We report the levels of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in seawater and air, and the air-sea dynamics through diffusive exchange analysis in Fildes Bay, King George Island, Antarctica, between November 2019 and January 30, 2020. Hexachlorobenzene (HCB) was the most abundant compound in both air and seawater with concentrations around 39 ± 2.1 pg m-3 and 3.2 ± 2.4 pg L-1 respectively. The most abundant PCB congener was PCB 11, with a mean of 3.16 ± 3.7 pg m-3 in air and 2.0 ± 1.1 pg L-1 in seawater. The fugacity gradient estimated for the OCP compounds indicate a predominance of net atmospheric deposition for HCB, α-HCH, γ-HCH, 4,4'-DDT, 4,4'-DDE and close to equilibrium for the PeCB compound. The observed deposition of some OCs may be driven by high biodegradation rates and/or settling fluxes decreasing the concentration of these compounds in surface waters, which is supported by the capacity of microbial consortium to degrade some of these compounds. The estimated fugacity gradients for PCBs showed differences between congeners, with net volatilization predominating for PCB-9, a trend close to equilibrium for PCB congeners 11, 28, 52, 101, 118, 138, and 153, and deposition for PCB 180. Snow amplification may play an important role for less hydrophobic PCBs, with volatilization predominating after snow/glacier melting. As hydrophobicity increases, the biological pump decreases the concentration of PCBs in seawater, reversing the fugacity gradient to atmospheric deposition. This study highlights the potential impacts of climate change, through glacier retreat, on the biogeochemistry of POPs, remobilizing those compounds previously trapped within the cryosphere which in turn will transform the Antarctic cryosphere into a secondary source of the more volatile POPs in coastal areas, influenced by snow and ice melting.
- Klíčová slova
- Antarctica, Biodegradation, Human impacts, Legacy, POPs, Snow amplification,
- MeSH
- chlorované uhlovodíky * analýza MeSH
- hexachlorbenzen analýza MeSH
- látky znečišťující vzduch * analýza MeSH
- monitorování životního prostředí MeSH
- mořská voda MeSH
- pesticidy * analýza MeSH
- polychlorované bifenyly * analýza MeSH
- zátoky MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Antarktida MeSH
- Názvy látek
- chlorované uhlovodíky * MeSH
- hexachlorbenzen MeSH
- látky znečišťující vzduch * MeSH
- pesticidy * MeSH
- polychlorované bifenyly * MeSH
Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.
- Klíčová slova
- cyclodiene pesticides, global fractionation, hexachlorobenzene, hexachlorocyclohexanes, long-range transport, organochlorine pesticides, passive sampler, polychlorinated biphenyls, silicone rubber,
- MeSH
- chlorované uhlovodíky * analýza MeSH
- hexachlorbenzen analýza MeSH
- látky znečišťující vzduch * analýza MeSH
- látky znečišťující životní prostředí * MeSH
- monitorování životního prostředí metody MeSH
- pesticidy * analýza MeSH
- polychlorované bifenyly * analýza MeSH
- sladká voda MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- chlorované uhlovodíky * MeSH
- hexachlorbenzen MeSH
- látky znečišťující vzduch * MeSH
- látky znečišťující životní prostředí * MeSH
- pesticidy * MeSH
- polychlorované bifenyly * MeSH
The species of Comamonas testosteroni is the most common human pathogen of the genus, which can be associated with acute appendicitis, infections of the bloodstream, the peritoneal cavity, cerebrospinal fluid, inflammatory bowel disease, and in general, bacteremia. According to the literature, Comamonas testosteroni has destructive activity to a wide range of toxic chemical compounds, including chlorobenzenes. The specified strains were isolated from the soil of the organochlorine waste landfill, where hexachlorobenzene (HCB) was predominant. These strains were expected to be capable of degrading HCB. Microbiological (bacterial enrichment and cultivating, bacterial biomass obtaining), molecular biology, biochemical (enzymatic activities, malondialdehyde measuring, peroxidation lipid products measuring), and statistical methods were carried out in this research. The reaction of both strains (UCM B-400 and UCM B-401) to the hexachlorobenzene presence differed in the content of diene and triene conjugates and malondialdehyde, as well as different catalase and peroxidase activity levels. In terms of primary peroxidation products, diene conjugates were lower, except conditions with 20 mg/L HCB, where these were higher up to two times, than the pure control. Malondialdehyde in strain B-400 cells decreased up to five times, in B-401, but increased up to two times, compared to the pure control. Schiff bases in strain B-400 cells were 2-3 times lower than the pure control. However, in B-401 cells Schiff bases under higher HCB dose were in the same level with the pure control. Catalase activity was 1.5 times higher in all experimental variants, compared to the pure control (in the strain B-401 cells), but in the B-400 strain, cells were 2 times lower, compared to the pure control. The response of the two strains to hexachlorobenzene was similar only in peroxidase activity terms, which was slightly higher compared to the pure control. The physiological response of Comamonas testosteroni strains to hexachlorobenzene has a typical strain reaction. The physiological response level of these strains to hexachlorobenzene confirms its tolerance, and indirectly, the ability to destroy the specified toxic compound.
