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Hadal trenches are unique geological and ecological systems located along subduction zones. Earthquake-triggered turbidites act as efficient transport pathways of organic carbon (OC), yet remineralization and transformation of OC in these systems are not comprehensively understood. Here we measure concentrations and stable- and radiocarbon isotope signatures of dissolved organic and inorganic carbon (DOC, DIC) in the subsurface sediment interstitial water along the Japan Trench axis collected during the IODP Expedition 386. We find accumulation and aging of DOC and DIC in the subsurface sediments, which we interpret as enhanced production of labile dissolved carbon owing to earthquake-triggered turbidites, which supports intensive microbial methanogenesis in the trench sediments. The residual dissolved carbon accumulates in deep subsurface sediments and may continue to fuel the deep biosphere. Tectonic events can therefore enhance carbon accumulation and stimulate carbon transformation in plate convergent trench systems, which may accelerate carbon export into the subduction zones., (© 2023. Springer Nature Limited.)

The present-day human footprint is traceable in all environments. Growing urban centers, tourism, agricultural and industrial activities in combination with fishery, aquacultures and intense naval traffic, result in a large output of pollutants onto coastal regions. The Algarve shelf (Portugal) is one exemplary highly affected coastal system. With this study the contemporary pollution was followed in eighteen offshore surface sediment samples. Heavy metals (e.g., Cr, Pb, Cu, Hg) and organic contaminants, such as linear alkylbenzenes, dichlorodiphenyltrichloroethane metabolites, polycyclic aromatic hydrocarbons, and hopanes, have been identified and quantified, that pose hazardous effects on the marine environment and biota. This study correlates spatial distribution patterns with the pollutant composition, potential sources and pathways, each sample's grain size, and local influences, such as discharging river systems and ocean currents. This study presents a blueprint-study that allows the methodological adaption to new shelf systems with regionally different ocean current-driven distribution patterns of anthropogenic pollutants., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

While it is well recognized that the frequency and intensity of flood events are increasing worldwide, the environmental, economic, and societal consequences of remobilization and distribution of pollutants during flood events are not widely recognized. Loss of life, damage to infrastructure, and monetary cleanup costs associated with floods are important direct effects. However, there is a lack of attention towards the indirect effects of pollutants that are remobilized and redistributed during such catastrophic flood events, particularly considering the known toxic effects of substances present in flood-prone areas. The global examination of floods caused by a range of extreme events (e.g., heavy rainfall, tsunamis, extra- and tropical storms) and subsequent distribution of sediment-bound pollutants are needed to improve interdisciplinary investigations. Such examinations will aid in the remediation and management action plans necessary to tackle issues of environmental pollution from flooding. River basin-wide and coastal lowland action plans need to balance the opposing goals of flood retention, catchment conservation, and economical use of water., (Copyright © 2021. Published by Elsevier B.V.)

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)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The tremendous increase of plastic production, its intensive usage in packaging, as transport material, and the insufficient management of plastic garbage have led to a rise in microplastic particles as an anthropogenic contaminant in our environment. To develop appropriate management and remediation strategies for this global pollution problem, reliable and consistent analytical procedures for measuring plastics in the complex matrices need to be designed. The applicability of an easy, robust and fast multi-step approach was tested on three sediment samples from riverine, beach and backwater areas of varying origin, grain size and organic matter content, and is reported here. The optimized method included grain size fractionation, density separation and μ-FTIR analyses. Identification was based on two complementary methods of μ -FTIR measurements, the Image mode for small microplastics (<1 mm) and the ATR method for bigger (1-5 mm) particles. The analyses revealed the identification of several polymers in various grain sizes at different pollution levels. Major findings are the dominance of PET particles and the highest frequency of microplastic particles in the midsize fraction of 100-500 μm. Generally, the method was able to reliably detect microplastic particles in several grain size fractions and down to very low contamination levels of approximately. ten particles per 50 g of sediments with different organic matter content and various grain size characteristics. Moreover, the presented multi-step approach represents a fast, easy and less cost-effective method as an alternative to more expensive and time-consuming methods.

