Nontarget Screening of Organohalogen Compounds in the Liver of Wild Birds from Osaka, Japan: Specific Accumulation of Highly Chlorinated POP Homologues in Raptors.

Nontarget screening studies have recently revealed the accumulation of typically unmonitored organohalogen compounds (OHCs) in various marine animals, but information for terrestrial food chains is still lacking. This study investigated the accumulation profiles of known and unknown OHCs in the liver of representative wild bird specimens from Osaka, Japan using nontarget analysis based on two-dimensional gas chromatography-time-of-flight mass spectrometry. A large number of unmonitored OHCs were identified, including anthropogenic contaminants and marine halogenated natural products (HNPs), and their accumulation profiles were considered to be influenced by terrestrial and brackish water-based diets. Anthropogenic OHCs were highly accumulated in terrestrial predator species (peregrine falcon, hawks, and black kite), and some unmonitored highly chlorinated contaminants reached the levels of microgram per gram lipid in the liver, i.e., C10-/C15-based chlordane related compounds (CHLs) and their epoxides, dichlorodiphenyldichloroethylene (DDE) homologues, and polychlorinated terphenyls (PCTs). In contrast, HNPs were accumulated at higher levels in piscivorous birds (gray heron and common cormorant). Considering the enrichment of the unmonitored C10-/C15-based CHLs, PCTs, and DDE homologues relative to structurally similar persistent organic pollutants (POPs) in high trophic-level species such as raptors, further studies are needed to elucidate their environmental levels, behavior in terrestrial food chains, and ecotoxicological impacts.

Marine and Anthropogenic Bromopyrroles Alter Cellular Ca2+ Dynamics of Murine Cortical Neuronal Networks by Targeting the Ryanodine Receptor and Sarco/Endoplasmic Reticulum Ca2+-ATPase.

Bromopyrroles (BrPyr) are synthesized naturally by marine sponge symbionts and produced anthropogenically as byproducts of wastewater treatment. BrPyr interact with ryanodine receptors (RYRs) and sarco/endoplasmic reticulum (SR/ER) Ca2+-ATPase (SERCA). Influences of BrPyr on the neuronal network activity remain uncharted. BrPyr analogues with differing spectra of RYR/SERCA activities were tested using RYR-null or RYR1-expressing HEK293 and murine cortical neuronal/glial cocultures (NGCs) loaded with Fluo-4 to elucidate their mechanisms altering Ca2+ dynamics. The NGC electrical spike activity (ESA) was measured from NGCs plated on multielectrode arrays. Nanomolar tetrabromopyrrole (TBP, 1) potentiated caffeine-triggered Ca2+ release independent of extracellular [Ca2+] in RYR1-HEK293, whereas higher concentrations produce slow and sustained rise in cytoplasmic [Ca2+] independent of RYR1 expression. TBP, 2,3,5-tribromopyrrole (2), pyrrole (3), 2,3,4-tribromopyrrole (4), and ethyl 4-bromopyrrole-2-carboxylate (5) added acutely to NGC showed differential potency; rank order TBP (IC50 ≈ 220 nM) > 2 ≫ 5, whereas 3 and 4 were inactive at 10 µM. TBP >2 µM elicited sustained elevation of cytoplasmic [Ca2+] and loss of neuronal viability. TBP did not alter network ESA. BrPyr from marine and anthropogenic sources are ecological signaling molecules and emerging anthropogenic pollutants of concern to environmental and human health that potently alter ER Ca2+ dynamics and warrant further investigation in vivo.

A systematic review on the effects of environmental exposure to some organohalogens and phthalates on early puberty.