- Klíčová slova
- Schiff bases, catalase, diene and triene conjugates, hexachlorobenzene, malondialdehyde, peroxidase,
- MeSH
- antioxidancia MeSH
- chlorbenzeny MeSH
- Comamonas testosteroni * MeSH
- hexachlorbenzen * MeSH
- katalasa MeSH
- lidé MeSH
- lipidy MeSH
- malondialdehyd MeSH
- peroxidace lipidů MeSH
- půda MeSH
- Schiffovy báze MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- antioxidancia MeSH
- chlorbenzeny MeSH
- hexachlorbenzen * MeSH
- katalasa MeSH
- lipidy MeSH
- malondialdehyd MeSH
- půda MeSH
- Schiffovy báze MeSH
Hexachlorobenzene (HCB), listed on the Stockholm Convention on persistent organic pollutants and regulated as a hazardous priority pollutant by the Water Framework Directive (WFD), is ubiquitously distributed in the environment and assumed to mildly biomagnify in aquatic foodwebs. The proposal to include trophic magnification factors (TMFs) in the procedure for comparing contaminant levels in biota at different trophic levels (TLs) with WFD environmental quality standards requires adequate selection of TMFs. In the first step of our study, we compared two independently obtained datasets of pentachlorobenzene (PeCB) and HCB concentration ratios from passive sampling (PS) in water and in fish through routine monitoring programs in Norway to evaluate possible biomagnification. In this procedure, PeCB is used for benchmarking the bioconcentration in fish, and the observed HCB/PeCB ratios in fish are compared with ratios expected in the case of (i) HCB bioconcentration or (ii) biomagnification using published TMF values. Results demonstrate that it is not possible to confirm that HCB biomagnifies in fish species that would be used for WFD monitoring in Norway and challenges the proposed monitoring procedures for such compounds in Norwegian or European waters. In the second step, fish-water chemical activity ratios for HCB and PeCB as well as for polychlorinated biphenyls where biota and PS were conducted alongside were calculated and found to rarely exceed unity for cod (Gadus morhua), a fish species with a TL of approximately 4.
- Klíčová slova
- biota, fish, hexachlorobenzene, passive sampling, polychlorinated biphenyls, water framework directive,
- MeSH
- bioakumulace MeSH
- chemické látky znečišťující vodu * analýza MeSH
- hexachlorbenzen analýza MeSH
- monitorování životního prostředí metody MeSH
- polychlorované bifenyly * analýza MeSH
- potravní řetězec MeSH
- ryby MeSH
- voda MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- chemické látky znečišťující vodu * MeSH
- hexachlorbenzen MeSH
- polychlorované bifenyly * MeSH
- voda MeSH
Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are ubiquitous and toxic contaminants. Their atmospheric deposition fluxes on the regional scale were quantified based on simultaneous sampling during 1 to 5 years at 1 to 6 background/rural sites in the Czech Republic and Austria. The samples were extracted and analysed by means of gas chromatography coupled to mass spectrometry. For all seasons and sites, total deposition fluxes for Σ15PAHs ranged 23-1100 ng m-2 d-1, while those for Σ6PCBs and Σ12OCPs ranged 64-4400 and 410-7800 pg m-2 d-1, respectively. Fluoranthene and pyrene were the main contributors to the PAH deposition fluxes, accounting on average for 19% each, while deposition fluxes of PCBs and OCPs were dominated by PCB153 (26%) and γ-hexachlorobenzene (30%), respectively. The highest deposition flux of Σ15PAHs was generally found in spring, while no seasonality was found for PCB deposition. For deposition fluxes for Σ12OCPs, no clear spatial trend was found, confirming the perception of long-lived regional pollutants. Although most OCPs and PCBs hardly partition to the particulate phase in ambient air, on average, 42% of their deposition fluxes were found on filters, confirming the perception that particle deposition is more efficient than dry gaseous deposition. Due to methodological constraints, fluxes derived from bulk deposition samplers should be understood as lower estimates, in particular with regard to those substances which in ambient aerosols mostly partition to the particulate phase.