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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Microplastic particles have been recognized as global hazardous pollutants in the last few decades pointing to the importance of analyzing and monitoring microplastics, especially in soils and sediments. This study focused on a multi-step approach for microplastic analysis combining grain size fractionation, density separation and identification by μ-FTIR-spectroscopy. Eight widely used polymers (polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), polystyrol (PS), polyethylenterephthalate (PET), polymethylmethacrylate (PMMA), polyurethane (PU) and polyamide (PA)) were fractionated into four groups of grain sizes (0.1-5 mm). Thereafter, sea sand was spiked with these particles to test a ZnCl 2 -based density separation for the polymer types and the various grain sizes. The obtained recovery rates were close to 100% showing that ZnCl 2 -based density separation is suitable to separate the polymer particles from a sandy matrix. This approach was extended on three further environmental matrices and recovery rates for two of them (sandy-silty and fine-grained sediment) also provided reliable values (94-106%). Lastly, the developed multi-step approach was verified by analyzing an environmental sample (sediment from river Tiranë, Albania) characterized by smaller grain size and moderate organic matter content. Identification of two polymer types in different grain size classes verified the suitability of the developed approach for microplastic analyses on particulate matter such as soils and sediments.

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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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 pesticide DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene) and its degradates are among the most persistent and abundant organochlorine contaminates in the environment, and DDT is still being produced in several Asian countries. In this study, we report for the first time on the detection of DDT-related compounds with one additional or missing chlorine atom at the phenyl group (DDX ±Cl ) in sediment and soil samples taken in the vicinity of former and current DDT production sites. These congeneric compounds most likely originate from production residues disposed of into the environment. In order to ensure an adequate identification and quantification of this novel organic pollutant group, individual DDX ±Cl were synthesized as reference compounds by simulating an impure production of DDT in the laboratory. In contrast to DDX ±Cl with (chloro)alkyl moieties, DDX ±Cl with (chloro)alkenyl moieties cannot be unambiguous assigned by gas-chromatographic/mass spectrometric (GC/MS) fragmentation and elution orders. The occurrence of DDX ±Cl in environmental samples allows to draw conclusions about the purity of the production process in the associated production sites. Moreover, they potentially can serve as molecular indicators to differentiate between industrial DDT emissions and insecticidal applications of DDT. This hypothesis has yet to be confirmed by further research., (Copyright © 2018 Elsevier B.V. All rights reserved.)

During the last decades, the global industrial production partly shifted from industrialized nations to emerging and developing countries. In these upcoming economies, the newly developed industrial centers are generally located in densely populated areas, resulting in the discharge of often only partially treated industrial and municipal wastewaters into the surface waters. There is a huge gap of knowledge about the composition of the complex organic pollutant mixtures occurring in such heavily impacted areas. Therefore, we applied a non-target screening to comprehensively assess river pollution in a large industrial area located in the megacity Jakarta. More than 100 structurally diverse organic contaminants were identified, some of which were reported here for the first time as environmental contaminants. The concentrations of paper manufacturing chemicals in river water-for example, of the endocrine-disrupting compound bisphenol A (50-8000 ng L -1 )-were as high as in pure untreated paper industry wastewaters. The non-target screening approach is the adequate tool for the identification of water contaminants in the new global centers of industrial manufacturing-as the first crucial step towards the evaluation of as yet unrecognized environmental risks.

The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH - , BBr 3 , RuO 4 , TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.

There is a lack of knowledge in environmental pollution of the anthropogenic contaminants in wastewater and surface water. Several organic compounds merit special attention, because of their potential risk to the aquatic environment. Therefore, gas chromatography-mass spectrometry-based screening analyses were performed in order to identify anthropogenic organic contaminants and to reveal information on the structural diversity of individual compounds and to characterize their environmental behavior. Wastewater samples from wastewater treatment plants in Germany, representing various capacities, and surface water samples from corresponding receiving waters were analyzed. Numerous substances were identified in the samples. Several compounds were treated inadequately during wastewater treatment, and their identification in surface waters highlights their potential impact on the aquatic environment. Contaminants were selected according to available information about their environmental relevance (e.g. persistence, bioaccumulation potential), their possible application or usage and their occurrence within the environment. Based on the results of this study, it is recommended that non-target screening analyses be undertaken to identify the structural diversity of anthropogenic organic contaminants and that further investigations of specific anthropogenic compounds be undertaken as a high priority.

