Wilhelm Püttmann

Occurrence and fate of organophosphorus flame retardants and plasticizers in urban and remote surface waters in Germany.

Within this study, concentration levels and distribution of the organophosphates tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris(2-butoxyethyl) phosphate (TBEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) were investigated at nine lentic surface waters under different anthropogenic impact between June 2007 and October 2009. Furthermore, the possibility of in-lake photochemical degradation of the analytes was studied in laboratory experiments using spiked ultrapure water and lake water samples incubated in Teflon bottles (which transmit sunlight). TBEP, TiBP, and TnBP were photochemically degraded in spiked lake water samples upon exposure to sunlight. Organophosphate concentrations in the more remote lakes were often below or close to the limits of quantification (LOQ). TCPP was the substance with the highest median concentration in rural volcanic lakes (7-18ngL(-1)) indicating an atmospheric transport of the compound. At urban lakes their median concentrations were in the range of 23-61ngL(-1) (TCEP), 85-126ngL(-1) (TCPP), <LOQ-53ngL(-1) (TBEP), 8-10ngL(-1) (TiBP), and 17-32ngL(-1) (TnBP). High variability but no significant seasonal trends were observed for all five organophosphates in urban lake water samples.

Occurrence and geochemical significance of 1,2,5,6-tetramethylnaphthalene

Analysis of aromatic hydrocarbon fractions of selected coal and shale samples reveals the predominance of two specific polyalkylnaphthalenes which have been identified as 1,2,5-trimethylnaphthalene and 1,2,5,6-tetramethylnaphthalene. The maturity of the samples is such that the source effect on the formation of individual molecules from biological precursors is expected to be recognisable. These alkylnaphthalenes are thought to be diagenetically derived from pentacyclic triterpenoids via 8,14-seco-triterpenoids, which are also detectable in some of the samples investigated. It is proposed that 1,2,5,6-tetramethylnaphthalene, in the coal samples, is formed by cleavage and methyl shift reactions from geminal C-4-methylated triterpenoids which contain a leaving group in position 3. For the shale samples, degradation of monoaromatic secohopanoids must be considered as an alternative pathway.

Monitoring of the three organophosphate esters TBP, TCEP and TBEP in river water and ground water (Oder, Germany)

The behaviour of the three organophosphate esters tributyl phosphate (TBP), tris(2-chloroethyl)phosphate (TCEP) and tris(2-butoxyethyl)phosphate (TBEP) during infiltration of river water to ground water has been investigated. The monitoring site is the Oder River and the adjacent Oderbruch aquifer. From March 2000 to July 2001, 76 ground water samples from monitoring wells located close to the Oder River and nine river water samples were collected. Additionally, influent and effluent samples from local waste water treatment plants, one sample of rain water and samples of roof runoff were collected. All samples were analysed by solid-phase-extraction followed by gas chromatography/mass spectrometry. TBP, TCEP and TBEP were detected at mean values of 622 ng l(-1), 352 ng l(-1), and 2955 ng l(-1), respectively in municipal waste water effluents. This points to a major input of these compounds into the Oder River by municipal waste water discharge. The concentrations of TBP and TBEP decreased downstream the Oder River possibly due to aerobic degradation. TBP, TCEP and TBEP were detected in ground water influenced predominantly by bank-filtered water. This demonstrates a transport of organic compounds by river water infiltration to ground water. TBP, TCEP and TBEP were also detected in rain water precipitation, roof runoff and ground water predominantly influenced by rain water infiltration. This hints to an input of these compounds to ground water by dry and wet deposition after atmospheric transport. Organophosphate esters were also detected in parts of the aquifer at 21 m depth. This demonstrates low anaerobic degradation rates of TBP, TCEP and TBEP.