BACKGROUND: Early puberty is a common worldwide problem. Different parameters as genetics, metabolic diseases, obesity, as well as environmental factors may affect the age of puberty. This systematic review aims to survey the related literature on the effects of environmental pollutants and especially organohalogens and phthalates on early puberty. MATERIALS AND METHODS: A systematic review of papers published in the English language was completed in January 2014. Studies on the associations of organohalogens and phthalates with the puberty time were included. A literature search was conducted in EMBASE, PubMed, Scopus, ISI Web of Science, and Cochrane Library from 1995 to January 2014; moreover manual search through references of relevant manuscripts was considered. The literature search identified 212 papers, of which 13 papers fulfilled the inclusion criteria of the current study. Two reviewers independently identified relevant papers for potential inclusion and assessed the methodological quality. RESULTS: This review included 6572 participants in nine countries from three continents (Europe, North America, and Asia). Different studies determined the effects of pollutants on maturation signs and pubertal stages and confirmed the association of organohalogens and phthalates with early puberty. CONCLUSION: Based on the studied literature, environmental pollutants surround and accumulate in human societies and their adverse health effects are well documented. It can be concluded that organohalogens and phthalates are disturbing the normal process of puberty timing; especially their influence on early maturation in girls should be underscored.

Macroalgal microbiomes unveil a valuable genetic resource for halogen metabolism.

BACKGROUND: Macroalgae, especially reds (Rhodophyta Division) and browns (Phaeophyta Division), are known for producing various halogenated compounds. Yet, the reasons underlying their production and the fate of these metabolites remain largely unknown. Some theories suggest their potential antimicrobial activity and involvement in interactions between macroalgae and prokaryotes. However, detailed investigations are currently missing on how the genetic information of prokaryotic communities associated with macroalgae may influence the fate of organohalogenated molecules. RESULTS: To address this challenge, we created a specialized dataset containing 161 enzymes, each with a complete enzyme commission number, known to be involved in halogen metabolism. This dataset served as a reference to annotate the corresponding genes encoded in both the metagenomic contigs and 98 metagenome-assembled genomes (MAGs) obtained from the microbiome of 2 red (Sphaerococcus coronopifolius and Asparagopsis taxiformis) and 1 brown (Halopteris scoparia) macroalgae. We detected many dehalogenation-related genes, particularly those with hydrolytic functions, suggesting their potential involvement in the degradation of a wide spectrum of halocarbons and haloaromatic molecules, including anthropogenic compounds. We uncovered an array of degradative gene functions within MAGs, spanning various bacterial orders such as Rhodobacterales, Rhizobiales, Caulobacterales, Geminicoccales, Sphingomonadales, Granulosicoccales, Microtrichales, and Pseudomonadales. Less abundant than degradative functions, we also uncovered genes associated with the biosynthesis of halogenated antimicrobial compounds and metabolites. CONCLUSION: The functional data provided here contribute to understanding the still largely unexplored role of unknown prokaryotes. These findings support the hypothesis that macroalgae function as holobionts, where the metabolism of halogenated compounds might play a role in symbiogenesis and act as a possible defense mechanism against environmental chemical stressors. Furthermore, bacterial groups, previously never connected with organohalogen metabolism, e.g., Caulobacterales, Geminicoccales, Granulosicoccales, and Microtrichales, functionally characterized through MAGs reconstruction, revealed a biotechnologically relevant gene content, useful in synthetic biology, and bioprospecting applications. Video Abstract.

Potential of Microbial Communities to Perform Dehalogenation Processes in Natural and Anthropogenically Modified Environments-A Metagenomic Study.

Halogenated organic compounds (HOCs) pose a serious problem for the environment. Many are highly toxic and accumulate both in soil and in organisms. Their biological transformation takes place by dehalogenation, in which the halogen substituents are detached from the carbon in the organic compound by enzymes produced by microorganisms. This increases the compounds' water solubility and bioavailability, reduces toxicity, and allows the resulting compound to become more susceptible to biodegradation. The microbial halogen cycle in soil is an important part of global dehalogenation processes. The aim of the study was to examine the potential of microbial communities inhabiting natural and anthropogenically modified environments to carry out the dehalogenation process. The potential of microorganisms was assessed by analyzing the metagenomes from a natural environment (forest soils) and from environments subjected to anthropopression (agricultural soil and sludge from wastewater treatment plants). Thirteen genes encoding enzymes with dehalogenase activity were identified in the metagenomes of both environments, among which, 2-haloacid dehalogenase and catechol 2,3-dioxygenase were the most abundant genes. Comparative analysis, based on comparing taxonomy, identified genes, total halogens content and content of DDT derivatives, demonstrated the ability of microorganisms to transform HOCs in both environments, indicating the presence of these compounds in the environment for a long period of time and the adaptive need to develop mechanisms for their detoxification. Metagenome analyses and comparative analyses indicate the genetic potential of microorganisms of both environments to carry out dehalogenation processes, including dehalogenation of anthropogenic HOCs.

