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Water science and technology 83(3), 532-542 (2021). doi:10.2166/wst.2020.600, Published by IWA Publishing, London

Per- and polyfluoroalkyl substances (PFAS) are persistent and toxic contaminants that are ubiquitous in the environment. They can incorporate into soil as nonextractable residues (NER) which are not detectable with conventional analytical protocols but are still possible to remobilize with changes of surrounding conditions, and thus will be bioavailable again. Therefore, there is a need to investigate thoroughly the long-term fate of NER-PFAS. In this study, a 240-day incubation of perfluorooctanesulfonate (PFOS) and its alternative 6:2 chlorinated polyfluorinated ether sulfonate (F-53B) in a silty clay topsoil was carried out. Solvent extraction, alkaline hydrolysis and sequential chemical degradation were applied on periodically sampled soil to obtain extractable, moderately bound and deeply bound PFAS, respectively. The results confirmed the formation of NER of both compounds but with different preferences of incorporating mechanisms. NER-PFOS was formed predominantly by covalent binding (via head group) and strong adsorption (via tail group). The formation of NER-F-53B was mainly driven by physical entrapment. Both bound compounds within the incubation period showed three-stage behaviors including an initial period with slight release followed by a (re) incorporating stage and a subsequent remobilizing stage. This work provides some first insights on the long-term dynamic behaviors of nonextractable PFAS and will be conducive to their risk assessment and remediation (e.g. estimating potential NER-PFAS level based on their free extractable level, and selecting remediation methods according to their prevailing binding mechanisms).

Nonextractable residues (NER) are pollutants incorporated into the matrix of natural solid matter via different binding mechanisms. They can become bioavailable or remobilize during physical-chemical changes of the surrounding conditions and should thus not be neglected in environmental risk assessment. Sediments, soils, and groundwater sludge contaminated with DDXs (DDT, dichlorodiphenyltrichloroethane; and its metabolites) were treated with solvent extraction, sequential chemical degradation, and thermochemolysis to study the fate of NER-DDX along different environmental aquatic-terrestrial pathways. The results showed that DDT and its first degradation products, DDD (dichlorodiphenyldichloroethane) and DDE (dichlorodiphenyldichloroethylene), were dominant in the free extractable fraction, whereas DDM (dichlorodiphenylmethane), DBP (dichlorobenzophenone), and DDA (dichlorodiphenylacetic acid) were observed primarily after chemical degradation. The detection of DDA, DDMUBr (bis( p-chlorophenyl)-bromoethylene), DDPU (bis( p-chlorophenyl)-propene) and DDPS (bis( p-chlorophenyl)-propane) after chemical treatments evidenced the covalent bindings between these DDXs and the organic matrix. The identified NER-DDXs were categorized into three groups according to the three-step degradation process of DDT. Their distribution along the different pathways demonstrated significant specificity. Based on the obtained results, a conceptual model of the fate of NER-DDXs on their different environmental aquatic-terrestrial pathways is proposed. This model provides basic knowledge for risk assessment and remediation of both extractable and nonextractable DDT-related contaminations.

The production of hexachlorocyclohexanes (HCHs) at Bitterfeld, Germany, caused heavy contamination of sediments in the receiving waters and soils of riverbanks and floodplains of the Spittelwasser creek with adverse effects on the rivers Mulde and Elbe. This study was launched to investigate the isomer specific behaviour of aged and non-aged hexachlorocyclohexanes focusing on their transformation, sorption and bioaccumulation. Spiked residues of α- and γ-HCH were transformed in aerobic water/sediment systems, while no elimination was observed for β-, δ- and ε-HCH. In contrast, aged residues of all HCH isomers were entirely stable under these aerobic conditions, while under anaerobic conditions a significant transformation was found for all spiked HCH isomers. Desorption hysteresis was identified for all isomers. Ageing led to an increase in the binding strength of HCH isomers to sediment, indicated by elevated logKOC-values and increased the persistence of HCH isomers in aerobic water/sediment systems. HCH bioaccumulated in benthic organisms of Spittelwasser creek and Schachtgraben canal. After their confluence the lipid normalised HCH concentrations in benthic organisms of Spittelwasser creek increased by a factor of 10, indicating the central role of HCH residues from the Schachtgraben canal for the HCH exposure of benthic biota in the aquatic system of the Spittelwasser creek.

Jakarta is an Indonesian coastal megacity with over 10 million inhabitants. The rivers flowing through the city receive enormous amounts of untreated wastewaters and discharge their pollutant loads into Jakarta Bay. We utilized a screening approach to identify those site-specific compounds that represent the major contamination of the cities' water resources, and detected a total number of 71 organic contaminants in Jakarta river water samples. Especially contaminants originating from municipal wastewater discharges were detected in high concentrations, including flame retardants, personal care products and pharmaceutical drugs. A flame retardant, a synthetic fragrance and caffeine were used as marker compounds to trace the riverine transport of municipal wastewaters into Jakarta Bay. These markers are also appropriate to trace municipal wastewater discharges to other tropical coastal ecosystems. This application is in particular useful to evaluate wastewater inputs from land-based sources to habitats which are sensitive to changing water quality, like coral reefs.

Non-target screening analyses were conducted in order to identify a wide range of organic contaminants in sediment and animal tissue samples from Jakarta Bay. High concentrations of di-iso-propylnaphthalenes (DIPNs), linear alkylbenzenes (LABs) and polycyclic aromatic hydrocarbons (PAHs) were detected in all samples, whereas phenylmethoxynaphthalene (PMN), DDT and DDT metabolites (DDX) were detected at lower concentrations. In order to evaluate the uptake and accumulation by economic important mussel (Perna viridis) and fish species, contaminant patterns of DIPNs, LABs and PAHs in different compartments were compared. Different patterns of these contaminant groups were found in sediment and animal tissue samples, suggesting compound-specific accumulation and metabolism processes. Significantly higher concentrations of these three contaminant groups in mussel tissue as compared to fish tissue from Jakarta Bay were found. Because P. viridis is an important aquaculture species in Asia, this result is relevant for food safety.

Various studies show a contamination of the marine environment with microplastics due to the material persistence and a resulting accumulation. Right now, the environmental impact of microplastics is not fully determined and in order to obtain further information on contaminated areas, water surface samples and (deep sea) sediment from the Atlantic Ocean south of Algarve Coast (Portugal) were taken and analysed. Microfibres, 3 black fibres, were visually detected in 2 of the 20 sediment samples without verifying their polymeric identity. Assuming that they are microplastics, concentration from 0.00–0.29 particles/g dry sediment result. In the eleven water samples, 81.8% contained microplastics including polymeric identification (0.00–14.09 particles/m3) with an average contamination of 1.36 ± 4.03 particles/m3. A significant positive correlation between the microplastic concentration in the water and the average water depth during sampling was identified. This regional study is one of a few that analysed also deep sea sediment and provides results about microplastics as anthropogenic contaminants south of the Algarve coast.