Sesqui- and diterpenoid biomarkers preserved in Taxodium-rich Oligocene oxbow lake clays, Weisselster basin, Germany

Several diterpenoids of the abietane, pimarane and phyllocladane type, and three cadalanetype sesquiterpenoids have been identified in the organic solvent extracts of Lower Oligocene clay sediments (Haselbach strata, Saxony, Germany). The sediment contains needles and cone scales of a fossil Taxodium species which represents the only conifer in the samples. A clear correlation between the observed conifer biomarkers and Taxodium is evident. Apart from diterpenoids detected previously in other sediments, a new diaromatic totarane diterpenoid is reported. In isolated fossil and Recent Taxodium needles and cone scales as well as in the Haselbach clays a phenolic diterpenoid of the abietane-type, ferruginol, has been identified. The results indicate that the Taxodium-rich clay samples contain several diterpenoids which so far have been used as biomarkers for other conifer families and thus the chemotaxonomical use of diterpenoid biomarkers for the differentiation of fossil conifer families has to be revised.

Occurrence of organophosphate esters in surface water and ground water in Germany

The present investigation was carried out to quantify the three organophosphate esters, tributyl phosphate (TBP), tris(2-chloroethyl) phosphate(TCEP) and tris(2-butoxyethyl) phosphate(TBEP), in river, rain and ground water obtained from several locations in Germany, and to compare the data with those obtained about 15 years ago. Additionally, one influent and one effluent sample of waste water from a local waste water treatment plant were investigated. The applied analytical method is based on solid phase extraction (SPE), in order to concentrate polar compounds from water samples, followed by gas chromatography-mass spectrometry (GC-MS) of the extracts. A total of 5 1 of the respective water samples was used for extraction purposes and analyte recoveries were all > or = 83%. The detection limit for the target analytes was 1 ng l(-1) and the relative standard deviations for replicate injections (n = 10) were 14.0% for TBP, 12.6% for TCEP and 9.9% for TBEP. The presence of the organophosphorus compounds, TBP, TCEP and TBEP, in Germany has resulted in water concentrations of 17-1,510 ng l(-1) in the Rhine, Elbe, Main, Oder, Nidda and Schwarzbach Rivers. The maximum value of TBP measured in the Rhine River was 17 times lower than the maximum value measured 10 years ago. The maximum value of TCEP measured in the Rhine River was 100 times lower than the maximum value measured in previous investigations. The maximum concentration of TBEP measured in the Elbe River was seven times higher than the value measured 16 years ago. Similar concentrations of TBP, TCEP and TBEP were also detected in ground water and rain water. The highest levels of these compounds were detected in samples of waste water.

Paleoenvironmental implications from biomarker and stable isotope investigations on the Pliocene Velenje lignite seam (Slovenia)

A Pliocene lignite seam up to 160 m thick occurs in the Velenje basin (Slovenia). The seam originated in a topogenous mire and evolved within a non-marine, transgressive setting. Differences in soluble organic matter yield and hydrocarbon content of borehole samples from the lignite are related to differences in the composition of free lipids of microbial origin and/or hydrocarbons derived from the biogeochemical degradation of plant tissue. Variations of the redox conditions within the mire are reflected by pristane/phytane ratios. The abundance of terpenoid biomarkers indicates the predominance of gymnosperms over angiosperms, which is consistent with palynomorphic spectra dominated by pollen of the Sequoia-Taxodium-Metasequoia plant community rather than by angiosperms. Evidence is also provided that the content of land plant derived biomarkers and the preservation of plant tissue is controlled by the input of resin-rich, decay-resistant conifers. Sections of the seam characterized by a high degree of gelification of humotelinite (gelification index) show high contents of hop-17(21)-ene but low hopane concentrations. The results suggest that the gelification of plant tissue may be governed by the activity of anaerobic rather than aerobic bacteria. Despite the minor variation in the proportions of gymnosperms versus angiosperms in the peat-forming vegetation, a general influence of the floral assemblage on carbon isotopic composition of the coals (δ13C=−25.3 to −27.0‰) is proposed. Carbon cycling during biogeochemical decomposition of plant tissue by bacteria is assumed to affect the δ13C value of the lignite. Petrographic and geochemical data of gelified and ungelified fossil wood provide evidence that gelification may be governed by microorganisms (e.g. anaerobic bacteria) different from those responsible for decreasing cellulose contents during early diagenetic, aerobic degradation of wood. Based on the molecular composition of terpenoid biomarkers, the wood fragments are identified as derived from gymnosperms. The relative proportions of saturated versus aromatic hydrocarbon fractions of fossil gymnosperms display a general tendency towards lower values in gelified wood remains. This indicates that bacteria involved in gelification of plant tissue may also be involved in aromatisation of diterpenoid hydrocarbons. The chemotaxonomical classification of the macrofossils as gymnosperms is corroborated by the mean carbon isotopic compositions of the macrofossils (δ13C=−24.5‰) and the extracted cellulose (δ13C=−22.0‰). The higher isotopic difference of about 2.5‰ between cellulose and fossil wood, compared to that found in modern trees, can most probably be explained by the smaller effect of 13C discrimination for cellulose when compared with wood during decomposition [Chem. Geol. 158 (1999) 121]. Compared with the coals, the δ13C values of wood and extracted cellulose are affected to a minor extent by microbial activity.