A probabilistic hazard and risk assessment of exposure to metals and organohalogens associated with a traditional diet in the Indigenous communities of Eeyou Istchee (northern Quebec, Canada).

Hunting, trapping, and fishing are part of an Indigenous lifestyle in subarctic Canada. However, this lifestyle may be a route of exposure to contaminants and may pose a risk for the people who rely on a subsistence diet. Monte Carlo simulations for the chemical concentration of eight game species and one fish species were carried out by randomly sampling 10,000 samples from the contaminant measures for each species. We then calculated a probabilistic non-carcinogenic hazard quotient or carcinogenic risk values to estimate the human health risk of exposure to contaminants. Of the species examined, ducks were of concern for potential carcinogenic risk. There was a modeled probabilistic 95th-percentile risk associated with the consumption of ducks and polybrominated biphenyl (PBB) congener 153 in boys, women, and men (1.09 × 10-6, 1.57 × 10-6, and 2.17 × 10-6, respectively) and, to a lesser extent, with geese and polychlorinated biphenyl (PCB) congener 153 in men (1.19 × 10-6). Contaminant concentration in the intake rate (food consumption) for PBB congener 153 exposure risk was more important than that for PCB congener 153, where intake rate had greater relevance. The consumption of waterfowl may increase the exposure to organohalogens; however, there are health and wellness benefits associated with the harvesting and consumption of subsistence foods that must also be considered. We recommend follow-up species-specific studies focused on ducks to clarify and elucidate the results in the present study.

A Multi-Matrix Metabolomic Approach in Ringed Seals and Beluga Whales to Evaluate Contaminant and Climate-Related Stressors.

As a high trophic-level species, ringed seals (Pusa hispida) and beluga whales (Delphinapterus leucas) are particularly vulnerable to elevated concentrations of biomagnifying contaminants, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and mercury (Hg). These species also face climate-change-related impacts which are leading to alterations in their diet and associated contaminant exposure. The metabolomic profile of marine mammal tissues and how it changes to environmental stressors is poorly understood. This study characterizes the profiles of 235 metabolites across plasma, liver, and inner and outer blubber in adult ringed seals and beluga whales and assesses how these profiles change as a consequence of contaminants and dietary changes. In both species, inner and outer blubber were characterized by a greater proportion of lipid classes, whereas the dominant metabolites in liver and plasma were amino acids, carbohydrates, biogenic amines and lysophosphatidylcholines. Several metabolite profiles in ringed seal plasma correlated with δ13C, while metabolite profiles in blubber were affected by hexabromobenzene in ringed seals and PBDEs and Hg in belugas. This study provides insight into inter-matrix similarities and differences across tissues and suggests that plasma and liver are more suitable for studying changes in diet, whereas liver and blubber are more suitable for studying the impacts of contaminants.

Exploration of marine natural resources in Indonesia and development of efficient strategies for the production of microbial halogenated metabolites.

Nature is a prolific source of organic products with diverse scaffolds and biological activities. The process of natural product discovery has gradually become more challenging, and advances in novel strategic approaches are essential to evolve natural product chemistry. Our focus has been on surveying untouched marine resources and fermentation to enhance microbial productive performance. The first topic is the screening of marine natural products isolated from Indonesian marine organisms for new types of bioactive compounds, such as antineoplastics, antimycobacterium substances, and inhibitors of protein tyrosine phosphatase 1B, sterol O-acyl-transferase, and bone morphogenetic protein-induced osteoblastic differentiation. The unique biological properties of marine organohalides are discussed herein and attempts to efficiently produce fungal halogenated metabolites are documented. This review presents an overview of our recent work accomplishments based on the MONOTORI study.

