Optimized microplastic analysis based on size fractionation, density separation and µ-FTIR.

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 ZnCl2-based density separation for the polymer types and the various grain sizes. The obtained recovery rates were close to 100% showing that ZnCl2-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.

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

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

Unusual tin organics, DDX and PAHs as specific pollutants from dockyard work in an industrialized port area in China.

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.

Formation and Fate of Point-Source Nonextractable DDT-Related Compounds on Their Environmental Aquatic-Terrestrial Pathway.

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.

Degree of phenyl chlorination of DDT-related compounds as potential molecular indicator for industrial DDT emissions.

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.

Complex organic pollutant mixtures originating from industrial and municipal emissions in surface waters of the megacity Jakarta-an example of a water pollution problem in emerging economies.

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.

Heavy metals in river and coast sediments of the Jakarta Bay region (Indonesia) - Geogenic versus anthropogenic sources.

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.

Spatial distribution and seasonal variation of the trace hazardous element contamination in Jakarta Bay, Indonesia.

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.

Master Plan Jakarta, Indonesia: The Giant Seawall and the need for structural treatment of municipal waste water.

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.

Accumulation patterns of lipophilic organic contaminants in surface sediments and in economic important mussel and fish species from Jakarta Bay, Indonesia.

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.

Hexa(methoxymethyl)melamine: An Emerging Contaminant in German Rivers.

Hexa(methoxymethyl)melamine (HMMM)-containing resins are used in the production of coatings and plastics for cans, coils, and automobiles. A previous study demonstrated that this compound was associated with acute toxic effects on daphnia. This study presents the first compiled data on the occurrence of HMMM as an emerging contaminant in German rivers. The compound occurred in 60 of 117 water samples from three river systems, with concentrations ranging between < 10 and 880 ng/L. Based on water concentrations and river flow on the day of sampling, the loads of HMMM were calculated for two rivers. The spatial distribution patterns of the loads showed large variations and did not follow clear trends along the stream course. These variations were attributed to effective removal processes, leading to sudden load decreases within short flow distances. The data suggest that HMMM could be discharged to the investigated rivers with wastewaters from the automotive industry and related branches.

Identification of characteristic organic contaminants in wastewaters from modern paper production sites and subsequent tracing in a river.

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.

A combined chemical and biological assessment of industrial contamination in an estuarine system in Kerala, India.

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.

Assessment of heavy metals in water samples and tissues of edible fish species from Awassa and Koka Rift Valley Lakes, Ethiopia.

The Ethiopian Rift Valley Lakes host populations of edible fish species including Oreochromis niloticus, Labeobarbus intermedius and Clarias gariepinus, which are harvested also in other tropical countries. We investigated the occurrence of six heavy metals in tissues of these fish species as well as in the waters of Lake Koka and Lake Awassa. Both lakes are affected by industrial effluents in their catchments, making them ideal study sites. Mercury concentrations were very low in the water samples, but concentrations in the fish samples were relatively high, suggesting a particularly high bioaccumulation tendency as compared with the other investigated metals. Mercury was preferentially accumulated in the fish liver or muscle. It was the only metal with species-specific accumulation with highest levels found in the predatory species L. intermedius. Lower mercury concentrations in O. niloticus could be attributed to the lower trophic level, whereas mercury values in the predatory C. gariepinus were unexpectedly low. This probably relates to the high growth rate of this species resulting in biodilution of mercury. Accumulation of lead, selenium, chromium, arsenic and cadmium did not differ between species, indicating that these elements are not biomagnified in the food chain. Values of cadmium, selenium and arsenic were highest in fish livers, while lead and chromium levels were highest in the gills, which could be related to the uptake pathway. A significant impact of the industrial discharges on the occurrence of metals in the lakes could not be detected, and the respective concentrations in fish do not pose a public health hazard.

Anthropogenic organic contaminants in water, sediments and benthic organisms of the mangrove-fringed Segara Anakan Lagoon, Java, Indonesia.

Segara Anakan, a mangrove-fringed coastal lagoon in Indonesia, has a high diversity of macrobenthic invertebrates and is increasingly affected by human activities. We found > 50 organic contaminants in water, sediment and macrobenthic invertebrates from the lagoon most of which were polycyclic aromatic compounds (PACs). Composition of PACs pointed to petrogenic contamination in the eastern lagoon. PACs mainly consisted of alkylated PAHs, which are more abundant in crude oil than parent PAHs. Highest total PAC concentration in sediment was above reported toxicity thresholds for aquatic invertebrates. Other identified compounds derived from municipal sewage and also included novel contaminants like triphenylphosphine oxide. Numbers of stored contaminants varied between species which is probably related to differences in microhabitat and feeding mode. Most contaminants were detected in Telescopium telescopium and Polymesoda erosa. Our findings suggest that more attention should be paid to the risk potential of alkylated PAHs, which has hardly been addressed previously.

Identification and chemical characterization of specific organic constituents of petrochemical effluents.

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.

The anthropogenic contribution to the organic load of the Lippe River (Germany). Part I: Qualitative characterisation of low-molecular weight organic compounds.

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.

The anthropogenic contribution to the organic load of the Lippe River (Germany). Part II: Quantification of specific organic contaminants.

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.