Analysis of limnic sediments can serve as a tool to assess sedimentary pollution for both the status quo as well as changes over time. However, in environmental studies, often only a small number of established well-studied contaminants are considered. This study focused on a more comprehensive investigation of sedimentary pollution of Djerdap Reservoir. Therefore, complementary analytical approaches were applied covering lipophilic organic contaminants and heavy metals. Investigations were performed on limnic sediment layers representing a period of 43 years of reservoir functioning. The core was sectioned on 11 samples and analyzed for, loss on ignition (LOI), and organic compounds (gas chromatography-mass spectrometry). Here, we report the quantitative data of 43 lipophilic organic compounds indicating both domestic and industrial emissions. Measured concentrations are generally low. Surprisingly, no polychlorinated biphenyls have been detected. Data concerning grain size, sedimentological, and inorganic composition were measured and published by in Kasanin-Grubin et al. (Kasanin-Grubin et al. 2019). This article has been corrected. Link to the correction: [https://cherry.chem.bg.ac.rs/handle/123456789/4275]

s & presentations / EGU General Assembly 2020 European Geoscience Union General Assembly, EGU 2020, online, 4 May 2020 - 8 May 2020; G��ttingen : Copernicus Gesellschaft mbH EGU2020-8218, 1 Seite (2020). doi:10.5194/egusphere-egu2020-8218, Published by Copernicus Gesellschaft mbH, G��ttingen

In order to recognize organic contaminants responsible for ecological stresses from intensive shipping traffic and dockyard works, this study aimed at characterizing the sediment contamination of a large industrialized port located in Hainan Island, China. Surface sediment samples were collected from 17 stations including the main docks, the dockyards and the major industrial wastewater outlets. Organotin compounds, the pesticide DDT (bis(chlorophenyl)trichloroethane) and its metabolites and polycyclic aromatic compounds were identified as main pollutant groups by GC/MS applying a non-target screening approach. The pesticide DDT and its metabolites were found in the same samples as the organotin derivatives pointing to similar emission sources. The concurrent presence of these compounds in the dockyard samples suggests a combined usage of organotin compounds and DDT as active ingredients in antifouling paints in Yangpu. As highly specific molecular indicators for dockyard activities, butyltin and phenyltin compounds were identified. Noteworthy, also tributylmethyltin and triphenylmethyltin were detected, likely resulting from microbial assisted biomethylation of synthetic organotin compounds in the sediments. The concentrations of PAHs, DDX and TBT in sediments from dockyards exceeded global sediment quality guidelines and the toxicity thresholds, and potentially have adverse biological effects on marine organisms.

Jakarta, the capital of Indonesia, is one of the rapidly growing coastal megacities in Asia. The implementation of the urban wastewater infrastructure is not keeping up with the rapid expansion of the city, leading to a severe deterioration of water and sediment quality in the metropolitan area. The present study aimed to assess sediment contamination with organic pollutants in Jakarta rivers and the related risks to the coastal ecosystem. To this end, the site-specific and most harmful organic pollutants in the sediments were quantified, and the obtained chemical data were compared to reported sediment toxicity thresholds for an impact assessment on the benthic community. The detected pollutant spectrum included several compounds, such as the detergent residues nonylphenols and the insect repellent DEET (N,N-diethyl-m-toluamide), that were previously reported as contaminants in industrialized countries but have been banned or partly substituted. The risk of sediment contamination for benthic macroinvertebrates was associated with PAHs (polycyclic aromatic hydrocarbons), DDT (bis(chlorophenyl)dichloroethane), nonylphenols and a synthetic fragrance. High concentrations of paper manufacturing educts, a compound class that was recently reported in industrialized areas with a flourishing paper industry, were found in Jakarta sediments. However, sediment quality guidelines or sediment toxicity thresholds for these compounds are not available, which limited the ecotoxicological risk assessment. More studies on sediment toxicities considering emerging industrial pollutants and test species from all climate regions are urgently required, as a prerequisite for an adequate impact assessment of sediment contamination.

International audience; Chapters: Maintenance and Conservation of Materials in the Built Environment. Nanotechnology in Water Treatment. Biodegradation of Organophosphate and Pyrethroid Pesticides by Microorganims. Non-target UHPLC/MS Analysis of Emerging Contaminants in Water. PAHs Pollution Monitoring by Bivalves. Selenium and its Role in Higher Plants. Aromatic Amines Sources, Environmental Impact and Remediation

The Palos Verdes Shelf (PVS) and the continental slope off the Palos Verdes Peninsula are highly contaminated by degradation products of the pesticide DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene). Sediment samples from two box cores were analyzed to obtain further information about the fate of DDT and its degradation products within the environment. After solvent extraction, an alkaline hydrolysis procedure was applied. A comprehensive screening for 26 DDT compounds revealed that DDT and its degradates contaminate not only the extractable fraction but also the fraction released by alkaline hydrolysis. A comparison of the quantitative distribution of DDT degradation products in the extractable fraction and released by alkaline hydrolysis showed a distinct difference. DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene), DDD (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethyl]benzene), DDMS (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethyl]benzene), and DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene) were predominant in the sediment extracts but minor components of the hydrolyzable fraction. The most abundant compounds released by the alkaline hydrolysis were DBP (bis(4-chlorophenyl)methanone), DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene), DDM (1-chloro-4-[(4-chlorophenyl)methyl]benzene) and the water-soluble DDA (2,2-bis(4-chlorophenyl)acetic acid). The release of DDA may point to the presence of an important degradation pathway in marine environments. Concentration levels of DDT-related compounds showed corresponding vertical profiles in both fractions, but were significantly lower in the fraction released by alkaline hydrolysis. In contrast to fluvial sediments contaminated by DDT and its degradates the alkaline hydrolysis products represented a minor portion of the total sedimentary burden in the analyzed marine sediments. These findings show the necessity of a comprehensive screening for all DDT isomers and breakdown products in the extractable and non-extractable fraction to assess the total contamination abundance and potential environmental risks.

Industrialization and urbanization in the more economically developed countries and also in emerging and developing nations have led to an intensive and still increasing use of water resources. The involved chemical contamination led to a deterioration of aquatic systems in many areas. Industries are important pollution sources and the discharged wastewaters may contain very diverse and potentially harmful organic compound groups. We therefore present here a comprehensive review of the current state of knowledge of organic contaminants from industrial wastewaters. The available studies proved the heterogenic chemical composition of industrial wastewaters, even from the same industry branches, and the presence of heterogenic organic contaminant mixtures from industrial sources in aquatic systems. We conclude that our knowledge of the chemical composition of industrial wastewaters and the occurrence of industrial organic contaminants in the environment is as yet very limited. A combination of chemical and toxicological methods enabled the identification of toxic organic constituents in industrial wastewaters. Chemical evaluations of industrial contamination linked to surveys of environmental impacts could relate toxic effects of field samples to the presence of specific contaminants. Exposure experiments in the field proved the bioaccumulation and toxicity of several industrial compounds. Ecological surveys in industrial areas combined with a comprehensive chemical characterization and toxicity evaluation are so far missing. Some of the identified organic contaminants are related to characteristic industrial production processes, and their presence in water, sediment or biota indicates the input of specific industrial wastewaters. Accordingly, these compounds can be used as industrial markers. We suggest the proceeding application of the marker concept, as markers are useful to verify the input of specific industrial wastewaters to aquatic systems and to investigate the spatial distribution of the emission. Such information helps to disentangle different emission sources for the subsequent investigation of potential impacts in the environment.

