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Natural hazards (2022). doi:10.1007/s11069-022-05391-y, Published by Springer Science + Business Media B.V., Dordrecht [u.a.]

Environmental monitoring and assessment 194(5), 385 (2022). doi:10.1007/s10661-022-09989-4, Published by Springer Science + Business Media B.V, Dordrecht [u.a.]

The molecular and isotopic composition of biomarkers in initial bitumen isolated from immature (0.41% Rr) oil shale samples (Aleksinac deposit) and liquid products obtained by pyrolysis in open (OS) and closed (CS) systems are studied. The influence of pyrolysis type and variations of kerogen type on biomarkers composition and their isotopic signatures in liquid products is determined. The applicability of pyrolysis type, numerous biomarkers and carbon isotopic compositions (δ13C) of n-alkanes in liquid pyrolysates is established. Pyrolysis experiments were performed on two selected samples that showed high content of total organic carbon and hydrocarbon generation potential, but also certain variations in sources/depositional environment of organic matter (type I and mixed type I/II kerogen) within previous research of the oil shales sample set. The biomarker signatures were evaluated using gas chromatography-mass spectrometry (GC-MS) and δ13C of individual n-alkanes in bitumen and liquid pyrolysates. The molecular composition of liquid pyrolysates from the OS is very similar to those in initial bitumen, independently on kerogen type, confirming algal origin of organic matter (OM) deposited in lacustrine environment, even more apparently than results of initial bitumen. Therefore, OS can be useful for assessment of source and depositional environment of OM. Pyrolysis in the CS caused more intense thermal alterations, therefore the source fingerprints sometimes notably disappear. The liquid pyrolysates from the CS have the distributions of biomarkers similar to those in crude oils. The biomarker maturity parameters showed slightly higher values in the CS pyrolysate of mixed type I/II kerogen in relation to type I kerogen. δ13C of n-alkanes in liquid pyrolysates from the OS are isotopically lighter in comparison to bitumen, independently on kerogen type. Oppositely, in liquid pyrolysates from the CS, they become heavier than in bitumen, indicating the thermal influence on δ13C signatures, with more pronounced difference for type I kerogen. This is the peer-reviewed version of the following article: Gajica, G.; Šajnović, A.; Stojanović, K.; Schwarzbauer, J.; Kostić, A.; Jovančićević, B. A Comparative Study of the Molecular and Isotopic Composition of Biomarkers in Immature Oil Shale (Aleksinac Deposit, Serbia) and Its Liquid Pyrolysis Products (Open and Closed Systems). Marine and Petroleum Geology 2022, 136, 105383. [https://doi.org/10.1016/j.marpetgeo.2021.105383] Published version: [https://cer.ihtm.bg.ac.rs/handle/123456789/4900]

s & presentations / EGU General Assembly 2021 EGU General Assembly 2021, EGU21, online, 19 Apr 2021 - 30 Apr 2021; G��ttingen : Copernicus Gesellschaft mbH EGU21-1985, 1 Seite (2021). doi:10.5194/egusphere-egu21-1985, Published by Copernicus Gesellschaft mbH, G��ttingen

М30 М33 The molecular and isotopic composition of biomarkers in initial bitumen isolated from raw immature oil shale samples from the Lower Miocene Aleksinac Basin (Serbia) and liquid products (LPs) obtained by pyrolysis in open (OS) and closed systems (CS) are studied. The influence of pyrolysis type and variations of kerogen type on biomarkers composition and their isotopic signatures in LPs is determined. The molecular composition of the LPs from the OS pyrolysis is very similar to those in initial bitumen, independently on kerogen type. The LPs from the CS pyrolysis have the distributions of biomarkers similar to those in crude oils generated in an early to main stage of “oil window“. The biomarker data suggests that mixed type I/II kerogen attained slightly higher maturity level by the CS pyrolysis than type I kerogen. The isotopic signatures of n-alkanes in LPs obtained by the OS pyrolysis are isotopically lighter than in initial bitumen, independently on kerogen type, whereas in liquid products from the CS they become heavier; showing more pronounced difference for type I kerogen. The results indicate that δ13C data should be used with caution in interpretation of samples having different maturity and particularly of LPs obtained by different system pyrolysis.