Stoichiometry of the Gene Products From the Tetrachloroethene Reductive Dehalogenase Operon pceABCT.

Organohalide respiration (OHR) is a bacterial anaerobic process that uses halogenated compounds, e.g., tetrachloroethene (PCE), as terminal electron acceptors. Our model organisms are Dehalobacter restrictus strain PER-K23, an obligate OHR bacterium (OHRB), and Desulfitobacterium hafniense strain TCE1, a bacterium with a versatile metabolism. The key enzyme is the PCE reductive dehalogenase (PceA) that is encoded in the highly conserved gene cluster (pceABCT) in both above-mentioned strains, and in other Firmicutes OHRB. To date, the functions of PceA and PceT, a dedicated molecular chaperone for the maturation of PceA, are well defined. However, the role of PceB and PceC are still not elucidated. We present a multilevel study aiming at deciphering the stoichiometry of pceABCT individual gene products. The investigation was assessed at RNA level by reverse transcription and (quantitative) polymerase chain reaction, while at protein level, proteomic analyses based on parallel reaction monitoring were performed to quantify the Pce proteins in cell-free extracts as well as in soluble and membrane fractions of both strains using heavy-labeled reference peptides. At RNA level, our results confirmed the co-transcription of all pce genes, while the quantitative analysis revealed a relative stoichiometry of the gene transcripts of pceA, pceB, pceC, and pceT at ~ 1.0:3.0:0.1:0.1 in D. restrictus. This trend was not observed in D. hafniense strain TCE1, where no substantial difference was measured for the four genes. At proteomic level, an apparent 2:1 stoichiometry of PceA and PceB was obtained in the membrane fraction, and a low abundance of PceC in comparison to the other two proteins. In the soluble fraction, a 1:1 stoichiometry of PceA and PceT was identified. In summary, we show that the pce gene cluster is transcribed as an operon with, however, a level of transcription that differs for individual genes, an observation that could be explained by post-transcriptional events. Despite challenges in the quantification of integral membrane proteins such as PceB and PceC, the similar abundance of PceA and PceB invites to consider them as forming a membrane-bound PceA2B protein complex, which, in contrast to the proposed model, seems to be devoid of PceC.

Reflections on chemical risk assessment or how (not) to serve society with science.

In this paper, we want to shed light on the demand for chemical and toxicological data growing ever more faster than science can supply and other aspects of assessing chemical risks, including the demand for 'ever greater safety'. The treatise that follows is on the one hand rooted in well-established toxicological theory and on the other hand utilises emerging toxicological insights. Both theoretical conceptions and empirical substantiations are discussed to build up a perspective that produces an outlook on innovation and proliferates insights into our inexorable and invaluable exposure to 'the chemical'. We propose that in toxicology, with the implicit mandatory linear routine of dose-response, there is no tangible scientific drive to understand and unearth the actual empirical dose-response curve for chemicals under scrutiny. This can and should be improved upon as to advance the science of toxicology and to optimise current and future regulatory efforts.

Baseline survey of marine sediments collected from the Kingdom of Bahrain: PAHs, PCBs, organochlorine pesticides, perfluoroalkyl substances, dioxins, brominated flame retardants and metal contamination.

A baseline survey of sediment contamination was undertaken at 14 locations around the coastline of Bahrain in May 2017, followed by a focused survey of 20 sites, in November 2019. Samples were assessed for industrial pollutants, including metals, PAHs and a suite of organohalogen compounds. The data generated indicated that levels of chemical contaminants were generally low and did not pose a toxicological risk when assessed against commonly applied sediment quality guidelines (SQG). The highest concentrations of PAHs and PCBs were identified in samples collected at coastal sites adjacent to a refinery area known to contain a diverse mix of industry. Tubli Bay, a heavily stressed small bay receiving high loads of sewage effluent, was also identified as an area warranting further investigation with elevated concentrations of BDE209, PFOS and metal contamination. Such data provides a useful baseline assessment of sediment contamination, against which management control measures can be assessed.