International audience; Chapters: Biodiesel from Microalgal Oil Extraction. Electrochemistry and Water Pollution. Heterogeneous Photocatalysis for Pharmaceutical Wastewater Treatment. Water Depollution Using Ferrites Photocatalysts. Bioindicators of Toxic Metals. Natural Dyes and Antimicrobials for Textiles. Surfactants in Agriculture. Cheap Materials to Clean Heavy Metal Polluted Waters. Water Quality Monitoring by Aquatic Bryophytes. Halogenated PAH Contamination in Urban Soils

1. School air quality: pollutants, monitoring and toxicity.- 2. Organic contaminants from industrial wastewaters: identification, toxicity and fate in the environment.- 3. Fly ash pollutants, treatment and recycling.- 4. Organotin compounds from snails to humans.- 5. Surfactants: chemistry, toxicity and remediation.- 6. Cadmium, lead, thallium: occurrence, neurotoxicity and histopathological changes of the nervous system.- 7. Lead, arsenic, cadmium, mercury: occurrence, toxicity and diseases.- 8. Plants as monitors of lead air pollution.- 9. Carcinogenic nitrosamines: remediation by zeolites.- 10. Dioxins and furans: sources, impacts and remediation.

International audience; Environmental chemistry is a fast developing science aimed at deciphering fundamental mechanisms ruling the behaviour of pollutants in ecosystems. Applying this knowledge to current environmental issues leads to the remediation of environmental media, and to new, low energy, low emission, sustainable processes. The topics that would be covered in this series, but not limited to, are major achievements of environmental chemistry for sustainable development such as nanotech applications; biofuels, solar and alternative energies; pollutants in air, water, soil and food; greenhouse gases; radioactive pollutants; endocrine disruptors and other pharmaceuticals; pollutant archives; ecotoxicology and health risk; pollutant remediation; geoengineering; green chemistry; contributions bridging unexpectedly far disciplines such as environmental chemistry and social sciences; and participatory research with end-users. The books series will encompass all scientific aspects of environmental chemistry through a multidisciplinary approach: Environmental Engineering/Biotechnology, Waste Management/Waste Technology, Pollution, general, Atmospheric Protection/Air Quality Control/Air Pollution, Analytical Chemistry. Other disciplines include: Agriculture, Building Types and Functions, Climate Change, Ecosystems, Ecotoxicology, Geochemistry, Nanochemistry, Nanotechnology and Microengineering, Social Sciences.

This study is focussed on a comprehensive investigation on the state of pollution of Danube and Sava rivers in Belgrade region. Different complementary analytical approaches have been used covering both (i) organic ccontaminants in river water by target analyses of hormones and neonicotinoids as well as non-target screening analyses and (ii) heavy metals in sediments. Finally, some common water quality parameters have been analysed. The overall state of pollution is on a moderate level. Bulk parameters did not reveal any unusual observation. Also quantification of preselected organic contaminants did not point to elevated pollution. A more significant contamination was measured for chromium, nickel, zinc and partially copper in sediments with values above target values according to Serbian regulations. Lastly, non-target screening analysis revealed a wider spectrum of organic contaminants comprising pharmaceuticals, technical additives, personal care products and pesticides. The study presented a comprehensive view on the state of pollution of Sava and Danube rivers and is the base for setting up further monitoring programs. As a superior outcome it has been illustrated how different chemical analyses can point to different assessments of the river quality. The comparison of target and non-target analyses pointed to potential misinterpretation of the real state of pollution.

Coaly material enters various environmental compartments from different emission sources and on diverse pathways. The complexity of both the emission processes and the quality of contamination in the Ostrava region avoids a simple source correlation for coal-derived pollution. Hence, this study focused on the application of different geochemical approaches for source apportionment using bulk parameters, aliphatic biomarkers and source-specific PAH ratios. Major aim was to prove the effectiveness of the applied methods for characterizing the impact of coal-derived contamination in complex emission systems such as in the Ostrava region. Individual emission sources were discriminated sufficiently by TOC vs. TEH relationship and two-dimensional correlations of PAH ratios. Additionally, aliphatic biomarkers revealed individual signatures for all classes of samples and pointed to a widespread distribution of fossil material also in the hydrosphere. On the contrary, indicative PAH ratios documented a dominance of pyrogenic over petrogenic-derived organic matter in the lake sediments investigated. These contradictory descriptions demonstrate clearly that only a comprehensive application of different marker systems allows a detailed view on the quality and quantity of coal-derived pollution. Lastly, it remains unclear whether coaly material in aquatic sediments acts as sink or source for PAHs. A proposed indicative marker, the ratio of phenanthrene over retene, failed.

This overview focuses on geochemical and geochronological investigations on dated sediment profiles, used for the evaluation of the inventory and fate of persistent pollutants within the aquatic environment over time and space. It includes a short description of the spectrum of sediment contaminants such as heavy metals, polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), pesticides, pharmaceuticals or personal care products, of the contamination sources and pathways, the prerequisites of the analytical approach as well as numerous case studies worldwide. The aim of the review was to summarise the current knowledge related to the historical input of organic and inorganic sediment contaminants into marine, limnic and fluvial sediment archives, their general contamination trends referring to the increase in sediment contamination during the nineteenth and the beginning of the twentieth century as well as source-specific trends of modern or present-day contaminants since the last four decades. Based on the available literature, it demonstrates the benefit of using correlated chronological and geochemical investigations as a tool for the evaluation of the chemical status and risk assessment of pollutants in aquatic sediment archives over long time intervals, for instance since urbanisation and industrialisation started.

The detailed characterization of the organic composition of industrial effluents discharged from various industrial branches and the distribution of the emitted pollutants in the surface waters in North Rhine-Westphalia have been done with the use of non-target screening analyses. Based on the characterization of molecular structures of wastewater constituents, their quantification as well as the available information on their origin and industrial applications, the identification of typical organic representatives for petrochemical and food effluents has been performed. Among a wide range of hydrocarbons detected in the petrochemical effluents, several novel organic wastewater constituents have been found for the first time. In the effluents from paper production plant, potential industrial indicators were distinguished, such as resin acids (abietic and dehydroabietic acids) and photoinitiators (Irgacure 184). The monitoring of the behaviour of certain environmentally relevant and newly described pollutants in the contaminated river systems allowed the identification of several industrial site-specific markers. Particularly, 2-(chloromethyl)-1,3-dioxolane, an unknown contaminant, exclusively found in the effluents from a chemical production complex, was present in the river under discharge at high concentrations downstream the contamination source. The comprehensive and detailed evaluation of the anthropogenic markers in the industrial effluents is a promising tool for the environmental assessment of industrial emissions, especially if accompanied with toxicological and ecotoxicological investigations of novel environmental contaminants.