- Klíčová slova
- Bulk atmospheric deposition, Central Europe, Deposition fluxes, OCPs, PAHs, PCBs, POPs,
- MeSH
- chlorované uhlovodíky analýza MeSH
- hexachlorbenzen analýza MeSH
- látky znečišťující vzduch analýza MeSH
- monitorování životního prostředí * MeSH
- pesticidy analýza MeSH
- plynová chromatografie s hmotnostně spektrometrickou detekcí MeSH
- polychlorované bifenyly analýza MeSH
- polycyklické aromatické uhlovodíky analýza MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
- Evropa MeSH
- Rakousko MeSH
- Názvy látek
- chlorované uhlovodíky MeSH
- hexachlorbenzen MeSH
- látky znečišťující vzduch MeSH
- pesticidy MeSH
- polychlorované bifenyly MeSH
- polycyklické aromatické uhlovodíky MeSH
Chlorophenols (CPs), including pentachlorophenol (PCP), are chemicals of concern due to their toxicity and persistence. Here we describe a successful reactor-based remediation of CP-contaminated soil and assess changes in the toxicity patterns and bacterial communities during the remediation. The remediation consisted of separating half of the contaminated soil to be ground (samples M) in order to test whether the grinding expedited the remediation, the other half was left unground (samples P). Both soils were mixed with wastewater treatment sludge to increase their bacterial diversity and facilitate the degradation of CPs, and the resultant mixtures were placed in 2 bioreactors, M and P, operated for 16 months under anaerobic conditions to favor dehalogenation and for an additional 16 months under aerobic conditions to achieve complete mineralization. Samples were taken every 4 months for toxicity and microbial analyses. The results showed a 64% removal of total CPs (ΣCPs) in reactor P after just 18 months of remediation, whereas similar depletion in reactor M occurred after ∼25 months, indicating that the grinding decelerated the remediation. By the end of the experiment, both reactors achieved 93.5-95% removal. The toxicity tests showed a decrease in toxicity as the remediation progressed. The succession of bacterial communities over time was significantly associated with pH, anaerobic/aerobic phase and the concentration of the majority of CP congeners. Our data indicate that the supplementation of contaminated soil with sludge and further incubation in pilot-scale bioreactors under consecutive anaerobic-aerobic conditions proved to be effective at the remediation of CP-contaminated soil.
