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 (7–18
ng
L
−1) indicating an atmospheric transport of the compound. At urban lakes their median concentrations were in the range of 23–61
ng
L
−1 (TCEP), 85–126
ng
L
−1 (TCPP), <LOQ–53
ng
L
−1 (TBEP), 8–10
ng
L
−1 (TiBP), and 17–32
ng
L
−1 (TnBP). High variability but no significant seasonal trends were observed for all five organophosphates in urban lake water samples.
An effective and sensitive method for the analysis of 1,4-dioxane in water has been available since 2008 (EPA 522). This method is increasingly being applied to investigate the distribution of ...1,4-dioxane in the aquatic environment. However, there is a need for more information about the possible occurrence of 1,4-dioxane in groundwater in Europe in general, and in Germany in particular, where virtually no data have been collected so far. The possible contamination of groundwater with 1,4-dioxane is of relevance to Germany because up to 70% of Germany's drinking water is obtained from groundwater and about 17% from river bank filtrate, which contains variable proportions of groundwater. The aim of the present study is to investigate selected and representative groundwater sites in Germany that have suspected occurrences of 1,4-dioxane. Five of the sites are well known for their volatile chlorinated hydrocarbon contamination, two sites have representative landfill leachate characteristics, and one site is negatively impacted by a detergent manufacturing plant. The presence of 1,4-dioxane was observed at each of these sites. Measured maximum concentration values ranged from 0.15μg/L to 152μg/L. An aquifer containing a trichloroethylene (TCE) plume with 1,4-dioxane as a co-contaminant was investigated in more detail. A perfect match was found between the concentrations of 1,4-dioxane and TCE in the vertical and horizontal distribution profiles. The results indicate the necessity for investigating groundwater contamination by 1,4-dioxane at sites with known 1,1,1-trichloroethane (TCA) and TCE contaminations, in landfill leachates, and at sites of detergent production.
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•1,4-Dioxane was evaluated in German groundwater and was detected at all sites tested.•Max. concentrations of 1,4-dioxane exceed the 0.1μg/L assessment value at each site.•Highest concentration of 1,4-dioxane was detected in a VCH plume (152μg/L).•Depth distribution of 1,4-dioxane exhibited strong correlation with TCE.
The concentrations of 9 organophosphate flame retardants (OPFRs) were determined in 56 indoor and 9 outdoor air samples in the Rhine/Main area in Germany. The indoor samples were collected from seven ...different indoor microenvironments including private cars, private homes, floor/carpet stores, building material markets, schools, offices, and day care centers, while outdoor samples were simultaneously collected close to the indoor sampling locations. The total OPFR concentrations (∑OPFRs) in indoor air ranged from 3.30 to 751.0 ng/m
3
with a median of 40.23 ng/m
3
, which was approximately eight times higher than those in outdoor air (median 5.38 ng/m
3
), indicating that sources of OPFRs predominate in the indoor environment. Tris(2-chloroisopropyl)phosphate (TCPP), tris(isobutyl)phosphate (TiBP), and tributyl phosphate (TnBP) were the dominating compounds both in indoor and outdoor air. The median concentration of ∑OPFRs in private cars (180.3 ng/m
3
) was significantly higher than that in private homes (12.51 ng/m
3
), schools (36.23 ng/m
3
), day care centers (31.80 ng/m
3
), and building material markets (31.17 ng/m
3
) (
p
< 0.05). Distribution profiles of OPFRs varied among different indoor microenvironments, which are evidenced by dominating indoor air concentrations of non-Cl-OPFRs in day care centers, floor/carpet stores, schools, and of Cl-OPFRs in other indoor microenvironments. Multivariate analyses revealed three distinct groups for OPFRs, i.e., TiBP/TnBP, TEP/TCEP/TDCPP, and TCPP, whose concentrations were closely associated with the distribution profiles and pollution characteristics of materials predominating in different indoor microenvironments.