Organo-clay complexes in soil are a major sink for xenobiotics and, thus, often enhance their persistence dramatically. However, the knowledge on environmental processes of non-extractable residue formation on a short time scale is very restricted. Therefore, this study examined the distribution of 4-(3,5-dimethylhept-3-yl)phenol (NP) and 4-chloro-2-methylphenoxyacetic acid (MCPA) in soil over a short time period of 48 h and in different soil sub-fractions. The overall proportion of organo-clay-associated bound residues was not only abundant but also in the same range for both substances (MCPA: 8%; NP: 11% of applied 14C-radioactivity). However, a more detailed view revealed two different distribution patterns: a higher proportion of clay-associated NP was accompanied by a lower content of bound residues, whereas a smaller fraction of clay-associated MCPA was characterized by a higher proportion of non-extractable residues. Further on, a selective accumulation of bound residues among clay-associated humic fractions was observed. NP residues were linked predominantly to humic acids, whereas MCPA residues tended to be incorporated more into fulvic acids. It was evident that the overall distribution was influenced primarily by the physico-chemical properties of the contaminants. This study demonstrates in detail a rapid initial incorporation accompanied by a specific distribution into soil sub-fractions for selected xenobiotics in soil and points to a complex interaction of clay-associated organic matter with low molecular weight compounds.

Lipophilic anthropogenic contaminants enter the environment from different kinds of human activities and corresponding emission sources. In the hydrosphere, they accumulate frequently in specific sedimentary zones, among others, and at coastal areas, forming reservoirs of pollutants. Marine and freshwater sediment samples as well as soil samples from a highly industrialized coastal area in Northern Greece have been analyzed in order to have a detailed view on the state of the particle-associated pollution. Noteworthy, based on extended GC/MS non-target screening analyses, interesting, so far unknown, or rarely documented contaminants have been identified and quantified comprising, e.g., mono- and dichlorocarbazoles, bromocarbazole, 2,6-di-tert-butyl-4-nitrophenol, etc. However, all relevant contaminants are discussed with respect to their spatial concentration profiles, their emission sources, and their pathway. In addition, numerous pollutants are suggested to become selected for environmental monitoring programs. Hence, this study can act as an example for adapting individual monitoring programs to the individual contamination in coastal areas.

Sediments and soils in coastal areas are frequently polluted by anthropogenic contaminants as the result of both riverine or terrestrial discharge and autochthonic marine emissions. In order to determine petrogenic contamination in the coastal industrial area of Kavala City in northern Greece, a combination of polycyclic aromatic hydrocarbon (PAH) and organic geochemical petroleum biomarker analyses has been performed on marine and freshwater sediments as well as soils. Soils, freshwater, and marine sediments have been treated by standard extraction methods. The dried and desulphurized sample extracts have been fractionated by column chromatography, followed by addition of surrogate standards. Qualitative and quantitative data were obtained by gas chromatograph connected with a flame ionization and electron capture detector (GC-FID/ECD) and by GC linked to a mass spectrometer (GC/MS), whereas identification of compounds was based on EI+-mass spectra and gas chromatographic retention times. Quantitative data were obtained by integration of specific ion chromatograms. The total PAH concentrations measured in the area varied highly, showing different levels from 18 up to 318,000 ng g−1 dry weight (dw). Several PAH ratios, as well as the ratio of pristane (Pr) to phytane (Phyt), have been considered. Out of 39 samples, 22 revealed a specific distribution of hopane fingerprints indicating petrogenic input. Finally, in numerous samples, the ratio of 17α(H)-22,29,30-trisnorhopane (Tm) and 18α(H)-22,29,30-trisnorhopane (Ts) was calculated, as well as the ratio of 22S-17α(H),21β(H)-30 homohopane (αβC31-hopane 22S) and 22R-17α(H),21β(H)-30 homohopane (αβC31-hopane 22R). Based on the specific PAH ratios, a group of samples was clearly characterized to be contaminated dominantly by combustion-derived emissions, whereas a second group of samples exhibited mixed influence from petrogenic and pyrogenic PAHs. On the other hand, the exhibition of specific hopane fingerprints in many samples indicates a direct petrogenic input. Finally, the values of the ratio of Tm/(Ts + Tm) and of αβC31-hopanes 22S/(22S+22R)-isomer demonstrated an input of highly mature organic matter that has to be clearly attributed to petroleum-derived contamination, while the ratio of Pr/Phyt showed that most samples exhibited an input of organic matter. The coastal area of Kavala is strongly affected by anthropogenic contaminants. Petrogenic emissions were pointed out firstly by PAH analyses that separated dominantly pyrogenic contaminated sites from areas affected by both pyrogenic and petrogenic emissions. However, analyses of organic geochemical biomarkers revealed a much higher sensitivity in identifying petroleum-derived contaminations and were successfully used to differentiate several petrogenic contaminations in the marine and terrestrial samples. Based on this study, it was recommended to use a complementary approach of source-specific substances to successfully characterize petrogenic emissions. Generally, a PAH-based source identification of petrogenic versus pyrogenic contaminations should be combined with petroleum biomarker analysis. PAH and biomarker ratios as well as individual biomarker fingerprints revealed a more comprehensive view on the quality and quantity of petrogenic emissions in sediments and soils.

Contaminated groundwater and a riverine sediment core heavily affected by the same industrial point source were analysed for hexachlorocyclohexanes (HCH) and its degradation products. A detailed quantification by GC/MS revealed contamination levels up to 730 μg/L and 396 ng/g in sum for the water and sediment samples, respectively. The isomer pattern differed significantly in both compartments. The ground water samples were depleted in γ-HCH, whereas a significant loss of α-HCH was evident in the sediments as compared to the technical composition. The data obtained revealed interesting insights into the transformation behaviour and fate of HCH mixtures in anaerobic environmental compartments. In the affected groundwater system an ongoing microbial degradation was pointed out by the identification of indicative anaerobic metabolites. On the contrary in the sedimentary system a high environmental stability or rather a hindered degradation was observed as indicated by unaltered concentration levels as compared to production rates as well as by the absence of metabolites. Interestingly, the environmental fate of HCH in subaquatic sediments as well as in anaerobic ground water differs highly in contrast to the behaviour in anaerobic soil or surface water systems. Further on, it has to be stated, that the knowledge about the long-term behaviour of HCH residues in sedimentary material under anaerobic conditions is rather limited so far.

The aim of this study is to identify potential toxic or environmentally relevant organic compounds in the aquifers of the Amynteo hydrogeological basin and to investigate a possible link of the identified organic contaminants with the Pliocene Amynteo lignites. For these purposes, 10 groundwater samples were collected from this area. A sequential liquid–liquid extraction procedure was applied and all extracts were analyzed by gas chromatography and gas chromatography–mass spectrometry (GC–MS) by means of a non-target screening approach. The results of the GC–MS analyses of the extracts are presented and discussed in this work. The identified organic compounds with a potential environmental relevance are: 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, triacetine, isopropyl palminate, isopropyl myristate, tributyl-, triethyl- and trioctylphosphates, N,N-dibutyl formamide, methyl dihydrojasmonate, nonylphenols and bumetrizole. However, all these organic micropollutants can derive either by anthropogenic emissions (plasticizers, industrial pollutants, pesticides, etc.) or by contaminations from the pump and the borehole structure itself. Noteworthy, coal-derived organic molecules (such as anthracene, fluorene, pyrene, phenanthrene, etc.) have not been detected. Hence, an influence of coal deposits to the groundwater quality is considered negligible.