- Klíčová slova
- 16S rRNA gene, Bioreactors, Chlorophenols, Microbial communities, Pentachlorophenol, Remediation,
- MeSH
- aerobióza MeSH
- anaerobióza MeSH
- biodegradace MeSH
- bioreaktory mikrobiologie MeSH
- chlorfenoly analýza MeSH
- látky znečišťující půdu analýza MeSH
- odpadní vody mikrobiologie MeSH
- pentachlorfenol analýza MeSH
- pilotní projekty MeSH
- půda chemie MeSH
- půdní mikrobiologie * MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- chlorfenoly MeSH
- látky znečišťující půdu MeSH
- odpadní vody MeSH
- pentachlorfenol MeSH
- půda MeSH
To further support implementation of monitoring by passive sampling, robust sampler-water partition coefficients (Kpw) are required to convert data from passive sampler into aqueous phase concentrations. In this work silicone-water partition coefficients were determined for ∼80 hydrophobic organic contaminants using the cosolvent method. Partition coefficients (Kpm) were measured in pure water and water-methanol mixtures up to a methanol mole fraction of 0.3 (50% v/v). Subsequently, logKpw in pure water was determined as the intercept of linear regression of the logKpm with the corresponding methanol mole fractions. LogKpw were determined for phthalates, musks, organo phosphorus flame-retardants, chlorobenzenes, pesticides, some PCBs and a number of miscellaneous compounds. The median standard error and 95% confidence interval of the measured logKpw was 0.06 and 0.13, respectively. The overall relationship between Kpw and Kow seems insufficient to predict Kpw for unknown compounds. Prediction may work within a group of compounds with similar nature, e.g. homologues but HCH isomers having the same Kow exhibit Kpw ranging over an order of magnitude. Long alkyl-chain phthalates and tris(2-ethylhexyl) phosphate; all having a molecular volume >400 Å3, deviated the most from the Kpw-Kow relationship.
- Klíčová slova
- Cosolvent, Hydrophobic organic compounds, Passive sampling, Silicone–water partition coefficient,
- MeSH
- chemické látky znečišťující vodu chemie MeSH
- chlorbenzeny chemie MeSH
- fosfáty chemie MeSH
- kyseliny ftalové chemie MeSH
- kyseliny mastné mononenasycené MeSH
- pesticidy chemie MeSH
- polychlorované bifenyly chemie MeSH
- retardanty hoření MeSH
- silikony chemie MeSH
- voda chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- chemické látky znečišťující vodu MeSH
- chlorbenzeny MeSH
- fosfáty MeSH
- kyseliny ftalové MeSH
- kyseliny mastné mononenasycené MeSH
- musk MeSH Prohlížeč
- pesticidy MeSH
- phthalic acid MeSH Prohlížeč
- polychlorované bifenyly MeSH
- retardanty hoření MeSH
- silikony MeSH
- voda MeSH
Based on the presence of carbamate moiety, twenty salicylanilide N-monosubstituted carbamates concomitantly with their parent salicylanilides and five newly prepared 4-chlorophenyl carbamates obtained from isocyanates were investigated using Ellman's method for their in vitro inhibitory activity against acetylcholinesterase (AChE) from electric eel and butyrylcholinesterase (BChE) from equine serum. The carbamates and salicylanilides exhibited mostly a moderate inhibition of both cholinesterase enzymes with IC50 values ranging from 5 to 235 µM. IC50 values for AChE were in a narrower concentration range when compared to BChE, but many of the compounds produced a balanced inhibition of both cholinesterases. The derivatives were comparable or superior to rivastigmine for AChE inhibition, but only a few of carbamates also for BChE. Several structure-activity relationships were identified, e.g., N-phenethylcarbamates produce clearly favourable BChE inhibition. The compounds also share convenient physicochemical properties for CNS penetration.
- Klíčová slova
- Acetylcholinesterase, Butyrylcholinesterase, Carbamate, Enzyme inhibition, In vitro inhibition, Salicylanilide,
- MeSH
- acetylcholinesterasa metabolismus MeSH
- butyrylcholinesterasa metabolismus MeSH
- chlorfenoly chemie farmakologie MeSH
- cholinesterasové inhibitory chemie farmakologie MeSH
- Electrophorus MeSH
- inhibiční koncentrace 50 MeSH
- karbamáty chemie farmakologie MeSH
- koně MeSH
- salicylanilidy chemie farmakologie MeSH
- vztahy mezi strukturou a aktivitou MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- 4-chlorophenol MeSH Prohlížeč
- acetylcholinesterasa MeSH
- butyrylcholinesterasa MeSH
- chlorfenoly MeSH
- cholinesterasové inhibitory MeSH
- karbamáty MeSH
- salicylanilidy MeSH
Electrophoretic focusing on inverse electromigration dispersion (EMD) gradient is a new analytical technique based on a unique separation principle where weak non-amphoteric ionogenic species are focused, separated and transported to the detector by an EMD profile of suitable properties. The present work extends the theoretical description of this method by introducing the concept of resolution and deriving the fundamental equation expressing resolution as function of basic system parameters. The results indicate that at constant current operation, resolution is proportional to the square root of time. For variable current regimes (e.g. constant voltage), the time variable is replaced by the product of electric current and passed electric charge. Computer simulations for a model pair of substances support the validity of the presented theory and confirm the theoretical conclusion that resolution can be increased by allowing longer electromigration of the gradient in terms of time or passed charge. The experimental example shown comprises an anionic electrolyte system based on maleic acid and 2,6-lutidine, combined with ESI-MS detection and operated in the reverse mode due to strong electroosmotic flow and ESI suction. The practical implementation of the proposed methodology is done by application of negative pressure at the inlet vial, resulting in very substantial resolution enhancement and baseline separation of otherwise unresolved substances. The performance and high sensitivity of the developed technique is demonstrated on the example of simultaneous analysis of four sulfonamides and three dichlorophenols in waters with limits of detection on the 1 nM level.