Peat depositional environments, the sites where and conditions under which peat accumulates, significantly influence a resultant coal's physical properties, chemical composition, and coal utilization ...behavior. Recognition of peat depositional environments for coal is a challenging endeavor because coal's observed compositional properties not only result from a variety of geological processes operating during peat accumulation, but also reflect the influence of adjoining or external depositional sedimentary environments and alteration during later diagenesis and/or epigenesis. The maceral or microlithotype composition of any one layer of peat can be the product of years or decades of plant growth, death, decay, and post-burial infiltration by roots in addition to the symbiotic, mutualistic, parasitic, and saprophytic relationships with non-plant biota, such as arthropods, fungi, and bacteria. The overprint of increasing thermal maturation and fluid migration through time on the resulting coal can make these relationships difficult to recognize. Therefore, published models based on maceral composition alone must be used with great caution. Lipid compositions, even from lipid-poor low-rank coals, can provide important information about depositional environments and paleoclimate, especially if combined with the results of organic petrography and paleontological studies. Just as sulfur derived from seawater provides environmental clues, the ratios of two particularly relevant trace elements rather than a single trace element can be used to interpret peat depositional environments. Epigenetic minerals, as well as their corresponding chemical compositions should not be used for such a purpose; similarly, resistant terrigenous minerals deposited during peat accumulation in many cases should be used with considerable caution. The interactions of the biota present in the peat-forming ecosystem, often determined using palynological and geochemical proxies, and their interpretation in the context of geography and paleoclimate are important means for deciphering peat depositional environments. Overall, a combination of evidence from geochemistry, mineralogy, palynology, and petrology of coal and from stratigraphy, sedimentology, and sedimentary facies of related rocks is necessary for accurate and comprehensive determination of depositional environments. The need for interdisciplinary studies is underscored by peat compositional properties, which have been greatly affected by various processes during the syngenetic, diagenetic or epigenetic stages of coal formation.
Potential health effects of 1,4-dioxane and the limited data on its occurrence in the water cycle command for more research. In the current study, mobility and persistence of 1,4-dioxane in the ...sewage-, surface-, and drinking water was investigated. The occurrence of 1,4-dioxane was determined in wastewater samples from four domestic sewage treatment plants (STP). The influent and effluent samples were collected during weekly campaigns. The average influent concentrations in all four plants ranged from 262 ± 32 ng L−1 to 834 ± 480 ng L−1, whereas the average effluent concentrations were between 267 ± 35 ng L−1 and 62,260 ± 36,000 ng L−1. No removal of 1,4-dioxane during water treatment was observed. Owing to its strong internal chemical bonding, 1,4-dioxane is considered non-biodegradable under conventional bio-treatment technologies. The source of increased 1,4-dioxane concentrations in the effluents was identified to originate from impurities in the methanol used in the postanoxic denitrification process in one of the STPs. In view of poor biodegradation in STPs, surface water samples were collected to establish an extent of 1,4-dioxane pollution. Spatial and temporal distribution of 1,4-dioxane in the Rivers Main, Rhine, and Oder was examined. Concentrations reaching 2200 ng L−1 in the Oder River, and 860 ng L−1 in both Main and Rhine River were detected. The average monthly load of 1,4-dioxane in the Rhine River was calculated to equal to 172 kg d−1. In all rivers, concentration of 1,4-dioxane increased with distance from the spring and was found to negatively correlate with the discharge of the river. Additionally, bank filtration and drinking water samples from two drinking water facilities were analyzed for the presence of 1,4-dioxane. The raw water contained 650 ng L−1–670 ng L−1 of 1,4-dioxane, whereas the concentration in the drinking water fell only to 600 ng L−1 and 490 ng L−1, respectively. Neither of the purification processes employed was able to reduce the presence of 1,4-dioxane below the precautionary guideline limit of 100 ng L−1 set by the German Federal Environmental Agency.
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•No removal of 1,4-dioxane was observed in the sewage treatment plants.•Methanol used for denitrification process contained 1,4-dioxane as an impurity.•In the surface waters concentration of 1,4-dioxane reached 2200 ng L−1.•Concentration of 1,4-dioxane in the rivers correlates negatively with the river discharge.•1,4-Dioxane was not eliminated during bank filtration and drinking water production.