Environmental compartments of riverine systems are polluted by organic contaminants in particular as a result of industrial activity. Sediments and soils of conjunct floodplains can act as archives for long-term anthropogenic pollution. While some chemicals are prevalent, several compounds show source specificity. Compounds closely related to industrial chemical processes comprise precursors, intermediates, and by- and side-products. To better understand the environmental fate of such contamination in aquatic systems, we examined historic sediments of the Mulde River, a riverine system adjacent to the former industrial area Bitterfeld-Wolfen, Germany. This industrial complex produced a variety of chemical compounds between 1950 and the late 1980s. Comparison with related, more recent soil samples from floodplains revealed the presence of these organic indicators (e.g., halogenated naphthalenes, tetrachlorothiophene, dichlorodiphenylsulfone, 1,1,1,2,2-pentachloroethylbenzene, chlorinated diphenylethers) in the uppermost soil layers even over 20 years after the general shutdown of industrial production. Concentrations of numerous non-source-specific pollutants such as DDT metabolites, chlorinated benzenes, and dinaphthyl sulfones were also elevated in most recent wetland soil layers. Generally, concentration profiles showed the highest concentration of compounds in the uppermost soil layer. With increasing soil depth, concentrations decreased. Therefore, the results suggest a continuous input of source and non-source specific contaminations over secondary pollution pathways. This long-term pollution of the environment poses a threat to the quality of riverine systems.

The Jakarta Bay Ecosystem is located in the vicinity of the megacity Jakarta, the capital city of Indonesia. Surrounding rivers and canals, carrying solid and fluid waste from households and several industrial areas, flow into the bay. Therefore, the levels of selected trace hazardous elements in water, surface sediments and animal tissues were determined. Samples were collected from two different seasons. The spatial distribution pattern of trace elements in sediment and water as well as the seasonal variation of the contamination were assessed. Quality assessment of sediment using the effects range median (ERM) showed that the concentrations of Hg, Cu and Cr at some stations exceeded the recommended values. Moreover, the concentrations of several trace hazardous elements in the sediments exceeded previously reported toxicity thresholds for benthic species.

The paper industry is one of the most significant industrial branches that contributes to water pollution. Recent studies regarding the chemical composition of wastewaters from modern paper production sites are sparse, and organic contaminants originating from this source may remain undetected and uncontrolled. Therefore, for this study, non-target screening analyses of wastewaters from five different paper production sites were performed, including an extended analysis of one facility, for the identification of volatile non-polar to semi-polar organic contaminants. The identified contaminants were also traced in the adjacent river. Several specific agents related to paper production, including photoinitiators, ink and thermal paper constituents, were present in most wastewaters and were therefore considered to be characteristic paper industry contaminants. A couple of contaminants identified in this study are being reported for the first time and might be toxic, but have been neglected in previous studies. Bisphenol A and 2,4,7,9-tetramethyl-5-decyne-4,7-diol were found in untreated wastewaters, treated wastewater and in river water. Bisphenol A was present in river water downstream from where the paper industry discharges at a concentration that was reported to affect the reproduction of gastropods. Thus, our findings imply that paper industry discharges pose a risk to the populations of sensitive macroinvertebrates.

Comprehensive GC/MS analysis was applied to both the mobile liquid phase (seepage water) and the immobile solid matter of discrete layers derived from a waste deposit landfill. The vertical distribution of organic compounds supports information on the transport, transfer and transformation processes with depth and, consequently, with time. Numerous low molecular weight organic contaminants of natural and xenobiotic origin were identified and partially quantified. Several were selected to act as molecular indicators for different processes. Interpretation of their occurrence and concentration profiles (considering possible waste sources) and their molecular properties allowed us to (i) differentiate immobile and mobile fractions, (ii) reveal restrictions in the vertical transport by transfer processes between particulate and water phase, (iii) identify dynamic accumulations of individual contaminants and (iv) estimate approximate residence times. In addition, intensive degradation processes were pointed out for the natural fraction of the organic matter by way of determination of specific transformation products. Besides the transformation of natural components, transformation of numerous xenobiotics was recognised. In particular, with respect to an important group of contaminants, the phthalate-based plasticisers, a detailed view of (i) the influence of transfer and transport phenomena on transformation processes as well as (ii) the consecutive appearance of different degradation steps in both seepage water and solid waste was pointed out. The information provides a valuable base for the prediction of the long term behaviour of organic contaminants in waste deposit landfills.

This study describes the application of a common analytical procedure adapted for compound-specific stable carbon isotope analyses of riverine contaminants. To evaluate the sensitivity of the analytical method and the precision of the isotopic data obtained, a set of numerous substances at different concentration levels were measured. For most of the anthropogenic contaminants investigated (including chlorinated aliphatics and aromatics, musk fragrances, phthalate-based plasticizers and tetrabutyl tin) acceptable carbon isotope analyses could be obtained down to amounts of approximately 5 ng absolutely applied to the gas chromatograph. These amounts correspond to concentrations in water samples at a natural abundance level of approximately 50–200 ng L−1 (low to medium contaminated river systems). However, it has to be considered that the precision and the sensitivity of the analytical method depend partially on the chemical properties of the substances measured. Five recovery experiments were conducted to...

The major goal of this study was to investigate the organic pollution of a river on a quantitative basis. To this end, 14 anthropogenic contaminants which were identified in Lippe River water samples as reported in part I (Dsikowitzky et al., submitted parallel to this manuscript) were surveyed. Dissolved organic loads of the specific compounds were calculated on the basis of their concentrations in water and river runoff on the day of sampling. The organic loads of each compound were compiled along the longitudinal section of the river in order to generate individual spatial pollution profiles. It was observed that distribution of organic loads along the river showed distinctive patterns, depending upon the input situation and physico-chemical properties of the compound. The compounds were classified into three types of which Type 1, due to their stability in the aqueous phase, are of special interest for potential application as anthropogenic markers.