Water 13(12), 1648 (2021). doi:10.3390/w13121648 special issue: "Special Issue "Microplastics in Water Bodies and in the Environment" / Special Issue Editors: Dr. Hrissi K. Karapanagioti, Guest Editor; Dr. Ioannis K. Kalavrouziotis, Guest Editor", Published by MDPI, Basel

Sedimentology : the journal of the International Association of Sedimentologists (2021). doi:10.1111/sed.12879, Published by Wiley-Blackwell, Oxford

s & presentations : EGU General Assembly 2021 EGU General Assembly 2021, vEGU21, online, 19 Apr 2021 - 30 Apr 2021; G��ttingen : Copernicus Gesellschaft mbH EGU21-14389, 2 Seiten (2021). doi:10.5194/egusphere-egu21-14389, Published by Copernicus Gesellschaft mbH, G��ttingen

Environmental earth sciences 80(8), 314 (2021). doi:10.1007/s12665-021-09531-8, Published by Springer, Berlin ; Heidelberg

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.

Japan, more precisely, the eastern coastal areas of Honshu, are one of the most affected areas of tsunamis in the world. Major events within the last century were three Sanriki-oki tsunamis (1896, 1933, 1968), and the most recent 2011 Tohoku-oki tsunami, triggered by the 9.1 MW Tohoku-oki earthquake, which caused massive damage along the coastlines.The 2011 Tohoku-oki tsunami overtopped the coastal defense walls with waves of 6-10 m height along the shores of the Aomori Prefecture in Northern Japan. The inundation reached up to 550 m inland, however, sandy tsunami deposits are limited to 250 – 350 m of the total inundation distance. At the field site of Misawa Harbor the well-preserved identifiable tsunami remains show up to 18 cm thick sand layers with sedimentary features, such as fining upward sequences, mud caps and rip-up clasts. The sandy deposits were enclosed in the soil of the coastal protection forest. Along with the sedimentary record of the tsunami, the use of organic geochemical indicators can provide a better understanding of the extend and processes, such as the deposition of tsunami layers and the backwash, of the inundation by the 2011 Tohoku-oki tsunami. The devastating damages caused by the interaction of tsunami and earthquake released pollutants associated as biological and anthropogenic markers. These released pollutants give the tsunami deposit an unique geochemical signature, that is distinguishable from the background sedimentation. Organic-geochemical results reveal a strong increase of anthropogenic (polycyclic aromatic hydrocarbons, pesticides and chlorinated compounds) and a variation of biological markers (i.e. n-alkanes, fatty acids) in the 2011 tsunami deposit close to the fishery port. During the analysis of the samples, another variation of biomarker and anthropogenic marker were identified right below the soil layer of the current forest. This layer is as well distinguishable from the paleo-dune that marks the lowest sedimentological unit at the field site. This differentiation shows the likely impact of a historical Sanriki-oki tsunami (1896, 1933 or 1968). These organic geochemical results in combination with local eyewitness reports of the tsunamis and lead to the assumption that the sedimentary archive of the Aomori coastline contains and preserved at two or more tsunami events of the last century.The inclusion of organic geochemical markers to expand the characterizing and identifying proxies used in tsunami research are important to get a better understanding of the processes and deposition during tsunamis. Furthermore, this method can detect tsunami deposits beyond the visible recognizability of sedimentological identification of tsunami deposits and therefore can serve as a blue-print for historical and paleo-tsunami studies, as most of them only rely on visible sand deposits as marker for inundation distances from the beach. The high-resolution geochemical application can gain more information than standard techniques, like the identification of the “invisible” tsunami layer exceeding the limits of sandy deposits or the deposition in similar sedimentary textures, capturing a broader picture of the event.

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.