For decades, plasticizers have been produced in high quantities to improve the flexibility and durability of products. One possible replacement product is alkylsulfonic acid phenylesters (ASEs), marketed as Mesamoll ® . This study aimed to quantify the ASE dust contamination of residences and daycare centers to obtain insight into the recent exposure situation. ASEs were quantified in dust samples collected from 25 residences and 25 daycare centers using GC/MS measurements. Median (95th percentile) values of the sum of tetra- to heptadecylphenylesters are higher in daycare centers, with a value of 19.6mg/kg (216mg/kg), compared to residences, with a value of 7.6mg/kg (171mg/kg). A daily non-dietary intake of 0.08 and 0.86μg/kg b.w., respectively, was observed using the median and 95th percentile values obtained from dust samples. These levels are 1250 and 115 times below a previously set temporary tolerable daily intake value. Nevertheless, the fact that basic data on toxicity and exposure via other pathways are limited or unavailable at present has to be considered., (Copyright © 2016 Elsevier GmbH. All rights reserved.)

Protecting our water resources in terms of quality and quantity is considered one of the big challenges of the twenty-first century, which requires global and multidisciplinary solutions. A specific threat to water resources, in particular, is the increased occurrence and frequency of flood events due to climate change which has significant environmental and socioeconomic impacts. In addition to climate change, flooding (or subsequent erosion and run-off) may be exacerbated by, or result from, land use activities, obstruction of waterways, or urbanization of floodplains, as well as mining and other anthropogenic activities that alter natural flow regimes. Climate change and other anthropogenic induced flood events threaten the quantity of water as well as the quality of ecosystems and associated aquatic life. The quality of water can be significantly reduced through the unintentional distribution of pollutants, damage of infrastructure, and distribution of sediments and suspended materials during flood events. To understand and predict how flood events and associated distribution of pollutants may impact ecosystem and human health, as well as infrastructure, large-scale interdisciplinary collaborative efforts are required, which involve ecotoxicologists, hydrologists, chemists, geoscientists, water engineers, and socioeconomists. The research network "project house water" consists of a number of experts from a wide range of disciplines and was established to improve our current understanding of flood events and associated societal and environmental impacts. The concept of project house and similar seed fund and boost fund projects was established by the RWTH Aachen University within the framework of the German excellence initiative with support of the German research foundation (DFG) to promote and fund interdisciplinary research projects and provide a platform for scientists to collaborate on innovative, challenging research. Project house water consists of six proof-of-concept studies in very diverse and interdisciplinary areas of research (ecotoxicology, water, and chemical process engineering, geography, sociology, economy). The goal is to promote and foster high-quality research in the areas of water research and flood-risk assessments that combine and build off-laboratory experiments with modeling, monitoring, and surveys, as well as the use of applied methods and techniques across a variety of disciplines.

The main objective of this study was the development of simple multi-parameter methods for the analyses of biocides in various environmental matrices (wastewater, surface water, and sewage sludge) for measurement and monitoring activities. Eight target substances (triclosan, methyltriclosan (transformation product of triclosan), cybutryne (Irgarol), and the azole fungicides propiconazole, tebuconazole, imazalil, thiabendazole, and cyproconazole) were chosen for determination in selected sample sets. For surface water and wastewater samples a solid-phase extraction (SPE) method and for sewage sludge samples an accelerated solvent extraction (ASE) were developed. The extracts were analyzed by gas chromatographic-mass spectrometric methods (GC/MS), and the analytical methods were checked to ensure sufficient sensitivity by comparing the limits of quantification (LOQs) to the predicted no effect concentrations (PNECs) of the selected biocides. For quality control, recovery rates were determined. Finally, developed methods were checked and validated by application on sample material from various matrices. Sampling took place in seven urban wastewater treatment plants and their corresponding receiving waters. The results revealed that the developed extraction methods are effective and simple and allow the determination of a broad range of biocides in various environmental compartments.