A large share of anthropogenic contamination of the coastal zone is a result of riverine contributions. Accordingly, the pollution of North Sea estuaries and coastal areas by organic xenobiotics is dominantly characterized by land-derived contamination. In a previous study, we identified a high number of organic contaminants in sediments of the German Bight emitted by industrial and municipal sources, primarily as a result of riverine contributions. Furthermore, a group of contaminants was identified representing Elbe-specific marker compounds. However, quantitative analyses are more adequate to describe the source specificity via the spatial distribution as compared to qualitative analyses. Hence, in the present investigation, the determination of various anthropogenic contaminants has been performed in order to evaluate the proposed Elbe-specific marker compounds. Numerous anthropogenic contaminants were quantified in seven surface sediment samples from the German Bight by means of gas chromatographic — mass spectrometric analyses. The analytical procedure includes extraction, reI moval of sulphur, fractionation, concentration and addition of internal standard. Two groups of Elbe-derived contaminants were differentiated. Substances of the first group appear only at sampling locations directly influenced by the Elbe river and include hexachlorobutadiene and alkylsulfonic acid phenyl esters. The second group consists of compounds, which occur additionally in minor concentrations at sites situated at a greater distance from the coastal area, which are therefore only influenced to a minor-degree by the Elbe river. However, their spatial and quantitative distribution characterizes them clearly as Elbe river-derived components. Compounds of the second group are tetra- to hexachlorinated benzenes, mono- and disubstituted chloronaphthalenes, tetrabutyltin, 4,4’-dichlorodiphenylsulfide and DDT related compounds In order to discern the discussed Elbe marker compounds from non-marker substances, several nonspecific contaminants were analyzed additionally. These contaminants include galaxolide, tonalide, tri-n-butylphosphate, 2,4,4-trimethylpentane-l,3-dioldi-iso-butyrate and 2,2,4,4,6,8,8-heptamethylnonane. No significant accumulation of these compounds was observed at sampling locations mainly influenced by either the Elbe river, or the Ems and Weser rivers. For the evaluation of the proposed Elbe marker compounds, the quantitative and spatial distribution was investigated and successfully discussed as the most important criterion to define their source specificity. Generally, these results illustrate how quantitative data on source-specific organic contaminants and the corresponding spatial distribution can be used to trace individual riverine contributions to the pollution of coastal areas. This approach might be especially useful to differentiate the contribution of several rivers discharging close together into the marine environment. Fingerprinting, the individual riverine contribution additionally allows one to quantify the individual, river-derived contamination. Subsequently, the level of coastal zone contaminations can be reduced more effectively. Further comprehensive analyses on numerous coastal and estuarine areas have to be done to support this approach.

The proportions of elemental sulphur species in sediment from a contaminated area and a reference sediment sample were compared with the acute toxicity measured in short-term toxicity tests. Octameric elemental sulphur was separated into three operationally defined fractions. Here we show that octameric elemental sulphur contributes to the acute toxicity measured by bioluminescence inhibition. Our findings show that only a small part of extractable elemental sulphur was effective during exposure to the test organisms. A firmly bound fraction of sulphur was found in a contaminated sediment. This information has to be taken into account while interpreting the acute sediment toxicity.

Specific anthropogenic substances derived from seepage and leakage water from a waste deposit landfill were analysed in groundwater and drainage effluents using gas chromatography-mass spectrometry (GC/MS). Here, we demonstrate the application of an organic marker approach to study lateral and vertical distribution of contamination as well as the long-term emission behaviour. Source-specific and environmentally-stable pesticides, plasticisers and pharmaceuticals, such as N,N-diethyl toluamide, N-butyl benzene sulfonamide, clofibric acid, mecoprop and bisphenol A, were quantitatively analysed. A distinct lateral expansion was detected. Although temporal variations were high, no significant trend was observed.

Organic-geochemical investigations were performed on layers of a dated sediment core taken from a riparian wetland of the Lippe river, Germany. The samples were collected from two distinct depth intervals representing sedimentation periods of 1944–1952 and 1972–1984, respectively. Comprehensive screening analyses by gas chromatography-mass spectrometry (GC-MS) revealed a complex mixture of anthropogenic contaminants. Here, we report the quantitative distribution of selected persistent lipophilic organic substances characterizing municipal as well as industrial emissions. Considering both geochemical and geochronological data, we deduced time-dependent information about industrial production and domestic effluents for the region investigated. In addition, usage and subsequent emission of characteristic pollutants into the riverine system were interpreted for both time periods monitored.

Organic-geochemical analyses have been applied to seepage water and leakage water samples of a waste deposit landfill in order to give a comprehensive view on the composition of the organic contaminants. Based on intense GC/MS screening analyses a wide variety of organic substances were identified and attributed to natural or xenobiotic waste components. Apart from plant material-derived compounds and degradation products of peptides, carbohydrates and lignin, numerous xenobiotic substances were identified and attributed to the groups of pharmaceuticals, plasticizers, pesticides or chlorinated aromatics. Not all of the substances identified in the seepage water samples were recovered in the leakage water sample due to degradation processes or dilution by uncontaminated water. Quantitative analysis of selected contaminants was used to discriminate substances affected by degradation processes and persistent compounds.

Due to the very limited number of studies dealing with the chemical composition of industrial wastewaters, many industrial organic contaminants still escape our view and consequently also our control. We present here the chemical characterization of wastewaters from different units of a chemical complex, thereby contributing to the characterization of industrial pollution sources. The chemicals produced in the investigated complex are widely and intensively used and the synthesis processes are common and applied worldwide. The chemical composition of untreated and treated wastewaters from the chemical complex was investigated by applying a non-target screening which allowed for the identification of 39 organic contaminants. According to their application most of them belonged to four groups: (i) unspecific educts or intermediates of industrial syntheses, (ii) chemicals for the manufacturing of pharmaceuticals, (iii) educts for the synthesis of polymers and resins, and (iv) compounds known as typical constituents of municipal sewage. A number of halogenated compounds with unknown toxicity and with very high molecular diversity belonged to the second group. Although these compounds were completely removed or degraded during wastewater treatment, they could be useful as "alarm indicators" for industrial accidents in pharmaceutical manufacturing units or for malfunctions of wastewater treatment plants. Three potential branch-specific indicators for polymer manufacturing were found in the outflow of the complex. Among all compounds, bisphenol A, which was present in the leachate water of the on-site waste deposit, occurred in the highest concentrations of up to 20 000 μg L(-1). The comparison of contaminant loads in the inflow and outflow of the on-site wastewater treatment facility showed that most contaminants were completely or at least significantly removed or degraded during the treatment, except two alkylthiols, which were enriched during the treatment process. The chemical composition of the inflow samples showed a very heterogenic composition and strongly varied, reflecting that large scale industrial synthesis is carried out in batches. The outflow contained mainly unspecific chlorinated educts or intermediates of industrial syntheses as well as compounds which are known as typical constituents of municipal wastewaters.

GC/MS analyses have been applied to sediment samples of the German Bight in order to document the state of organic contamination as well as to identify specific molecular markers that are appropriate to estimate the discharge of anthropogenic compounds derived from the Elbe river. Detailed screening analyses revealed a wide variety of organic lipophilic compounds of biogenic, petrogenic as well as anthropogenic origin. Potential marker compounds indicating the contribution of the Elbe river could be attributed mainly to the chlorinated aromatic contaminants. Specifically, these include tetra- to hexachlorobenzenes, mono- to dichloronaphthalenes, hexachlorobutadiene, tetrabutyl tin, alkylsulfonic acid phenylesters, 1,2,3,6,7,8-hexahydro-1,1,6,6-tetramethyl-4-isopropyl- as -indacene and 4,4′-dichlorodiphenylsulfide. These compounds are suitable to indicate the spatial distribution of Elbe river derived organic matter.

Sediments from the Elbe River and from its major tributaries are shown to be contaminated with arylesters of alkylsulfonic acids. Here we report on the structure elucidation and quantification of aryl esters of alkylsulfonic acids. Chromatographic separation and mass spectrometric properties are discussed. Congener-specific analyses revealed a highly similar pattern throughout the area investigated. Alkylsulfonic acid phenylesters were present at almost all sampling locations. Amounts ranged from 33 000 μg/kg near the industrial region of Bitterfeld to 15 μg/kg in wadden sea sediments. Concentrations of alkylsulfonic acid cresylesters were between 10–40% of the phenylesters, and fell below the detection limit only in the Elbe estuary. The presence of aryl esters of alkylsulfonic acids in all sediment samples analyzed indicates a widespread distribution of these compounds in the environment. Previous literature described these compounds erroneously as phenoxyalkanes.