- Klíčová slova
- Capillary electrophoresis, Chlorophenols, Focusing, Resolution, Sulfonamides, Water analysis,
- MeSH
- chlorfenoly analýza MeSH
- elektroforéza kapilární MeSH
- elektrolyty chemie MeSH
- hmotnostní spektrometrie s elektrosprejovou ionizací * MeSH
- limita detekce MeSH
- maleáty chemie MeSH
- pitná voda analýza MeSH
- pyridiny chemie MeSH
- sulfonamidy analýza MeSH
- tlak MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- 2,6-lutidine MeSH Prohlížeč
- chlorfenoly MeSH
- elektrolyty MeSH
- maleáty MeSH
- maleic acid MeSH Prohlížeč
- pitná voda MeSH
- pyridiny MeSH
- sulfonamidy MeSH
Toxicity of mine dump effluent containing five hexachlorocyclohexane (α, β, γ, δ and ε-HCH, sum 159.4 μg/L) and two trichlorobenzene (TCB, sum 65.2 μg/L) isomers to two microalgae (Scenedesmus quadricauda and Coccomyxa subellipsoidea) was studied over 24 h exposure and also with 2- and 10-fold diluted stock solution (i.e. 1×, 0.5× and 0.1× strength). Individual isomers revealed rather dose-dependent accumulation typically higher in Scenedesmus than in Coccomyxa (max. sum of HCH 14.99 μg/g DW with bioaccumulation factor 94) and δ-HCH was dominant isomer. TCB isomers showed low accumulation in algae. 0.1× dose elevated chlorophylls and carotenoids in Coccomyxa while enzymatic activities (SOD, CAT, and APX), thiols (glutathione and phytochelatin 2) and ascorbic acid were rather elevated by 1× dose in both species. Malic acid, rather than citric acid, increased in response to 0.5× and 1× concentration. Sum of fatty acids was higher in Coccomyxa than in Scenedesmus with palmitic, oleic, linoleic and α-linolenic acids being dominant compounds in both species. Detailed profiling revealed that saturated and monounsaturated fatty acids increased in Coccomyxa while polyunsaturated fatty acids in Scenedesmus in response to increasing dose of organochlorines. Accumulation of organochlorines and metabolic responses in algae are reported here for the first time.
- Klíčová slova
- Algae, Antioxidants, Gas chromatography, Organic pollutants, Organochlorines,
- MeSH
- chemické látky znečišťující vodu toxicita MeSH
- chlorbenzeny toxicita MeSH
- Chlorophyta účinky léků metabolismus MeSH
- hexachlorcyklohexan toxicita MeSH
- hornictví MeSH
- mastné kyseliny metabolismus MeSH
- mikrořasy účinky léků metabolismus MeSH
- průmyslový odpad MeSH
- sulfhydrylové sloučeniny metabolismus MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- chemické látky znečišťující vodu MeSH
- chlorbenzeny MeSH
- hexachlorcyklohexan MeSH
- mastné kyseliny MeSH
- průmyslový odpad MeSH
- sulfhydrylové sloučeniny MeSH
- trichlorobenzene MeSH Prohlížeč