Jakarta Bay, next to the Jakarta Metropolitan Area with around 30 million inhabitants, is facing extreme pollution. Although local coral reefs are degraded and marine resources heavily exploited, they provide livelihoods for millions of people. This study investigates anthropogenic pressures on local fisheries resources and associated livelihoods. Questionnaire surveys were conducted in 15 coastal communities (10 coastal neighborhoods in Jakarta Bay on the mainland and 5 of the offshore Thousand Islands). The most economically valuable species were Caesio cuning (Redbelly yellowtail fusilier) on the islands and Rastrelliger kanagurta (Indian mackerel) on the mainland. Over 80% of all interviewed fishermen regarded the current state of marine resources as declining, mainly due to pollution and overexploitation. While perceptions of declining resources were equally high on the islands and the mainland, pollution was listed as the principal cause of degradation significantly more on the mainland. Findings are discussed in the context of coastal livelihood vulnerability., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Sediment geochemistry of the Jakarta region, a densely populated tropical coast, is studied - with particular focus on rivers discharging to Jakarta Bay. Weathering volcanics in the river catchment area control the composition of major elements, As, Cr and in part Cu. In contrast, Zn, Ni, Pb and partly Cu are affected by anthropogenic sources, mainly in central Jakarta City. The data reflect a high variability of local emission sources, among which metal processing industries, fertilizers or untreated animal waste may be important. In particular, the role of street dusts is emphasized. Locally, heavy metals reach levels considered to have adverse biological effects. River discharge leads to anthropogenic enrichment of heavy metals in the coastal sediments. Element data also show geogenic effects on the composition of the coastal sediments, such as mixing of detrital silicates with biogenic carbonates as well as suspended particulate matter from the ocean., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In order to take actions against the annual flooding in Jakarta, the construction of a Giant Seawall has been proposed in the Master Plan for National Capital Integrated Coastal Development. The seawall provides a combination of technical solutions against flooding, but these will heavily modify the mass transports in the near-coastal area of Jakarta Bay. This study presents numerical simulations of river flux of total nitrogen and N,N-diethyl-m-toluamide, a molecular tracer for municipal waste water for similar scenarios as described in the Master Plan. Model results demonstrate a strong accumulation of municipal wastes and nutrients in the planned reservoirs to extremely high levels which will result in drastic adverse eutrophication effects if the treatment of municipal waste water is not dealt with in the same priority as the construction of the Giant Seawall., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Side and initial degradation products of the persistent organic pollutant hexachlorocyclohexane (HCH) were largely neglected in environmental analysis so far. However, these compounds can be indicative for biodegradation or emission sources. Thus, several samples from a contaminated riverine system in vicinity to a former HCH production site in Central Germany were analyzed. This area adjacent to the industrial megasite Bitterfeld-Wolfen is known for elevated concentrations of various organic industrial pollutants as legacy of decades of industrial activity and subsequent deposition of chemical waste and emission of waste effluents. In environmental compartments of this riverine system, several isomers of HCH related compounds were detected comprising the two lower chlorinated species tetrachlorocyclohexene (TeCCH) and pentachlorocyclohexene (PeCCH) and the higher chlorinated species heptachlorocyclohexane (HpCCH). Except for the uppermost soil of an analyzed riparian wetland, concentrations of these compounds were low. Detected isomers in sediment, water, and soil samples correlated and dominant isomers of PeCCH and HpCCH were observed in the alluvial deposits. Comparisons with industrial HCH waste revealed isomeric patterns similar to patterns found in soil samples. Therefore, the application of HpCCH as an indicator of industrial HCH pollution is suggested., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Investigations of the bioavailability and toxicity of polycyclic aromatic compounds (PAC) have rarely considered the heterogeneity of coals and the impact of more polar PAC besides polycyclic aromatic hydrocarbons (PAH). Earlier, we investigated the toxicity of eight heterogeneous coals and their extracts. In the present study, the hazard potential with respect to mechanism-specific toxicity of polar fractions of dichloromethane extracts from coals was studied. Polar extract fractions of all coal types except for anthracite induced EROD activity (determined in RTL-W1 cells), independent of coal type (Bio-TEQs between 23 ± 16 and 52 ± 22 ng/g). The polar fractions of all bituminous coal extracts revealed mutagenic activity (determined using the Ames Fluctuation test). No significant mutation induction was detected for the polar extract fractions from the lignite, sub-bituminous coal and anthracite samples, which indicates a higher dependency on coal type for polar PAC here. Additionally, information on bioavailability was derived from a bioaccumulation test using the deposit-feeding oligochaete Lumbriculus variegatus which was exposed for 28 days to ground coal samples. Despite the high toxic potential of most coal extracts and a reduced biomass of Lumbriculus in bituminous coal samples, bioaccumulation of PAH and mortality after 28 days were found to be low. Limited bioaccumulation of PAH (up to 3.6 ± 3.8 mg/kg EPA-PAH) and polar PAC were observed for all coal samples. A significant reduction of Lumbriculus biomass was observed in the treatments containing bituminous coals (from 0.019 ± 0.004 g to 0.046 ± 0.011 g compared to 0.080 ± 0.025 g per replicate in control treatments). We conclude that bioavailability of native PAC from coals including polar PAC is low for all investigated coal types. In comparison to lignite, sub-bituminous coals and anthracite, the bioavailability of PAC from bituminous coals is slightly increased., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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.