The Cochin Backwaters in India are part of the Vembanad-Kol system, which is a protected wetland and one of the largest estuarine ecosystems in South Asia. The backwaters are a major supplier of fisheries resources and are developed as tourist destination. Periyar River discharges into the northern arm of the system and receives effluents from chemical, petrochemical and metal processing industries which release huge amounts of wastewaters after little treatment. We investigated water and sediment contamination in the industrial vicinity and at one station further away including organic and inorganic contaminants. In total 83 organic contaminants were found, e.g. well known priority pollutants such as endosulfan, hexachlorobenzene, DDT, hexachlorocyclohexane and their metabolites, which likely stem from the industrial manufacturing of organochlorine pesticides. Furthermore, several benzothiazole, dibenzylamine and dicyclohexylamine derivatives were detected, which indicated inputs from rubber producing facilities. Several of these compounds have not been reported as environmental contaminants so far. A comparison of organic contaminant and trace hazardous element concentrations in sediments with reported sediment quality guidelines revealed that adverse effects on benthic species are likely at all stations. The chemical assessment was combined with an investigation of macrobenthic diversity and community composition. Benthic organisms were completely lacking at the site with the highest trace hazardous element concentrations. Highest species numbers, diversity indices and abundances were recorded at the station with the greatest distance to the industrial area. Filter feeders were nearly completely lacking, probably leading to an impairment of the filter function in this area. This study shows that a combination of chemical and biological methods is an innovative approach to achieve a comprehensive characterization of industrial contamination, to evaluate associated risks for bottom dwelling consumers regarding sediment quality guidelines, and to observe related adverse effects on the benthic community directly in the field.

Industrialization and urbanization in the industrial nations and increasingly also in emerging and developing nations have led to an intensive and still increasing use of freshwater resources. Industries are one of the most important pollution sources and the discharged wastewaters may contain very diverse organic compound groups. Among those, lipophilic contaminants possessing functional groups which are not common in nature rank among the compounds which are most persistent. There have been strong efforts in environmental sciences for a comprehensive characterization of chemical contamination and the related impacts, in order to provide data as a basis for management measures. Here we review the current state of knowledge about organic contaminants from industrial sources. We present information about (i) the identification of organic contaminants in industrial wastewaters, (ii) how these compounds are traced in aquatic systems, and (iii) on their toxicity for aquatic organisms as observed in laboratory experiments and in the field.

It is well known that during biodegradation of oil under natural geological conditions, or oil pollutants in the environment, degradation of hydrocarbons occurs according to a well-defined sequence. For example, the major changes during the degradation process of n-alkanes occur in the second, slight and third, moderate level (on the biodegradation scale from 1 to 10). According to previous research, in the fourth, heavy level, when intensive changes of phenanthrene and its methyl isomers begin, n-alkanes have already been completely removed. In this paper, the ex situ natural bioremediation (non-stimulated bioremediation, without addition of biomass, nutrient substances and biosurfactant) of soil contaminated with heavy residual fuel oil (mazut) was conducted during a period of 6 months. Low abundance of n-alkanes in the fraction of total saturated hydrocarbons in the initial sample (identification was possible only after concentration by the urea adduction technique) showed that the investigated oil pollutant was at the boundary between the third and the fourth biodegradation level. During the experiment, an intense degradation of phenanthrene and its methyl-, dimethyl- and tri-methyl-isomers was not accompanied by the removal of the remaining n-alkanes. The abundance of n-alkanes remained at the initial low level, even at end of the experiment when the pollutant reached one of the highest biodegradation levels. These results showed that the non-stimulated biodegradation of some hydrocarbons, despite their high biodegradability, had not proceeded completely to the end, even at final degradation stages. Under the condition of reduced availability of some hydrocarbons, microorganisms tend to opt for the less biodegradable but more accessible hydrocarbons. Dobro je poznato da se u toku biodegradacije nafte u prirodnim geološkim uslovima, ili naftnog zagađivača u životnoj sredini, degradacija ugljovodonika odigrava prema definisanom rasporedu. Na primer, glavne promene u procesu razgradnje normalnih alkana dešavaju se u toku drugog, "blagog", i trećeg, "umerenog", stupnja (na skali biodegradacije od 1 do 10). Prema dosadašnjim istraživanjima, u četvrtom stupnju, kada počinju intenzivne promene fenantrena i njegovih metil izomera, normalni alkani su već u potpunosti uklonjeni. U ovom radu u toku perioda od 6 meseci izvođena je ex situ prirodna bioremedijacija (nestimulisana bioremedijacija bez dodatka biomase, hranljivih sastojaka i biosurfaktanata) zemljišta zagađenog mazutom. Niska obilnost normalnih alkana u frakciji ukupnih zasićenih alkana u početnom uzorku (identifikacija je bila mogućna tek nakon koncentrovanja pomoću karbamida) pokazala je da je ispitivani naftni zagađivač na granici između trećeg i četvrtog stupnja biodegradacije. Tokom eksperimenta, intenzivnu razgradnju fenantrena i njegovih metil, dimetil i trimetil izomera nije pratilo uklanjanje ostatka normalnih alkana. Njihova obilnost je ostala na početnom, niskom nivou i na kraju eksperimenta kada je zagađivač dostigao jedan od najviših stepena biodegradacije. Dobijeni rezultati su pokazali da se razgradnja pojedinih ugljovodonika uprkos njihovoj visokoj biodegradabilnosti ne odigrava do potpunog kraja ni u završnim fazama degradacije. U uslovima njihove smanjene dostupnosti, mikroorganizmi se opredeljuju za teže degradabilne, ali dostupnije ugljovodonike.

GC/MS non target screening has been applied to water samples taken during 1992–1994 from the Elbe river and its tributaries Mulde, Saale, Weise Elster, Schwarze Elster, and Havel. Based on full scan electron impact mass spectra and supplemented by extensive use of chemical ionisation and high resolution data as well as by synthetic reference compounds, several new classes of compounds, whose possible environmental effects are yet unknown at present, have been identified. Tetrachlorinated bis-(propyl)ethers are new among the most prominent contaminants throughout the Elbe river. The confluence with the Mulde river adds a variety of compounds, related to the chemistry of chloro- and nitroaromatics, azo dyes, benzanilides, carbamates, thiophosphates, and pesticides. The combined load of the Weise Elster and Saale rivers carries oligoformals, oxathiamacrocycles, and dichloro- and trichloro-bis-(propyl)ethers, whereas chloropropylphosphates are introduced via the Schwarze Elster. The majority of these compounds, originating from sources at the tributaries, are still present at the mouth of the Elbe river. In addition to specific industrial emissions, a variety of more generally observed organic compounds like long chain aliphatics, sterols, phenylalkanes, and plasticizers as well as ubiquitous environmental trace pollutants like polycyclic aromatic hydrocarbons, chlorobenzenes, and hexachlorocyclohexane isomers have been encountered throughout the Elbe river drainage system.