Molecular insights into the formation and remobilization potential of nonextractable anthropogenic organohalogens in heterogeneous environmental matrices.

Anthropogenic organohalogens (AOHs) are toxic and persistent pollutants that occur ubiquitously in the environment. An unneglectable portion of them can convert into nonextractable residues (NER) in the natural solid substances. NER-AOHs are not detectable by conventional solvent-extraction, and will get remobilized through changes of surrounding environment. Consequently, the formation and fate of NER-AOHs should be investigated comprehensively. In this study, solvent extraction, sequential chemical degradation and thermochemolysis were applied on different sample matrices (sediments, soils and groundwater sludge, collected from industrial areas) to release extractable and nonextractable AOHs. Covalent linkages were observed most favorable for the hydrophilic-group-containing monocyclic aromatic AOHs (HiMcAr-AOHs) (e.g. halogenated phenols, benzoic acids and anilines) incorporating into the natural organic matter (NOM) as NER. Physical entrapment mainly contributed to the NER formation of hydrophobic monocyclic aromatic AOHs (HoMcAr-AOHs) and polycyclic aromatic AOHs (PcAr-AOHs). The hypothesized remobilization potential of these NER-AOHs follow the order HiMcAr-AOHs > HoMcAr-AOHs/ aliphatic AOHs > PcAr-AOHs. In addition, the NOM macromolecular structures of the studied samples were analyzed. Based on the derived results, a conceptual model of the formation mechanisms of NER-AOHs is proposed. This model provides basic molecular insights that are of high value for risk assessment and remediation of AOHs.

Particulate organohalogens in edible brown seaweeds.

Brown algae, rich in antioxidants and other bioactive compounds, are important dietary seaweeds in many cultures. Like other marine macroalgae, brown seaweeds are known to accumulate the halogens iodine and bromine. Comparatively little is known about the chemistry of chlorine in seaweeds. We used synchrotron-based X-ray absorption spectroscopy to measure total non-volatile organochlorine and -bromine in five edible brown seaweeds: Laminaria digitata, Fucus vesiculosus, Pelvetia canaliculata, Saccharina latissima, and Undaria pinnatifida. Organochlorine concentrations range from 120 to 630 mg·kg-1 dry weight and organobromine from 150 to 360 mg·kg-1, comprising mainly aromatic organohalogens in both cases. Aliphatic organochlorine exceeds aliphatic organobromine but is positively correlated with it among the seaweeds. Higher organochlorine levels appear in samples with more lipid moieties, suggesting lipid chlorination as a possible formation pathway. Particulate organohalogens are not correlated with antioxidant activity or polyphenolic content in seaweed extracts. Such compounds likely contribute to organohalogen body burden in humans and other organisms.

Association of thyroid hormone concentrations with levels of organochlorine compounds in cord blood of neonates.

BACKGROUND: Thyroid hormones are important regulators of brain development. During critical periods of development, even transient disorders in thyroid hormone availability may lead to profound neurologic impairment. Animal experiments have shown that certain environmental pollutants, including heavy metals and organochlorine compounds such as polychlorinated biphenyls (PCBs) and dioxins, can interfere with thyroid hormone homeostasis. Whether these contaminants can affect circulating levels of thyroid hormones in humans is unclear, however, because the results of available studies are inconsistent. OBJECTIVES: The aim of the present study is to examine the possible relationships between concentrations of environmental pollutants and thyroid hormone levels in human umbilical cord blood. METHODS: We measured concentrations of environmental pollutants [including selected PCBs, dioxin-like compounds, hexachlorobenzene, p,p'-DDE (dichlorodiphenyldichloroethylene), cadmium, lead] and thyroid hormones in the cord blood of 198 neonates. RESULTS: A statistically significant inverse relationship between concentrations of organochlorine compounds and levels of both free triiodothyronine (fT3) and free thyroxine (fT4), but not thyroid-stimulating hormone, was observed. We found no association between concentrations of heavy metals and thyroid hormone levels. CONCLUSIONS: Our results suggest that environmental chemicals may affect the thyroid system of human neonates. Although the differences in fT3 and fT4 levels associated with the organochlorine compounds were within the normal range, the observed interferences may still have detrimental effects on the neurologic development of the individual children, given the importance of thyroid hormones in brain development.