Due to the high population density and sensitive infrastructures, coastal areas are highly vulnerable to various geohazards such as tsunamis. The impact of tsunamis is traceable in sedimentary archives providing an important tool for reconstructing these events. Here, geochemical and physical evidence of the resulting inundations have been discussed over the last years with increasing interest on identifying and using highly specific tsumanite indicators. To investigate a broader range of potential organic indicators, a multi-tiered geochemical analysis has been applied on tsunami deposit from Japan and Hawaii in this study with the aim to detect and quantify a more comprehensive set of suitable marker compounds. Both areas of investigation differed especially in terms of population and anthropogenic influence. The analyzed fractions of organic matter covered not only the low molecular weight compounds of the extractable and hydrolysable fraction (a part of the non-extractable fraction), but also the macromolecular matter. Three consecutive analytical approaches including extraction, alkaline hydrolysis and pyrolysis have been applied on the sedimentary organic matter to study their potential to contrast between tsunami and non-tsunami layers. The analyses of compound ratios as well as individual concentration profiles in tsunami and non-tsunami layers revealed two parameters, the TARFA (terrigenous to aquatic ratio of fatty acids) and the C29/C27 sterol ratio, which exhibit a high potential to act as tsunamite indicators. Further parameters (TARALK - terrigenous to aquatic ratio of n-alkanes, concentration profiles of long-chain n-aldehydes) showed a minor potential but are worth to be considered in organic geochemical analyses of tsunami affected sediment archives in the future.

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.

The contribution corrects an equation from the paper: Hagemann, L.; Kasanin-Grubin, M.; Gajica, G.; Strbac, S.; Sajnovic, A.; Jovancicevic, B.; Vasic, N.; Schwarzbauer, J. Four Decades of Organic Anthropogenic Pollution: A Compilation for Djerdap Lake Sediments, Serbia. Water, Air, and Soil Pollution 2019, 230 (10). [https://doi.org/10.1007/s11270-019-4277-8]

The southwest of the Iberian peninsula is, due to its border position between Africa and Europe, a key territory of major geoarchaeological interest, as well as a reservoir of biodiversity and a wildlife refuge area during the Holocene. Bioclimatic conditions have been significantly unstable during this period in the Western Mediterranean. Therefore, further studies are still required to understand how abrupt climate changes such as the 8.2 and 4.2 ka cal BP events impacted societies and environment. In November 2018 the RV Meteor cruise M-152 retrieved 19 vibracores and 4 gravity cores along the Algarve coast after mapping the bathymetry. One of these cores, GeoB23519-01, was taken 65 m below present sea level and recovered 365 cm of sediment. Four potential event layers were identified over the last 11 ka cal BP and, at least two of them, are related to tsunami deposits (ca. 4370 cal BP and AD 1755). This sedimentary archive was analysed in a multi-proxy approach, including palynological and micropalaeontological analyses, which allow characterizing palaeoenvironmental changes along the core. However, considering the characteristics of these deposits, we raise questions about how complex this palynological record is and how it mirrors some short-term events, climate dynamics, and cultural disruptions.

The activity of radiocesium in alluvial sediment is a widely used proxy for sediment age determination for the period after its first occurrence in the environment in 1952. In a continuous and undisturbed sediment archive, the results of this method are reliable as shown by various studies. However, depending on the specific characteristics of an archive provided by alluvial sediment, the results might be unreliable or biased. This article describes the challenges and ambiguous results obtained by the measurement of radiocesium in a soil profile that provides a time marker with a concrete structure of known age. The applicability of radiocesium for the study area was successfully tested on a floodplain profile. The results showed radiocesium peaks up to 22.5 Bq/kg that correspond to the years 1963 and 1986. As a result of different hydromorphological conditions and sedimentation rates at the sampling locations, the peaks occurred in different depths. In the floodplain, the 137Cs-peaks are significantly more distinguished than in the profile at the concrete structure. There, the radiocesium content is scattered, which queries the function of the structure as a chronological marker. The scattering might be caused by various syn-sedimentary and post-sedimentary processes and factors, such as scouring and redeposition of contaminated sediment, topsoil recycling by vegetation uptake and dieback, or input of eroded sediments from the hinterland forest soils. Thus, the concrete structure creates and at the same time destroys the possibility of using it as a chronological marker.

