Bernhard Aichner

Levels and Spatial Distribution of Persistent Organic Pollutants in the Environment: A Case Study of German Forest Soils

The Of/Oh-horizons of 447 forest stands in Germany were evaluated for concentrations and spatial distribution of selected polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). While concentrations of dichlorodiphenyltrichloroethane (DDT) and PCBs show similar spatial distribution patterns for all measured compounds within each compound class, significantly different distributions were identified for concentrations of low-molecular-weight PAHs [2- and 3-ring PAHs plus fluoranthene (FLA) and pyrene (PYR)] in contrast to high-molecular-weight PAHs (4-6-ring PAHs without FLA and PYR). Maxima of persistent organic pollutant (POP) concentrations could be mostly explained by specific locatable sources. Because of the slow degradation rates of these target substances, this is especially relevant for historic contamination sources, such as extensive 1980s DDT usage in the former German Democratic Republic and industrial facilities that produced hexachlorobenzene (HCB) or PCBs. A contribution of ubiquitous background pollution derived from long-range atmospheric transport is likely for some compounds in the studied area, e.g., DDT in the western part of Germany and dieldrin. However, most target compounds appear to be mainly sourced from local or regional emissions. This is supported by the absence of clear dependencies between POP concentrations and most evaluated environmental and local parameters. We suggest that these results generally reflect the distribution of POPs in densely populated and industrialized countries located in temperate regions.

Regionalized concentrations and fingerprints of polycyclic aromatic hydrocarbons (PAHs) in German forest soils

Samples of 474 forest stands in Germany were analysed for concentrations of polycyclic aromatic hydrocarbons (PAHs) in three sampling depths. Enhanced concentrations were mainly found at spots relatively close to densely industrialized and urbanized regions and at some topographically elevated areas. Average enrichment factors between mineral soil and humic layer depend on humus type i.e. decrease from mull via moder to mor. Based on their compound-patterns, the observed samples could be assigned to three main clusters. For some parts of our study area a uniform assignment of samples to clusters over larger regions could be identified. For instance, samples taken at vicinity to brown-coal strip-mining districts are characterized by high relative abundances of low-molecular-weight PAHs. These results suggest that PAHs are more likely originated from local and regional emitters rather than from long-range transport and that specific source-regions can be identified based on PAH fingerprints.

Persistent endosulfan sulfate is found with highest abundance among endosulfan I, II, and sulfate in German forest soils

Endosulfan - an agricultural insecticide and banned by Stockholm Convention - is produced as a 2:1 to 7:3 mixture of isomers endosulfan I (ESI) and endosulfan II (ESII). Endosulfan is transformed under aerobic conditions into endosulfan sulfate (ESS). The study shows for 76 sampling locations in German forests that endosulfan is abundant in all samples with an opposite ratio between the ESI and ESII than the technical product, where the main metabolite ESS is found with even higher abundance. The ratio between ESI/ESII and ESS show clear dependence on the type of stands (coniferous vs. deciduous) and humus type and increases from deciduous via mixed to coniferous forest stands. The study argues for a systematic monitoring of ESI, ESII, and ESS and underlines the need for further research, specifically on the fate of endosulfan including biomagnifications and bioaccumulation in soil.

Leaf wax n -alkane distributions record ecological changes during theYounger Dryas at Trzechowskie paleolake (Northern Poland)without temporal delay

While of higher plant origin, a specific source assignment of sedimentary leaf wax n-alkanes remains difficult. In addition, it is unknown how fast a changing catchment vegetation would be reflected in sedimentary leaf wax archives. In particular, for a quantitative interpretation of nalkane C and H isotope ratios in terms of paleohydrological and paleoecological changes, a better understanding of transfer times and dominant sedimentary sources of leaf wax n-alkanes is required. In this study we tested to what extent compositional changes in leaf wax n-alkanes can be linked to known vegetation changes by comparison with high-resolution palynological data from the same archive. We analyzed leaf wax n-alkane concentrations and distributions in decadal resolution from a sedimentary record from Trzechowskie paleolake (TRZ, northern Poland), covering the Late Glacial to early Holocene (13 360–9940 yr BP). As an additional source indicator of targeted n-alkanes, compound-specific carbon isotopic data have been generated in lower time resolution. The results indicated rapid responses of n-alkane distribution patterns coinciding with major climatic and paleoecological transitions. We found a shift towards higher average chain length (ACL) values at the Allerød–Younger Dryas (YD) transition between 12 680 and 12 600 yr BP, coevaled with a decreasing contribution of arboreal pollen (mainly Pinus and Betula) and a subsequently higher abundance of pollen derived from herbaceous plants (Poaceae, Cyperaceae, Artemisia), shrubs, and dwarf shrubs (Juniperus and Salix). The termination of the YD was characterized by a successive increase in n-alkane concentrations coinciding with a sharp decrease in ACL values between 11 580 and 11 490 yr BP, reflecting the expansion of woodland vegetation at the YD–Holocene transition. A gradual reversal to longer chain lengths after 11 200 yr BP, together with decreasing n-alkane concentrations, most likely reflects the early Holocene vegetation succession with a decline of Betula. These results show that n-alkane distributions reflect vegetation changes and that a fast (i.e., subdecadal) signal transfer occurred. However, our data also indicate that a standard interpretation of directional changes in biomarker ratios remains difficult. Instead, responses such as changes in ACL need to be discussed in the context of other proxy data. In addition, we find that organic geochemical data integrate different ecological information compared to pollen, since some gymnosperm genera, such as Pinus, produce only a Published by Copernicus Publications on behalf of the European Geosciences Union. 1608 B. Aichner et al.: Leaf wax n-alkane distributions record ecological changes very low amount of n-alkanes and for this reason their contribution may be largely absent from biomarker records. Our results demonstrate that a combination of palynological and n-alkane data can be used to infer the major sedimentary leaf wax sources and constrain leaf wax transport times from the plant source to the sedimentary sink and thus pave the way towards quantitative interpretation of compound-specific hydrogen isotope ratios for paleohydrological reconstructions.