Depositional environment of the Late Miocene Hausruck lignite (Alpine Foreland Basin): Insights from petrography, organic geochemistry, and stable carbon isotopes

Abstract Lignites and fossil wood from two boreholes in the late Miocene Hausruck district (Alpine Foreland Basin, Austria) were investigated with respect to organic carbon and total sulfur contents, ash yields, maceral composition, organic geochemistry, and stable carbon isotope ratios. The lignites from the two sampled profiles differ in sulfur contents and petrography-based facies indicators (gelification index [GI], tissue preservation index [TPI]). The results point to drier and more acidic conditions in the part of the mire sampled at drill site Lukasberg, whereas the lignites from Kalletsberg formed under near neutral conditions due to a raised (ground) water table. The different depositional environments are supported by the paleogeographic positions of the boreholes: borehole Lukasberg is located within a paleo-valley, whereas borehole Kalletsberg is located at the deeper part of a basin situated south and southwest of the Hausruck area. Environmental changes with time within the mire are confirmed by the molecular composition of the soluble organic matter (SOM). Differences in pristane/phytane ratio, isomerisation of hopanes at position 17, concentrations of hopanes, and in the ratio of hopanes to hop-17(21)-enes are related to the extent of gelification of plant tissue, sulfur content and pH values, caused by differences in (ground) water table. The variable contents of individual terpenoid hydrocarbons derived from land plants indicate that angiosperms and conifers contribute to peat formation in the Hausruck district in variable proportions. Overall, angiosperm biomarkers slightly predominate. The tissue preservation index (TPI) within the Kalletsberg profile is probably governed by the proportion of decay-resistant conifers, as indicated by the correlation between TPI and biomarker composition of the coals. Correlations between δ 13 C values of the lignites (between −24.9‰ and −27.4‰) and their non-hopanoid terpenoid composition indicate the major influence of changes in peat-forming vegetation on the carbon isotopic composition of the coals in the Hausruck district. Carbon isotope data of macrofossils are consistent with their taxonomical classification as conifers ( δ 13 C between −22.7‰ and −25.1‰) and angiosperms ( δ 13 C between −25.5‰ and −26.6‰), respectively. The δ 13 C data of the extracted cellulose reveal clear differences between fossil wood from gymnosperms (average δ 13 C=−21.0‰) and angiosperms (mean δ 13 C=−23.4‰).

The secondary oxidation of organic material and its influence on Kupferschiefer mineralization of southwest Poland

Organic geochemical analyses were applied to a series of sixteen extracts obtained from Kupferschiefer samples collected in the Konrad and Rudna mines, southwest Poland. Results show that the content of saturated hydrocarbons in the extracts is reduced relative to the content of aromatic and heteroaromatic compounds. The extent of this effect depends on the intensity of secondary oxidation processes which affected the Kupferschiefer zone. Compounds like phenanthrene, dibenzofuran, dibenzothiophene and biphenyl are enriched by secondary oxidation processes in this sulphide-rich sedimentary rock. The ratio of phenanthrene to the sum of methylphenanthrenes provides a measure of the degree of oxidation in the investigated samples. The most oxidized zone is at the base of the Kupferschiefer. The degree of oxidation decreases upwards. It is envisaged that ascending solutions with an oxidizing, high metal content migrated into the Kupferschiefer which was initially deposited under reducing conditions. Thereby, redox reactions between H-rich organic matter and oxidizing metal solutions occurred and resulted in the secondary enrichment of metals in the Kupferschiefer zone.