Although pyrolytic analysis of polymers allows a quantitative determination, reports on pyrolysis-based quantifications are very scarce, most probably as the result of some critical aspects that need to be considered. This is valid especially for environmental analysis of microplastics that require a detection at low concentrations in complex matrices. Therefore, an off-line pyrolysis approach to quantify five polymers representing the most relevant constituents of microplastics (polyethylene PE, polypropylene PP, poly(ethylene terephthalate) PET, polystyrene PS, poly(vinyl chloride) PVC) was studied. The analytical approach was critically evaluated and discussed covering the basic analytical parameters specificity, sensitivity, reproducibility and applicability on real samples. Off-line pyrolysis-based analysis of PS and PP provided the best results with a high specificity of pyrolysis products, very good limit of quantification around 1 to 3 μg based on S/N ratios as extrapolated from standard material analyses (without matrix effects) and a recovery from real sample matrix higher than 50%. Hence, for these synthetic polymers the presented analytical method exhibits a high potential for quantification at low concentration levels in real environmental samples. Although for PE a partly lower specificity of pyrolysis products, a little lower sensitivity and reproducibility but a very good recovery from real sample matrix can be summarized, the off-line pyrolysis-based approach seems to be applicable successfully also for PE. Analyses of PVC and PET revealed the highest inconsistencies and drawbacks in particular only minor specificity, less reproducibility and a low recovery. Thus, both polymers can be quantified only with a very low degree of reliance and need complementary analysis to verify the pyrolysis-based quantitative results. Noteworthy, most of the critical aspects revealed by this study are also worth discussing for on-line pyrolysis approaches.

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.

Various factors influence the isomeric composition of hexachlorocyclohexanes which are released to the environment. Original compositions in technical mixtures may vary slightly, but higher shifts are observable for transfer processes, bioaccumulation and microbial transformation. Consequently, the isomeric composition in environmental samples is a superposition of these processes. In this study, isomeric distributions and concentrations of hexachlorocyclohexanes were analyzed in water, sediment, and soil samples of a riverine system known to be highly contaminated by hexachlorocyclohexanes. To assess desorption of hexachlorocyclohexanes from particulate matter to water, batch shaking and percolation experiments were conducted complementary. Analyzed samples exhibited total hexachlorocyclohexane concentrations of up to 2.8 µg/g in sediments and up to 21 µg/L in river water predominated by the α-isomer. Downstream hexachlorocyclohexane pattern changed toward δ-isomer domination, while overall hexachlorocyclohexane concentrations decreased. Desorption experiments supported the assumption of discrimination by preferred association of the α- and β-isomers with particulate matter, showing elevated mobilization of γ-, δ- and e-hexachlorocyclohexanes and lower mobilization of the α- and β-isomers. Soil samples of a riparian wetland exhibited elevated concentrations of hexachlorocyclohexanes exceeding 200 µg/g and predominance of α-hexachlorocyclohexanes in the top soil layer. Subjacent soil layers showed rapidly decreasing hexachlorocyclohexane concentrations and an isomeric shift toward the β-isomer. The assumed preferential mobilization of β-hexachlorocyclohexane was supported by desorption experiments. This study demonstrated firstly that transfer processes influence substantially hexachlorocyclohexane isomer distribution in the aquatic environment. Secondly, conditions of aging determine strength of association and remobilization potential of hexachlorocyclohexane residue down to an isomer-specific level.

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.

We studied the influence of an immobilized laccase from Trametes versicolor on non-extractable residue (NER) formation of the systemic fungicide 14C-metalaxyl in soil. We added the enzyme (130 mU/g DW) to soil sterilized by gamma irradiation and observed that the amount of NER (6.3 % of applied radioactivity) after 10 days of incubation was enhanced about twofold compared to the sterile soil without laccase addition. Residues formed within samples without enhanced enzyme activity were mainly bound via ester linkages to all fractions of humic matter, i.e., fulvic acids, humic acids, non-humines, and humines, respectively. In contrast, residues formed in presence of immobilized laccase were more strongly bound by covalent linkages such as ether and C-C bonds, especially to humic acids. After chemical degradation of the humic matter, it could be observed that all NER contained the first major transformation product, i.e., metalaxyl acid. The findings underline that the residue formation of metalaxyl in soil may be partly catalyzed by immobilized extracellular oxidative enzymes through oxidative coupling reactions within the humic matter.