Sediment archives are mind of aquatic systems.We report historical trends of marine, limnic and fluvial sediment contamination. Over the last four decades, the increasing problems of environmental contamination induced a growing interest in the fate and sources of pollution. Environmental contaminants emitted by human activities can be stored ultimately in sediments which act under these circumstances as a sink. In this context, historical monitoring studies of aquatic sediment archives are used to assess the extent and effect of human inputs in the past towards the present. This review gives a summary of the available literature concerning definitive time trends of the contamination load determined in estuarine, fluvial and limnic sedimentary archives. It gathers information about main input sources and contamination pathways as well as the spectrum of anthropogenic contaminants in aquatic sediment deposits. In addition, special chapters point to (i) the prerequisites of the methodical approach, (ii) the spectrum of sediment contaminants, (iii) suitable sedimentary archives as well as (iv) the standard methods of sediment dating. Finally, this review highlights representative studies on pollution histories exemplifying the potential of geochronological investigations on common and modern pollutants.

Data interpretation of the Porewater Chemistry (PC) experiment at the Mont Terri Rock Laboratory has led to unexpected observations of anaerobic microbial processes which caused important geochemical perturbations of the Opalinus Clay water in the borehole. The increases of acetate to 146 mg C/L, of DIC to 109 mg C/L and of CH4 to 0.5 mg C/L were unexpected and could not be explained without the presence of a C source in the system. The organic C fuelling the observed microbial activity was until then unknown. Leaching tests were performed on several polymers used for the fabrication of the PC equipment to identify the source of organic matter (OM). Polyethylene (PE) appears to be very inert and does not release detectable concentrations of dissolved organic C (DOC) (

Building up a comprehensive accurate monitoring program requires the knowledge on the contamination in principal, complemented by detailed information on individual contaminants. The selection of pollutants to be considered in monitoring actions is based dominantly on the information available about their environmental relevance (e.g., persistence, bioaccumulation potential, toxicological and ecotoxicological properties) and their occurrence within the affected environmental system. Therefore, this study focused on the identification of organic contaminants in selected German and European rivers to demonstrate the usefulness of a screening approach as complementary base for the compound selection process within monitoring activities.Gas chromatography-mass spectrometry-based screening analyses were performed on five and six samples from German and European rivers, respectively. Identification of individual contaminants was based on the investigation of mass spectral and gas chromatographic properties compared with databases and reference materials.This study summarized the results of non-target screening analyses applied to river water samples and focused dominantly on, so far, unnoticed organic contaminants. Numerous compounds have been identified belonging to the groups of pharmaceuticals, technical additives, pesticides, personal care products, and oxygen-, nitrogen-, and sulfur-containing compounds of obviously anthropogenic origin. They are discussed in terms of their structural properties, their possible application or usage, and the environmental information available so far.Generally, two different groups of compounds have been differentiated that might contribute to potential monitoring programs. Firstly, more specific contaminants characterizing the individual riverine systems have been depicted (e.g., 4-chloro-2-(trifluoromethyl)aniline, di-iso-propylurea). The consideration of these substances in monitoring analyses to be applied to the corresponding catchment areas is recommended in order to monitor the real state of pollution. Secondly, contaminants have been introduced that appeared with higher multiplicity throughout the different river systems (e.g., TMDD, TXIB). Since these compounds tend to obviously have an elevated environmental stability accompanied by a widespread distribution, it is recommended to consider them in international high-scale monitoring programs.For monitoring purposes, a fundamental knowledge on the diversity of pollutants is an important precondition, which can be supported by screening analyses. Obviously, numerous organic contaminants have been neglected so far in environmental studies on river water, comprising also investigation on potential harmful effects and, therefore, their implementation in monitoring activities has been hindered.Therefore, based on the results of this study, screening analyses should be established as principle tools to improve and complement the substance spectra for monitoring purposes. Secondly, scientific efforts should be strengthened to expand our knowledge on actually appearing organic contaminants in riverine systems.

Based on extensive GC/MS screening analyses, the molecular diversity of petrochemical effluents discharged to a river in North Rhine-Westphalia was characterised. Within a wide spectrum of organic wastewater constituents, specific compounds that might act as source indicators have been determined. This differentiation was based on (i) the individual molecular structures, (ii) the quantitative appearance of organic compounds in treated effluents and (iii) the information on their general occurrence in the technosphere and hydrosphere. Principally, site-specific indicators have been distinguished from candidates to act as general petrochemical indicators. Further on, monitoring the environmental behaviour of target organic contaminants in an aquatic system shortly after their release into the river allowed a first evaluation of the impact of the petrogenic emission in terms of the quantity and spatial distribution. The identification of petrogenic contaminants was not restricted to constituents of the effluents only, but comprised the compounds circulating in the wastewater systems within a petrochemical plant. A number of environmentally relevant and structurally specific substances that are normally eliminated by wastewater treatment facilities were identified. Insufficient wastewater treatment, careless waste handling or accidents at industrial complexes are potential sources for a single release of the pollutants. This study demonstrates the relevance of source specific organic indicators to be an important tool for comprehensive assessment of the potential impact of petrochemical activities to the contamination of an aquatic environment.

Identification of persistent and emerging organic contaminants in green mussels (Perna viridis), various fishes, banana shrimp (Penaeus merguiensis) and sediment samples from Jakarta Bay has been employed. A non-target GC-MS screening approach has identified more than 60 individual organic compounds from the whole fractions either non-polar, semi-polar or acidic-polar compounds. The substances comprised as persistent organic pollutants (POPs) including DDT (dichlorodiphenyl trichloroethane) and its metabolites as well as high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs). Noteworthy, a number of emerging contaminants detected in the present study have never been reported previously either from the same location or from Asian waters. They include some priority contaminants of non-persistence halogens and emission of technical products, such as di-iso-propylnaphthalenes (DIPNs) dichlorobenzene (DCB), dichlorodiphenyl chloroethene (DDMU) and phenylmethoxynaphthalene (PMN). In general, the concentration order of the priority organic contaminants was sediment > green mussel > fishes > shrimp. Further analysis based on the spatial distribution, individual concentrations and bioavailability suggested that some contaminants are applicable as molecular marker for the assessment of anthropogenic emission in Jakarta Bay, i.e. DIPNs, linear alkylbenzenes (LABs), phenylmethoxynaphthalene (PMN), PAHs, dichlorobenzene, DDT and its metabolites.

Eight terrestrial and four marine water samples were collected from the industrial section of the city of Kavala in northern Greece to determine the occurrence and distribution of organic contaminants, as well as to identify the molecular markers of different emission sources. The samples were analyzed by means of non-target screening analyses. The analytical procedure included a sequential extraction of the samples, GC-FID, GC/MS analyses, and additional quantitative analyses of selected pollutants. The results show a wide variety of compounds including halogenated compounds, technical additives and metabolites, phosphates, phthalates, benzothiazoles, etc. A close relationship between many of the contaminants and their emission sources was determined based on their molecular structures and information on technical applications.