Historical Changes in Levels of Organic Pollutants in Sediment Cores from Brno Reservoir, Czech Republic

Results of a comprehensive study are presented on the spatial and depth-related distribution of persistent organic pollutants (POPs) in sediments of the Brno reservoir, Czech Republic. Based on sedimentological observations, three major historic phases were identified related to the evolution of the depositional environment, flow rate, and material input. Data on organic carbon, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides showed specific distribution patterns in a 3-m-deep core. The analysis of the depth trends of the geochemical data combined with sedimentology made it possible to distinguish between remote sources of the pollutants, early weathering alterations of POPs, transport by river associated with organic matter as sorbent on one hand, and local sources weakly related to lithology on the other hand. The integrated sedimentological and environmental geochemical archive provided an improved dynamic view of the pollution in historical terms.     

Organic-geochemical Differentiation of Petroleum-type Pollutants and Study of Their Fate in Danube Alluvial Sediments and Corresponding Water (Pančevo Oil Refinery, Serbia)

A review is given in this paper of the up-to-date results observed in differentiation and transformation studies on petroleum-type pollutants in underground and surface waters. Water and particulate matter derived from the locality of Pan?evo Petroleum Refinery, Serbia (River Danube alluvial formations). It was shown that distributions of n-alkanes, steranes and triterpanes, and δ¹³C_PDB values of n-alkanes may successfully be used for qualitatively differentiating the petroleum-type pollutants from native organic matter in recent sedimentary formations. In underground waters, a petroleum-type pollutant is exposed to microbiological degradation which is manifested through relatively fast degradation of n-alkanes. Following an almost complete degradation of crude oil n-alkanes in underground water, the biosynthesis of novel, even carbon-number C₁₆–C₃₀ n-alkanes may be observed. It is shown that the n-alkane distribution observed in a petroleum-type pollutant may depend on the intensity of its previous interaction with water. The fate of petroleum-type pollutants in environmental waters may be predicted through laboratory simulative microbiological degradation experiments by using microorganism consortiums similar to those observed under relevant natural conditions, as well as on corresponding nutrient base.     

Organic geochemical parameters for estimation of petrogenic inputs in the coastal area of Kavala City,Greece

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

Transformation of Petroleum Saturated Hydrocarbons during Soil Bioremediation Experiments

This paper presents transformations of saturated hydrocarbons of petroleum type pollutants during ex situ bioremediation of soil on the pilot heap (halde), during a period of 6 months, within the grounds of Petroleum Refinery Pan?evo (Serbia). Samples for analysis were taken in time intervals of 2 weeks (P₁–P₁₂ samples). Organic substance was extracted by Soxhlet’s method and quantified. Isoprenoid aliphatics, in particular pristane and phytane, and polycyclic aliphatics of sterane and triterpane types in saturated hydrocarbon fractions were analysed by GC-MS (SIM method). Significant amounts of n-alkanes have not been detected. The MS-chromatogram revealed only marginal amounts of pristane and phytane in sample P₁. Pristane and phytane occurred in sample P₈, and in even higher quantities in the final sample P_12. The proceeding bioremediation process was accompanied by the decrease of the relative amounts of pentacyclic terpanes of hopane type, compared to tri- and tetracyclic terpanes. In the initial sample P₁ the distribution of steranes and hopanes follows a pattern, which is characteristic for crude oils. However, their identification by SIM method was not possible in samples P₈ and P₁₂ because of the reduced concentration. The observed changes in the alkane fractions’ compositions may be considered as atypical, referring to the fact that during oil biodegradation under natural conditions, decomposition of isoprenoids occurs much easier and faster than decomposition of polycyclic alkanes of tri-, tetra- and pentacyclic terpane, sterane and diasterane types, after the decomposition of n-alkanes has been almost completed.     

Enhanced non-extractable residue formation of 14C-metalaxyl catalyzed by an immobilized laccase

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.     

The impact of SFM-certification on forest product markets in Western Europe — an analysis using a forest sector simulation model

In the international discussion on labels for sustainably produced wood products based on the certification of sustainable forest management (SFM), little attention has been paid to what is probably the most crucial part of any market-based instrument: the potential impact on forest products markets. This paper analyses the potential impact of SFM-certification on forest products markets using a simulation model of the Western European forest sector. Two scenarios with assumptions regarding certification (chain-of-custody costs, timber supply reduction from certified forests) are projected for the period 1995–2015 and tested against the results of a base scenario (‘business as usual’). In general, the results show that rather modest changes are to be expected from SFM-certification in forest products markets. The market impact of a timber supply reduction from certified forest would be more distinct than the impacts of chain-of-custody costs. Industry gross profits would decrease more than production. Due to the large share of roundwood costs in total costs, the sawmill industry would be affected more by even small changes in raw-material prices than the panel and paper industry.     

Exhaustive Screening of Long-Term Pollutants in Riverbank Sediments of the Wurm River,Germany

Fluvial sediments can act as archives for long-term pollution. However, in environmental studies, often only preselected contaminants and, therefore, only a limited part of the pollution are considered. Herein, geochemical investigations of riverbank samples of the Wurm River (catchment <?400 km²) depict the anthropogenic impact of the city Aachen (250,000 inhabitants) to its main outlet resulting in an exhaustive list of present pollutants including their concentrations. The study is based on 14 riverbank sediment samples at eight sampling sites on a 7.6-km-long segment of the Wurm River. The sediment samples were analyzed for grain size composition (laser diffraction particle size analyzer), total organic carbon (TOC), trace element inventory (X-ray fluorescence), and organic compounds (chromatography-mass spectrometry). Here, we report quantitative data for 71 persistent organic substances as well as six trace elements (Cu, Zn, As, Ba, Hg, and Pb) entering the Wurm River due to domestic and industrial emissions. In general, a slight decline of, e.g., PTEs, DDX, and PCB concentrations with decreasing sampling depth points to a steady improvement of conditions. Whereas no clear trends can be seen for organic pollutants along the investigated reach with increasing distance to the main source of pollution (Aachen city). As obtained concentrations for organic pollutants indicate a rather low level of pollution, trace element values exceed geogenic background values by far. Furthermore, we used selected compounds as time markers for a rough estimation of sedimentation rates. Obtained values point to a highly complex morphodynamic regime with changing sedimentation rates (0.6 to 3.0 cm a^?1) within barely 100 m of river course.     

Geochemical analysis of Lake Bant sediments to ascertain inorganic and organic indicators for warfare residues

Purpose  

The immediate time period after the Second World War (1945–1946) was characterised by an urgent need to dispose large amounts of ammunition residues. Although the environmental relevance of explosives released to soils is intensively investigated, to date, their fate and effects in marine ecosystems are not well known. Surface sediments from Lake Bant, Germany, for which deposition of an enhanced amount of ammunition after World War II has been reported, were analysed to identify organic and inorganic indicators for warfare residues. Additionally, samples of ammunition residues collected from the Wadden Sea, Germany, were analysed in order to obtain information on the long-term behaviour of explosives in undamaged ammunition left in the aquatic environment and to obtain first insights into the spectrum of organic substances which are possibly released to the aquatic environment by such ammunition residues.