This study explores the comparability of results of two different pyrolysis methods applied to macromolecular geochemical material: laser-pyrolysis–gas chromatography/mass spectrometry (La-Py–GC/MS) and Curie Point-pyrolysis–gas chromatography/mass spectrometry (CP-Py–GC/MS). Six samples of different fossil (megaspores, prasinophytes, scolecodonts, amber, vitrain) and extant (sporopollenin) biomaterials were analysed at various pyrolysis temperatures by CP-Py–GC/MS and by La-Py–GC/MS. The qualitative composition of the pyrolysates obtained from both methods was similar. However, La-Py–GC/MS produced shorter aliphatic pyrolysis products in almost all samples. Results obtained from megaspores and prasinophytes indicate a laser temperature higher than the highest Curie temperature applied (920 °C). The application of La-Py–GC/MS was successful for material with a predominantly aromatic structure and/or a high thermal maturity (scolecodonts, vitrain). For extant or immature materials CP-Py–GC/MS appears to be a more suitable method as the applied temperature can be regulated much more accurately.

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.

'On-line' pyrolysis coupled with gas chromatography (GC) was performed for quantitative determination of poly(vinylpyrrolidone) (PVP) in wastewater sample. Gas chromatography-mass spectrometry (GC-MS) showed that the main product of pyrolysis of PVP, at high temperatures, was N-vinylpyrrolidone (NVP). After that, different amounts of commercial PVP were pyrolyzed in order to establish the correlation between the amount of generated NVP (its GC peak area) and the initial mass of pyrolyzed PVP. GC-FID analysis was used for construction of the calibration curve and for quantitative determination of PVP. Very good linear correlation was obtained between the area of NVP peak, generated during pyrolysis, and the initial mass of PVP (r2 = 0.998). Further, solutions of known concentration of PVP were prepared in destilled water ('spiked samples'). Spiked samples were preextracted with diethyl ether and n-hexane, after which the water-layer was evaporated and dissolved again in methanol. Analysis of pyrolysates of preextracted spiked samples showed that the 'recovery' of PVP was above 96 mass%. This finding suggested that pre-extraction could be applied to reduce the concentration of organic substances that could also be pyrolyzed, and thus hinder identification and quantitative determination of PVP, without significant loss of polymer. The sample of an industrial wastewater from Pančevo, Serbia was investigated in the last part of this work. The sample was preextracted in the same way as the spiked samples and than pyrolyzed. NVP was identified by GC-MS in obtained pyrolysate, which was the evidence that PVP was present in the wastewater sample. NVP was quantified on the basis of the peak area in GC-FID chromatogram, and than the concentration of PVP in wastewater sample was calculated based on calibration curve. Concentration of PVP in industrial wastewater amounted 2.5 mg/L. U ovom radu je primenjena metoda 'on-line' pirolize u sprezi sa gasnom hromatografijom (GC) za kvantitativno određivanje poli(vinilpirolidona) (PVP) u uzorku otpadne vode. Najpre je gasnomhromatografsko-masenospektrometrijskom analizom (GC-MS) utvrđeno da pirolizom PVP na visokim temperaturama kao glavni proizvod degradacije nastaje monomer, N-vinilpirolidon (NVP). Nakon toga su različite količine komercijalnog PVP pirolizovane da bi se uspostavila korelacija između količine nastalog NVP i inicijalne mase pirolizovanog polimera. Za konstruisanje kalibracione krive i kvantitativno određivanje PVP u rastvorima poznate koncentracije u destilovanoj vodi ('spiked samples'), kao i u uzorku otpadne vode, korišćena je GC analiza. Analizom rastvora komercijalnog PVP poznate koncentracije ustanovljeno je da PVP 'recovery', nakon ekstrakcije n-heksanom i dietil-etrom, iznosi iznad 96 mas.%. U poslednjem delu rada ispitan je uzorak industrijske otpadne vode iz Pančeva, Srbija. Pokazano je da je PVP bio prisutan u otpadnoj vodi i da je njegova koncentracija bila daleko iznad uobičajenih koncentracija niskomolekularnih organskih zagađivača.

The release of unburnt coal particles and associated polycyclic aromatic hydrocarbons (PAHs) may cause adverse impacts on the environment. This study assessed variations in the concentration and composition of PAHs in a set of fifty coal samples from eleven coal basins worldwide. The maximum PAH concentrations at high volatile bituminous rank were recorded in samples from a single basin. Considering the entire sample set, the highest PAH concentrations were in fact found outside of this rank range, suggesting that the maceral composition and thus the coal's origin also influenced PAH concentrations. The examination of the PAH compositions revealed that alkylated 2-3 ring PAHs remain dominant compounds irrespective of coal rank or origin. Multivariate analysis based on PAH and maceral content, bulk and maturity parameters allowed the recognition of seven groups with different rank and origin within the coal sample set.