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., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A simple and effective experimental approach has been developed and tested to study the temperature dependence of high-pressure methane sorption in moist organic-rich shales. This method, denoted as "multi-temperature" (short "multi-T") method, enables measuring multiple isotherms at varying temperatures in a single run. The measurement of individual sorption isotherms at different temperatures takes place in a closed system ensuring that the moisture content remains constant. The multi-T method was successfully tested for methane sorption on an organic-rich shale sample. Excess sorption isotherms for methane were measured at pressures of up to 25 MPa and at temperatures of 318.1 K, 338.1 K, and 348.1 K on dry and moisture-equilibrated samples. The measured isotherms were parameterized with a 3-parameter Langmuir-based excess sorption function, from which thermodynamic sorption parameters (enthalpy and entropy of adsorption) were obtained. Using these, we show that by taking explicitly into account water vapor as molecular species in the gas phase with temperature-dependent water vapor pressure during the experiment, more meaningful results are obtained with respect to thermodynamical considerations. The proposed method can be applied to any adsorbent system (coals, shales, industrial adsorbents) and any supercritical gas (e.g., CH4, CO2) and is particularly suitable for sorption measurements using the manometric (volumetric) method.

The incorporation process of a defined (13)C- and (14)C-labeled nonylphenol isomer (4-(3,5-dimethylhept-3-yl)phenol) into soil-derived organo-clay complexes was investigated. Isolated organo-clay complexes were separated into humic subfractions. Noninvasive ((13)C-CP/MAS NMR) and invasive methods (sequential chemical degradation, pyrolysis) were applied to obtain detailed information about the mode of incorporation, chemical structure, and change of the incorporation character of nonextractable residues in course of incubation. (13)C-CP/MAS NMR measurements of humic acids revealed an increasing incorporation of phenolic compounds during the experimental time which was referred to residues of the introduced (13)C-labeled NP isomer. Detailed investigations by means of sequential chemical degradation indicated a predominant incorporation of nonextractable NP isomer residues via reversible ester (amide) bonds. In course of time, the amount of releasable compounds decreased, pointing to altering processes which affected the mode of incorporation. BBr3-treatment, RuO4 oxidation, and thermochemolysis released only low portions of nonextractable radioactivity giving evidence of strongly incorporated residues. With the comprehensive application of complementary methods (e.g., humic matter fractionation, (13)C-CP/MAS NMR, sequential chemical degradation) it was possible to provide a comparatively detailed insight into the incorporation behavior of the applied NP isomer.

The structural diversity of the wastewater composition was described by the use of detailed non-target screening analyses of industrial effluents from chemical production sites. Determination of the indicative organic compounds acting as potential molecular indicators for industrial emissions from chemical production industries has been possible due to (i) detailed characterisation of industrial contaminants and identification of compounds with high source specificity, (ii) quantitative determination of the organic constituents in the industrial effluents and (iii) the review of their industrial applications. The determination of potential site-specific markers and industrial molecular indicators corresponding to certain production processes (production of starting materials for manufacturing paper and printing inks, powder coatings as well as epichlorohydrin production) was performed in this work. The results of this study allowed significant contributions to the chemical characterisation of industrial contaminants and isolation of indicators that can act as representatives of industrial effluents in the aquatic environment., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, (14)C- and (13)C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied (14)C was mineralized. The bioavailable, water extractable portion was low (9 % of applied (14)C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied (14)C was incorporated into organo-clay complexes as NER, whereas 9 % of applied (14)C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.