Independent Maternal and Fetal Genetic Effects on Midgestational Circulating Levels of Environmental Pollutants.

Maternal exposure to environmental pollutants could affect fetal brain development and increase autism spectrum disorder (ASD) risk in conjunction with differential genetic susceptibility. Organohalogen congeners measured in maternal midpregnancy blood samples have recently shown significant, but negative associations with offspring ASD outcome. We report the first large-scale maternal and fetal genetic study of the midpregnancy serum levels of a set of 21 organohalogens in a subset of 790 genotyped women and 764 children collected in California by the Early Markers for Autism (EMA) Project. Levels of PCB (polychlorinated biphenyl) and PBDE (polybrominated diphenyl ether) congeners showed high maternal and fetal estimated SNP-based heritability (h2g ) accounting for 39-99% of the total variance. Genome-wide association analyses identified significant maternal loci for p,p'-DDE (P = 7.8 × 10-11) in the CYP2B6 gene and for BDE-28 (P = 3.2 × 10-8) near the SH3GL2 gene, both involved in xenobiotic and lipid metabolism. Fetal genetic loci contributed to the levels of BDE-100 (P = 4.6 × 10-8) and PCB187 (P = 2.8 × 10-8), near the potential metabolic genes LOXHD1 and PTPRD, previously implicated in neurodevelopment. Negative associations were observed for BDE-100, BDE153, and the sum of PBDEs with ASD, partly explained by genome-wide additive genetic effects that predicted PBDE levels. Our results support genetic control of midgestational biomarkers for environmental exposures by nonoverlapping maternal and fetal genetic determinants, suggesting that future studies of environmental risk factors should take genetic variation into consideration. The independent influence of fetal genetics supports previous hypotheses that fetal genotypes expressed in placenta can influence maternal physiology and the transplacental transfer of organohalogens.

Validation of a novel and rapid method for the simultaneous determination of some phenolic organohalogens in human serum by GC-MS.

Over the last decades, more and more studies focused on the impact of endocrine disruptors on the environment and human health. Among them, phenolic organohalogens (POHs) are a particular concern because of their structural resemblance with natural hormones. There are different methods that are known to quantify these compounds in human serum, however, the current extraction techniques are long, fastidious and using harmfull chemicals such as diazomethane and sulfuric acid. Consequently, we developed an alternative, sensitive and faster method to simultaneously quantify pentachlorophenol (PCP), tetrabromobisphenol A (TBBPA), 4 bromophenols, 7 hydroxypolychlorinated biphenyls (OH-PCBs) and 3 hydroxy-polybrominated diphenyl ether (OH-PBDEs) in human serum sample. The clean-up and the enrichment of the sample were performed in a single extraction step using strong anion-exchange solid phase cartridge. After a rapid liquid-liquid extraction step to remove acidic traces, the extract was derivatized using trimethylsilyldiazomethane (TMSD) and finally analyzed by a gas-chromatograph coupled with an electron negative capture chemical ionization source combined with a triple quadrupole mass spectrometer (GC-ENCI-MS) operating in single ion monitoring. The whole procedure was validated according to the total error approach. The inter and intra assay precision were demonstrated to be lower than 20% and the relative bias to be lower than 15% in the dosing range of concentrations. The limit of quantification (LOQ) ranged from 2pgmL-1 and 5pgmL-1, except for the PCP (44.6pgmL-1) and for the 2,4,6-tribromophenol (49.6pgmL-1). Finally, the method was successfully applied to measure the POH background contamination in serum samples collected from 20 Belgian blood donors recruited in CHU Mont-Godinne (Namur, Belgium) aged between 21 and 69 years old.

