In this study, toxicological and chemical analyses were combined for spatial contamination profiling using an innovative passive sampling approach. A novel Dynamic Passive Sampler (DPS) was employed as a mobile sampler from a ship cruising along 2130km of the Danube river during the Joint Danube Survey 3 (JDS3). The sampling was performed in eight subsequent river stretches with two types of complementary passive samplers: silicone rubber sheets (SR) used for non-polar chemicals and SDB-RPS Empore™ disks (ED) for more hydrophilic compounds. Besides extensive chemical analyses, the bioactivity of samples was characterized by a battery of reporter gene bioassays. Cross-calibration of the employed passive samplers enabled robust estimation of water concentrations applicable for compounds with a wide range of physicochemical properties. DPS was suitable for sampling of water contaminants even at pgL-1 levels, with 209 of 267 analyzed compounds detected in the samples. Biological effects were detected in both ED and SR extracts across all river stretches by bioassays focused on xenobiotic metabolism mediated by the aryl hydrocarbon and pregnane X receptors, endocrine disruptive potential mediated by estrogen and androgen receptors and the oxidative stress response. The bioassay responses expressed as bioanalytical equivalent concentrations (BEQbio) were comparable with data obtained from large volume active sampling. The extracts of the ED samplers were more biologically active than extracts of SR samplers. Except of estrogenicity, where the analyzed chemicals explained on average 62% of the effects in ED samples, the detected chemicals explained <8% of BEQbio values. The study shows the utility of the combination of the innovative passive sampling approach with effect-based tools for efficient and fast monitoring even in water bodies with relatively low levels of contamination.


Assuntos
Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise , Bioensaio , Monitoramento Ambiental/instrumentação , Estrogênios , Rios/química
15.
Environ Sci Pollut Res Int ; 24(35): 27334-27344, 2017 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-28971343

RESUMO

The freely dissolved concentration of persistent organic pollutants (POPs) is one of the most important parameters for risk assessment in aquatic environments, due to its proportionality to the chemical activity. Chemical activity difference represents the driving force for a spontaneous contaminant transport, such as water-aquatic biota or water-sediment. Freely dissolved concentrations in sediment pore water can be estimated from the concentrations in a partition-based passive sampler equilibrated in suspensions of contaminated sediment. Equilibration in the sediment/passive sampler system is slow, since concentrations of most POPs in the water phase, which is the main route for mass transfer, are very low. Adding methanol to sediment in suspension increases the POPs' solubility and, consequently, the permeability in the water phase. The resulting higher aqueous concentrations enhance POPs mass transfer up to three times for investigated POPs (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides) and shorten equilibrium attainment to less than 6 weeks. The addition of methanol to the aqueous phase up to a molar fraction of 0.2 changed the POPs equilibrium distribution ratio between sediment and passive sampler by less than a factor of two. As a result, the pore water concentrations of POPs, calculated from their amounts accumulated in a passive sampler, are affected by methanol addition not more than by the same factor.


Assuntos
Monitoramento Ambiental/métodos , Sedimentos Geológicos/análise , Praguicidas/análise , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Poluentes Químicos da Água/análise , Hidrocarbonetos Clorados/análise , Metanol/química , Solubilidade
16.
Environ Sci Pollut Res Int ; 24(32): 25061-25070, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-28920186

RESUMO

2-Ethylhexyl methoxycinnamate (EHMC) is one of the most used ultraviolet filters in personal care products. It undergoes cis/trans isomerization in sunlight, and there is limited toxicological understanding of the effects of the cis-isomer. It is known that two geometric isomers of one compound can have different physico-chemical properties and effects. However, there are no studies focusing on toxicokinetics of EHMC isomerization products to compare their potential difference in dermal exposure to cis-EHMC and trans-EHMC due to the difference in their dermatotoxicokinetics. In this study, dermal absorption of the parental trans-EHMC and its cis isomer was studied. A commercially available sunscreen lotion containing trans-EHMC and spiked with laboratory-prepared cis-EHMC was locally applied on the forearm skin of two volunteers. After 8 h of skin exposure, the stratum corneum (SC) layer was removed by tape stripping. The removed thickness of the SC was determined spectrophotometrically using a total protein assay. The concentration of both isomers in the removed SC was measured by HPLC-DAD. A new diffusion and permeability coefficient of both EHMC isomers in SC were determined by Fick's second law of diffusion in vivo. The difference in dermatotoxicokinetic parameters between the two isomers was not statistically significant. However, separate toxicological studies of isomeric forms and the determination of their dermatotoxicokinetic parameters are crucial for refinement of human risk assessment.