Hintergrund und Ziel der Studie Elbsedimente zeigen seit Jahren hohe Toxizitaten im Algenwachstumshemmtest, ohne deren stofflichen Hintergrund umfassend zu kennen. Daher wurde in einem Gemeinschaftsprojekt nach einer ersten screeningorientierten Analytik eine Wirkungsfraktionierung auf Basis einer Festphasenanreicherung mit nachfolgender sequentieller Elution entwickelt und zur wirkungsorientierten Analytik eingesetzt. Dadurch konnte neben Ammonium eine zweite organische Wirkkomponente isoliert werden, die sich durch eine hohe Lipophilie und Thermostabilitat sowie niedrige Polaritat und geringe Fluchtigkeit auszeichnet. Eine eindeutige chemische Identifizierung ist bislang nicht gelungen. In einem zweiten Untersuchungsabschnitt wurde fur die Algentoxizitat in Elbsedimenten an zwei Standorten eine hohe ortliche Varianz sogar im kleinraumigen Masstab belegt.

Future enrichment of atmospheric CO2 and its effect on ecosystems were studied using grassland free air CO2 enrichment (FACE) experiments. Plant waxes have been shown to be directly modified under elevated CO2 concentration. Lipids, as major components of plant waxes, are important constituents of plant surfaces and their position at the plant/atmosphere interface makes them susceptible to environmental change. The main focus of this study was to improve knowledge about modifications to stable carbon isotopic (δ13C) values of individual lipids within plant biomass and soils as a result of the increased atmospheric CO2 concentration, implying an addition of 13C labelled CO2. The isotopically labelled biomass facilitates turnover time determination of lipids in soils due to the direct comparison of identical plants grown under ambient and 13C-depleted atmospheric conditions. We demonstrate which lipids were influenced by modified CO2 concentration and how the lipid isotopic values of plant biomass and soil were influenced under elevated vs. ambient CO2 conditions. Most plant carboxylic acids and alkanes were uniformly depleted in 13C by ca. 6‰ when compared to plant biomass bulk isotope values. In soil, short chain carboxylic acids (

The experiment of ex situ soil bioremediation was performed at the locality of the Oil Refinery in Pancevo (alluvial formation of the Danube River, Serbia) polluted with an oil type pollutant. The experiments of biostimulation, bioventilation and reinoculation of an autochthonous microbial consortium were performed during the six-month period (May-November 2006). The changes in the quantity and composition of the pollutant, or the bioremediation effect, were monitored by analysis of the samples of the polluted soil taken in time spans of two weeks. In this way, from the beginning until the end of the experiment, 12 samples were collected and marked as P1-P12 (Pancevo 1-Pancevo 12). The results obtained showed that more significant changes in the composition of the oil pollutant occurred only during the last phases of the experiment (P8-P12). The activity of microorganisms was reflected in the increase of the quantity of polar oil fractions, mainly fatty acid fractions. In this way, the quantity of total eluate increased, and the quantity of the insoluble residue was reduced to a minimum, whereby the oil pollutant was transformed to a form that could be removed more efficiently and more completely from the soil, as a segment of the environment.

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.

The occurrence and distribution of alkyl naphthalenes and alkyl phenanthrenes in 39 Late Palaeozoic coal and sediment samples, containing predominantly terrestrial organic matter, is related to thermal maturity and biological source input. This study investigates the relationship between aromatic hydrocarbons and the corresponding aldehydes, ketones, carboxylic acids and dicarboxylic acids based on the naphthalene skeleton. It is suggested that alkyl naphthalenes are oxygenated in the sediments. The behaviour of alkyl phenanthrenes and their oxygenated analogues is discussed in this context. Alkyl naphthalenes and phenanthrenes were abundant in all samples. The low polarity nitrogen, sulfur and oxygen compound fraction was characterised by the presence of alkyl naphthaldehydes and naphthyl ketones for the majority of the samples. The presence of naphthalene carboxylic acids and anthracene/phenanthrene carboxylic acids was restricted to samples of relatively enhanced maturity (vitrinite reflectance, Rr, 0.67–1.26%), with one exception. The correlations between the different classes of compounds based on the naphthalene skeleton led to the hypothesis that, within the maturity range investigated, aldehydes and ketones were readily formed from the corresponding aromatic hydrocarbons, while the carboxylic acids were formed at elevated maturity. For alkyl naphthalene dicarboxylic acids, two formation pathways are suggested, because of two different distribution patterns. A direct correlation of these dicarboxylic acids with the occurrence of other compounds having a naphthalene skeleton was not apparent.