A review on current knowledge and future prospects of organohalogen contaminants (OHCs) in Asian birds.

The release of harmful chemicals in the Asian environment has recently increased dramatically due to rising industrial and agricultural activities. About 60% of the global human population is currently living on the Asian continent and may thus be exposed to a large range of different chemicals. Different classes of organohalogen chemicals have indeed been reported in various environmental compartments from Asia including humans and wildlife, but this issue has received less attention in birds. In this article, we reviewed the available literature on levels of legacy persistent organic pollutants (POPs) and various flame retardants (FRs) in Asian avifauna to analyze the existing pool of knowledge as well as to identify the gaps that should be addressed in future research. Furthermore, we discussed the variation in levels of organohalogens based on differences in regions, trophic level, dietary sources and migratory behaviors of species including distribution patterns in different tissues of birds. Although the mass of published literature is very low and even absent in many important regions of Asia, we deduced from the reported studies that levels of almost all classes of organohalogens (OHCs) including FRs were highest in East Asian countries such as Japan, China and South Korea, except for HCHs that were found at maximum levels in birds of South India. Concentrations (ng/g LW) of different OHCs in Asian birds ranged between

The natural chlorine cycle - Formation of the carcinogenic and greenhouse gas compound chloroform in drinking water reservoirs.

Chlorine cycle in natural ecosystems involves formation of low and high molecular weight organic compounds of living organisms, soil organic matter and atmospherically deposited chloride. Chloroform (CHCl3) and adsorbable organohalogens (AOX) are part of the chlorine cycle. We attempted to characterize the dynamical changes in the levels of total organic carbon (TOC), AOX, chlorine and CHCl3 in a drinking water reservoir and in its tributaries, mainly at its spring, and attempt to relate the presence of AOX and CHCl3 with meteorological, chemical or biological factors. Water temperature and pH influence the formation and accumulation of CHCl3 and affect the conditions for biological processes, which are demonstrated by the correlation between CHCl3 and ΣAOX/Cl(-) ratio, and also by CHCl3/ΣAOX, CHCl3/AOXLMW, CHCl3/ΣTOC, CHCl3/TOCLMW and CHCl3/Cl(-) ratios in different microecosystems (e.g. old spruce forest, stagnant acidic water, humid and warm conditions with high biological activity). These processes start with the biotransformation of AOX from TOC, continue via degradation of AOX to smaller molecules and further chlorination, and finish with the formation of small chlorinated molecules, and their subsequent volatilization and mineralization. The determined concentrations of chloroform result from a dynamic equilibrium between its formation and degradation in the water; in the Hamry water reservoir, this results in a total amount of 0.1-0.7 kg chloroform and 5.2-15.4 t chloride. The formation of chloroform is affected by Cl(-) concentration, by concentrations and ratios of biogenic substrates (TOC and AOX), and by the ratios of the substrates and the product (feedback control by chloroform itself).

The English Channel: Contamination status of its transitional and coastal waters.

The chemical contamination (organic compounds, metals, radionuclides, microplastics, nutrients) of English Channel waters has been reviewed, focussing on the sources, concentrations and impacts. River loads were only reliable for Pb, whereas atmospheric loads appeared robust for Cd, Pb, Hg, PCB-153 and γ-HCH. Temporal trends in atmospheric inputs were decreasing. Contaminant concentrations in biota were relatively constant or decreasing, but not for Cd, Hg and HBCDD, and deleterious impacts on fish and copepods were reported. However, data on ecotoxicological effects were generally sparse for legacy and emerging contaminants. Intercomparison of activity concentrations of artificial radionuclides in sediments and biota on both Channel coasts was hindered by differences in methodological approaches. Riverine phosphate loads decreased with time, while nitrate loads remained uniform. Increased biomass of algae, attributable to terrestrial inputs of nutrients, has affected benthic production and shellfisheries. A strategic approach to the identification of contaminant impacts on marine biota is recommended.