Assuntos
Cinamatos/farmacocinética , Epiderme/metabolismo , Absorção Cutânea , Protetores Solares/farmacocinética , Adulto , Cinamatos/química , Feminino , Humanos , Estereoisomerismo , Protetores Solares/química , Toxicocinética
17.
Environ Sci Technol ; 51(19): 11250-11257, 2017 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-28901764

RESUMO

Passive sampling is widely used to measure levels of contaminants in various environmental matrices, including fish tissue. Equilibrium passive sampling (EPS) of persistent organic pollutants (POP) in fish tissue has been hitherto limited to application in lipid-rich tissue. We tested several exposure methods to extend EPS applicability to lean tissue. Thin-film polydimethylsiloxane (PDMS) passive samplers were exposed statically to intact fillet and fish homogenate and dynamically by rolling with cut fillet cubes. The release of performance reference compounds (PRC) dosed to passive samplers prior to exposure was used to monitor the exchange process. The sampler-tissue exchange was isotropic, and PRC were shown to be good indicators of sampler-tissue equilibration status. The dynamic exposures demonstrated equilibrium attainment in less than 2 days for all three tested fish species, including lean fish containing 1% lipid. Lipid-based concentrations derived from EPS were in good agreement with lipid-normalized concentrations obtained using conventional solvent extraction. The developed in-tissue EPS method is robust and has potential for application in chemical monitoring of biota and bioaccumulation studies.


Assuntos
Peixes , Lipídeos , Poluentes Químicos da Água , Animais , Monitoramento Ambiental , Controle de Qualidade
18.
Sci Total Environ ; 576: 720-737, 2017 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-27810758

RESUMO

Water is a vital resource for natural ecosystems and human life, and assuring a high quality of water and protecting it from chemical contamination is a major societal goal in the European Union. The Water Framework Directive (WFD) and its daughter directives are the major body of legislation for the protection and sustainable use of European freshwater resources. The practical implementation of the WFD with regard to chemical pollution has faced some challenges. In support of the upcoming WFD review in 2019 the research project SOLUTIONS and the European monitoring network NORMAN has analyzed these challenges, evaluated the state-of-the-art of the science and suggested possible solutions. We give 10 recommendations to improve monitoring and to strengthen comprehensive prioritization, to foster consistent assessment and to support solution-oriented management of surface waters. The integration of effect-based tools, the application of passive sampling for bioaccumulative chemicals and an integrated strategy for prioritization of contaminants, accounting for knowledge gaps, are seen as important approaches to advance monitoring. Including all relevant chemical contaminants in more holistic "chemical status" assessment, using effect-based trigger values to address priority mixtures of chemicals, to better consider historical burdens accumulated in sediments and to use models to fill data gaps are recommended for a consistent assessment of contamination. Solution-oriented management should apply a tiered approach in investigative monitoring to identify toxicity drivers, strengthen consistent legislative frameworks and apply solutions-oriented approaches that explore risk reduction scenarios before and along with risk assessment.

19.
Talanta ; 161: 405-412, 2016 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-27769425

RESUMO

In situ extraction of steroid hormones from waste water using adsorption-based integrative passive samplers represents a promising approach for their monitoring in water at ultra-trace concentrations. Three passive samplers, namely a POCIS, a Chemcatcher fitted with an Empore SDB-RPS disk, and an Empore SDB-RPS disk-based sampler with enhanced water flow, were calibrated in situ in treated municipal wastewater for the purpose of monitoring five estrogens (17-ß-estradiol, 17-α-estradiol, 17-α-ethinylestradiol, estrone and estriol) at sub ng per litre concentrations. Uptake of steroids to samplers during 14-day exposure in wastewater was compared with steroid concentrations in daily collected composite water samples. Sampling rates were obtained from a numerical solution of first order uptake kinetics equations describing the uptake of compounds into a passive sampler over time. Mass transfer of steroids in the Chemcatcher fitted with naked Empore disks was more than two times faster than in the POCIS sampler. The uptake capacity of the applied Empore disk was not sufficient for integrative uptake of all tested steroids during the entire 14-day exposure. Time-weighted average concentrations of steroids estimated at concentrations in units of ngL-1 using the in situ-calibrated samplers were within a factor of two from values obtained using composite water samples.


Assuntos
Monitoramento Ambiental/instrumentação , Congêneres do Estradiol/análise , Estrogênios/análise , Águas Residuárias/análise , Poluentes Químicos da Água/análise , Calibragem
20.
Chemosphere ; 151: 225-33, 2016 May.
Artigo em Inglês | MEDLINE | ID: mdl-26945239

RESUMO

Two groups of perfluorined compounds (PFCs), i.e. perfluoroalkyl sulfonates (PFASs) and perfluoroalkyl carboxylates (PFCAs) were analysed during a period of 1 year in monthly collected riverbed sediment samples from five sampling sites in an industrial region in Morava River catchment in Czech Republic. Levels of PFCs determined in sediment samples were up to 6.8 µg kg(-1) of dry weight. Among PFCs analysed, mainly short-chain PFASs (C6 to C8) including PFOS were found in sediment samples and their levels were similar to those found in comparable river basins in other parts of Europe. Concentrations of PFCs were correlated with organic carbon content and their variations were mainly correlated by high flow events on Morava River and its tributaries. The changes in PFC concentrations were induced by displacing of PFCs containing particles to the river sediment during these elevated flow events.


Assuntos
Monitoramento Ambiental , Fluorcarbonetos/análise , Sedimentos Geológicos/química , Rios/química , Poluentes Químicos da Água/análise , República Tcheca
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