Groundwater samples contaminated by an industrial point source were analysed in order to reveal the structural diversity of halogenated organic contaminants. Particular focus was laid on the metabolites and derivatives related to the pesticides DDT (2,2-bis(chlorophenyl)-1,1,1-trichlorethane) and lindane (γ-hexachlorocyclohexane). Additionally, a wide range of chlorinated and brominated xenobiotics were identified. These results represent a high degree of contamination with organochlorine compounds illustrating a considerable structural diversity in groundwater in the vicinity of the industrial plant. The polar DDT-metabolite DDA (2,2-bis(chlorophenyl)acetic acid), which has been neglected in water studies widely, represents the main DDT metabolite analysed in the water samples. Besides DDA, some unknown substances with structural relation to DDA and DDT were detected and identified, in detail 2,2-bis(4-chlorophenyl)acetic acid N-methyl amide (DDAMA) and 2,2-bis(4-chlorophenyl)acetic acid n-butyl ester (DDABE). As an overall implication of this study it has to be demanded that analysis of industrially affected ground waters have to be based on screening analysis for a comprehensive view on the state of pollution., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

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.

Subaquatic sediment samples derived form Elbe and Mulde Rivers, Germany, were analyzed for extractable and non-extractable anthropogenic organic compounds by a non-target screening approach. Applied methodologies were gas chromatography-mass spectrometry, dispersion extraction and degradation procedures, particularly alkaline and acidic hydrolysis, boron tribromide treatment, ruthenium tetroxide oxidation as well as pyrolysis and TMAH (tetramethylammonium hydroxide)-thermochemolysis. Numerous compounds were identified, including halogenated benzenes, anisoles, styrenes, alkanes, diphenylmethane derivates, anilines, phenols and diphenyl ethers. The results were interpreted with respect to compound specific modes of incorporation as well as to potential sources (e.g. municipal, agricultural, industrial). Extractable and non-extractable fractions differed significantly with respect to their qualitative and quantitative composition. For example, quantities in the extractable and non-extractable fractions of chlorinated benzenes differed up to factor 50. Among other significant results, the investigation revealed hints for a dependence of the mode of incorporation of chlorinated benzenes on their substitution pattern.

Eighteen pre-extracted samples derived from a subaquatic riverine sediment core taken from the Teltow Canal, Berlin (Germany), were treated by off-line TMAH-thermochemolysis and subsequently analyzed by GC-MS to investigate release and thermodegradation of non-extractable anthropogenic organic compounds (bound residues). Furthermore, six selected samples from the lower core section were additionally treated by off-line pyrolysis. Due to former investigations of the extractable fraction of Teltow Canal sediments, high amounts of compounds structurally related to the pesticide DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) were anticipated within the nonextractable fraction. It has been shown that DDT-related bound residues can be gathered by pyrolysis and TMAH-thermochemolysis. Among other compounds, the experiments revealed two DDT-related degradation products (DDPU (3,3-bis(4-chlorphenyl)-1-propene) and DDPS (1,1-bis(4-chlorophenyl)propane)) which were detected for the first time in the environment. The latter compounds may represent formerly unknown metabolites or hints for the existence of carbon-carbon incorporated DDT-metabolites. Both methods tend to produce artifacts which complicate the interpretation of the results. With more knowledge on mechanisms occurring during application of pyrolysis and thermochemolysis, both methods can serve as valuable tools for analyzing bound residues in sediments.