Platinum group elements (Pt, Pd, Rh) in airborne particulate matter in rural vs. urban areas of Germany: Concentrations and spatial patterns of distribution

This study examines platinum group element concentrations (PGE) (i.e. platinum (Pt), palladium (Pd) and rhodium (Rh)) and their spatial distribution in airborne particulate matter fractions (PM) of human health concern in urban and rural areas of Germany. Fractionated airborne dust and PM(10), PM(2.5) and PM(1) samples were collected along a busy road in Frankfurt am Main from July 2008 to April 2010. PM(10) was also sampled in Deuselbach and Neuglobsow between January 2008 and July 2009 to examine their concentrations at rural locations and potential for long-range transport. Pt, Pd and Rh were isolated and pre-enriched in samples using a combination of Te and Hg co-precipitation methods. Concentrations were determined using isotope dilution ICP-Q-MS (in collision mode with He). The highest airborne PGE concentrations were measured in PM(10) from Frankfurt (e.g. 12.4pg Pt/m(3) (mean)), while the rural locations of Deuselbach and Neuglobsow exhibited the lowest levels (e.g. 2pg Pt/m(3) (mean)). PGE concentrations were observed to decline with increasingly smaller PM size fractions from PM(10) to PM(1). All size fractions generally contained higher levels of Pd compared to Pt and Rh, an element of greater concern due to its solubility. PM(2.5) collected in Frankfurt had a mean of 16.1pg Pd/m(3), compared to 9.4pg/m(3) for Pt. PGE concentrations also demonstrated a distinct seasonal relationship, with the greatest levels occurring in winter. Compared to a previous study in 2002, PGE concentrations in fractionated airborne dust have significantly increased over time. Elevated PGE levels were also measured for PM(10) sampled in Neuglobsow and Deuselbach, which could not be attributed to local emission sources. Using the diagnostic meteorological model, CALMET, trajectory analyses confirmed our hypothesis that PGE are being transported over longer distances from other areas of Europe.

Organic geochemistry of the Lower Miocene Oberdorf lignite (Styrian Basin, Austria): its relation to petrography, palynology and the palaeoenvironment

Abstract In the Oberdorf trough at the northwestern margin of the Styrian Basin (Austria), an up to 36-m thick Lower Miocene (Ottnangian) lignite seam occurs within the fluvial Koflach–Voitsberg Formation. Previous results indicate that the lignite originated in a topogenous mire within a wet-forest swamp palaeoenvironment. Differences in soluble organic matter (SOM) yield of borehole samples from the lignite seam are related to free lipids present in plant waxes or resins and the presence of thermally labile polymers indicated by the contents of liptinite macerals (i.e., resinite, suberinite, and liptodetrinite). The n -alkane distribution patterns are dominated by high-molecular weight lipids with marked odd over even predominance, originating from plant waxes. A contribution of algae to the even numbered short-chain lipids, observed in considerable amounts in the footwall sediments is proposed. Terpenoid biomarkers characteristic for conifers and angiosperms were detected, consistent with palynomorphic spectra which are dominated by forest swamp pollen (Taxodiaceae–Cupressaceae) and pollen from plants living in a mixed mesophytic forest. Excellent relationships between higher plant biomarker composition and palynologic data indicate that the organic geochemical results reflect the varying inputs of coniferales vs. angiosperms. The data further imply that cuparene may be used for taxonomical differentiation of coniferales families. Organic geochemical data provide evidence that the content of land plant-derived biomarkers is controlled by the input of resin-rich conifers. Concentrations of hopanoids, dominated by hop-17(21)-ene, generally increase towards the top of the lignite, a section characterised by high extents of aromatisation of triterpenoid biomarkers. The results suggest that the aromatisation of angiosperm-derived biomarkers may be governed by the activity of anaerobic rather than by aerobic bacteria. However, changes in the depositional environment and palynologic facies during peat formation probably influenced the origin and fate of angiosperm-derived triterpenoids. The results indicate how biomarker composition may contribute to the evaluation of environmental changes. Cross-correlations of organic geochemical parameters with palynological data and petrography-based facies indicators will provide further insights in the peat-forming vegetation and biogeochemical activities in the mire.