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.

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.

This paper presents the results of a detailed study on the occurrence and distribution of alkylnaphthalenes and alkylphenanthrenes in 39 coal and sediment samples from the Late Palaeozoic containing predominantly terrestrial organic matter. Most of the samples represent the Euramerian flora realm and originate from locations beyond the Variscan front in Eastern, Northern and Central Europe, i.e. especially England and the Moscow Basin. The samples are of relatively low maturity (0.32 to 1.80% Rr) and consist mainly of mixtures of type III and II kerogen. Quantification of the C0- to C4-naphthalenes and the C0- to C4-phenanthrenes showed that these compound classes were highly abundant in all samples. Aromatic hydrocarbon maturity parameters in general are in good agreement with measured vitrinite reflectance values. 1,2,7-Trimethylnaphthalene, an assumed diagenetic product of oleanane type biomarkers was present in all investigated samples. This observation provides evidence that oleanane type lipids were biosynthesised by organisms predating the evolution of angiosperms or that assumed formation pathways for 1,2,7-trimethylnaphthalene are insecure. 1,2,8-Trimethylphenanthrene was significantly enriched in samples from the Permian and the one sample from the Devonian investigated in this study. The precursor(s) of 1,2,8-trimethylphenanthrene therefore may have been produced by organisms which were least abundant in the Carboniferous depositional environments represented by our samples.

A subaquatic sediment core was taken from the Rhine River to determine substance specific concentration profiles in correlation to time and depth. Based on these data emission histories were related for selected contaminants. Significant emission sources and emission pathways were compiled. In correlation to investigations of national and international monitoring programmes a significant reduction of environmental emissions up to a tenth of previous values were found since 1998. Some selected compounds, discharged by municipal and industrial activities, for example disinfectants (methyltriclosan), flame retardants (tris(chloropropyl)phosphate), chlorinated benzenes, anilines and naphthalenes, can be classified as significant synthetic substances in the scope of the Water Framework Directive. Because of their chemical characters, their persistence, bioaccumulation and ecotoxicity, as well as their occurrence within the sediment core, these compounds create a significant potential risk for water quality, but a reduction of these synthetic compounds to zero cannot be expected for the next future. In summary, this study provides a comprehensive reconstruction of the pollution history of anthropogenic contaminants, their fate and behaviour in the fluvial system. In addition, an estimation of the time period required for environmental measurements and monitoring programmes to improve, achieve and save a good status of the river systems are given.

Twenty-five crude oils originating from the Velebit oil field (SE Pannonian Basin), the most important oil field in Serbia, were investigated. Saturated biomarkers (n-alkanes, isoprenoids, steranes and triterpanes) were analyzed by gas chromatography-mass spectrometry (GC-MS). Based on the distribution and abundance of these compounds, a large number of source and maturation parameters were calculated, particularly those most often used in correlation studies of oils. The examined samples were classified according to their origin and level of thermal maturity using factor, cluster and discriminant analyses. According to the source and maturation parameters, combined factor and cluster analyses using the Ward method enabled the categorization of the investigated oils into three groups. The cluster Ward analysis was shown to be of greater susceptibility and reliability. However, in addition to the two aforementioned methods, K-Means cluster analysis and discriminant analysis were shown to be necessary for a more precise and detailed categorization in the case of a large number of samples in one group. Consequently, it was concluded that factor and cluster K-Means and Ward analyses can generally be used for the interpretation of saturated biomarkers in correlation studies of oils, but the observed results have to be checked, i.e., confirmed by discriminant analysis.