To study the recent contamination history of DDT (1,1,1-trichloro-2,2-bis(chlorophenyl)ethane) and its metabolites, as well as methoxychlor (1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane), chlorfenson (4-chlorophenyl-p-chlorobenzenesulfonate), and further halogenated aromatics, a sediment core was collected from the Teltow Canal in Berlin (Germany). The sampling site is located nearby a former industrial point source, where recently analyses on pre-samples have indicated high concentrations of halogenated organic compounds. The deposition time of the investigated sediments was determined by gamma-spectrometrical dating. Pollution trends of selected contaminants were attributed to a time period between 5 and 10 years. Concentration profiles reflect not only the recent pollution history of these compounds, but also the time-depending effects of the ban, restriction and termination of DDT-production in the German Democratic Republic (GDR). DDT and other chlorinated aromatic compounds were produced onsite until the late 1980s. Maximum values of 133 mg kg(-1) (dry weight) for p,p'-DDD (1,1-dichloro-2,2-bis(chlorophenyl)ethane) and approximately 100 mg kg(-1) (dry weight) for p,p'-DDMS (1-chloro-2,2-bis(chlorophenyl)ethane), main metabolites of the anaerobic degradation of DDT, were determined. The occurrence of all selected contaminants, most of which have been banned more than 10 years ago, demonstrate recent contamination pathways, and the necessity of a continuous long-term monitoring of the affected environment.

Detailed gas chromatographic-mass spectrometric analyses applied to eight Rhine river water samples constituted a comprehensive characterization of the low molecular weight organic contamination. Within the group of predominant anthropogenic contaminants, only a few compounds were characterized as frequently detected or priority pollutants. Numerous compounds exhibiting physiological or ecotoxicological properties are only rarely reported or still unnoticed riverine contaminants. Information on environmental behaviour or ecotoxicological effects is still limited for most of these substances. In particular, several brominated compounds (mono- and dibrominated (methoxyphenyl)propionic acids and hydroxymethylacetophenones) were identified for the first time as environmental contaminants. Quantitative analyses differentiated five groups of pollutants with respect to their concentration profiles. The spatial distribution and the intensity of emission sources on the one hand and the environmental stability as well as the tendency to adsorb on the particulate matter on the other hand determined the quantitative occurrence of individual compounds.

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.

GC/MS-screening analyses of water samples from the Lippe River, Germany, revealed the presence of a wide spectrum of low-molecular weight organic compounds ranging from non-polar constituents like aliphatic hydrocarbons to polar constituents like n-carboxylic acids and phenols. Most of the identified compounds could be attributed to anthropogenic input and are used as plasticizers, flame retardants, pharmaceutical drugs or fragrances. Some of them had rarely been noticed as organic pollutants of aquatic environments before. These are, among others, 9-methylacridine, the plasticizer 2,2,4-trimethyl-1,3-pentandioldiisobutyrate (TXIB), the surfactant 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD), triphenylphosphinoxide and the flame retardant tris(chloropropyl)phosphate. On the other hand, most of the identified trialkyl phosphates, pharmaceutical drugs and synthetic fragrances have been reported in surface waters by several authors so far. Input pathways of the detected compounds were traced back by sampling various input sources of organic matter such as discharges of wastewater and Lippe River tributaries. Several contaminants were ubiquitous in Lippe River water and also occurred in sewage effluent from a municipal sewage treatment plant and in samples from the tributaries. This observation suggests that they are typical sewage derived contaminants and have the potential to be used as anthropogenic molecular markers.

Sediment samples of the Lippe river (Germany) taken between August 1999 and March 2001 were investigated by GC-MS-analyses. These analyses were performed as non-target-screening approaches in order to identify a wide range of anthropogenic organic contaminants. Unknown contaminants like 3,6-dichlorocarbazole and bis(4-octylphenyl)amine as well as anthropogenic molecular marker compounds were selected for quantification. The obtained qualitative and quantitative analytical results were interpreted in order to visualize the anthropogenic contamination of the Lippe river including spatial distribution, input effects and time dependent occurrence. Anthropogenic molecular markers derived from municipal sources like polycyclic musks, 4-oxoisophorone and methyltriclosan as well as from agricultural sources (hexachlorobenzene) were gathered. In addition molecular markers derived from effluents of three different industrial branches, e.g. halogenated organics, tetrachlorobenzyltoluenes and tetrabutyltin, were identified. While municipal and agricultural contaminations were ubiquitous and diffusive, industrial emission sources were spatially isolated. Specific seasonal trends of distribution patterns were not observed.

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.