Environmental concentrations of platinum group elements (PGE) have been increasing since the introduction of automotive catalytic converters to control harmful emissions. Assessments of the human ...health risks of exposures to these elements, especially through the inhalation of PGE-associated airborne particulate matter (PM), have been hampered by a lack of data on their bioaccessibility. The purpose of this study is to apply in vitro methods using simulated human lung fluids artificial lysosomal fluid (ALF) and Gamble's solution to assess the mobility of the PGE, platinum (Pt), palladium (Pd), and rhodium (Rh) in airborne PM of human health concern. Airborne PM samples (PM(10), PM(2.5), and PM(1)) were collected in Frankfurt am Main, Germany. For comparison, the same extraction experiments were conducted using the standard reference material, Used Auto Catalyst (monolith) (NIST 2557). Pt and Pd concentrations were measured using isotope dilution ICP-Q-MS, while Rh was measured directly with ICP-Q-MS (in collision mode with He), following established matrix separation and enrichment procedures, for both solid (filtered residues) and extracted sample phases. The mobilized fractions measured for PGE in PM(10), PM(2.5), and PM(1) were highly variable, which can be attributed to the heterogenic nature of airborne PM and its composition. Overall, the mobility of PGE in airborne PM samples was notable, with a mean of 51% Rh, 22% Pt, and 29% Pd present in PM(1) being mobilized by ALF after 24 h. For PM(1) exposed to Gamble's solution, a mean of 44% Rh, 18% Pt, and 17% Pd was measured in solution after 24 h. The mobility of PGE associated with airborne PM was also determined to be much higher compared to that measured for the auto catalyst standard reference material. The results suggest that PGE emitted from automotive catalytic converters are likely to undergo chemical transformations during and/or after being emitted in the environment. This study highlights the need to conduct bioaccessibility experiments using samples collected in the field to enable an adequate assessment of risk.
► Paleoenvironmental changes during deposition of oil shales investigated. ► Salinity stratification of the water column reconstructed. ► Anoxic cycles during Late Cretaceous outlined. ► Sources of ...organic matter discussed.
Excellent hydrocarbon source rocks (oil shales), containing Type I organic matter (OM), were deposited in the continental Songliao rift basin during the Late Cretaceous. A major contribution of aquatic organisms (dinoflagellates, green algae, botryococcus) and minor input from macrophytes and land plants to OM accumulation is indicated by n-alkane distribution, steroid composition and δ13C values of individual biomarkers. Microbial communities included heterotrophic bacteria, cyanobacteria and chemoautotrophic bacteria, as well as purple and green sulfur bacteria. The presence of methanotrophic bacteria is indicated by 13C-depleted methyl hopane. The sediments were deposited in a eutrophic, alkaline palaeolake. Highly reducing (saline) bottom water conditions and a stratified water column existed during OM accumulation of the Qingshankou Formation and Member 1 of the Nenjiang Formation. This is indicated by low pristane/phytane, gammacerane index and MTTC ratios, and the presence of β-carotane and aryl isoprenoids. However, an abrupt change in environmental conditions during deposition of Member 2 of the Nenjiang Formation is indicated by significant changes in salinity and redox-sensitive biomarker ratios. A freshwater environment and suboxic conditions in the deep water prevailed during this period. Higher input of terrigenous OM occurred during deposition of the upper Nenjiang Formation.
Good oil-to-source rock correlation was obtained using biomarker fingerprints of oil-stained sandstone from the Quantou Formation and oil shales from the Qingshankou Formation. Based on the extent of isomerisation of C31 hopanes, the oil was most probably derived from oil shales of the Qingshankou Formation in deeper parts of the basin.
To investigate seasonal fluctuations and trends of organophosphate (flame retardants, plasticizers) concentrations in rain and snow, precipitation samples were collected in 2007–2009 period at a ...densely populated urban sampling site and two sparsely populated rural sampling sites in middle Germany. In addition, storm water runoff was sampled from May 2008 to April 2009 at an urban storm water holding tank (SWHT). Samples were analyzed for tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCP), tris(2-butoxyethyl) phosphate (TBEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) by gas chromatography–mass spectrometry after solid phase extraction. Among the six analyzed organophosphates (OPs), TCPP dominated in all precipitation and SWHT water samples with maximum concentrations exceeding 1000
ng
L
−1. For all analytes, no seasonal trends were observed at the urban precipitation sampling site, although atmospheric photooxidation was expected to reduce particularly concentrations of non-chlorinated OPs during transport from urban to remote areas in summer months with higher global irradiation. In the SWHT a seasonal trend with decreasing concentrations in summer/autumn is evident for the non-chlorinated OPs due to in-lake degradation but not for the chlorinated OPs. Furthermore, an accumulation of OPs deposited in SWHTs was observed with concentrations often exceeding those observed in wet precipitation. Median concentrations of TCPP (880
ng
L
−1), TDCP (13
ng
L
−1) and TBEP (77
ng
L
−1) at the SWHT were more than twice as high as median concentrations measured at the urban precipitation sampling site (403
ng
L
−1, 5
ng
L
−1, and 21
ng
L
−1 respectively).
► Degradation of the target compounds in water followed a first-order kinetic model. ► Rates of direct photodegradation were very low for all of the target compounds. ► Indirect photodegradation of ...the compounds in river water is likely to occur. ► Biotic degradation in surface water occur at very low rates (⩽0.00029h−1).
The photodegradation and biotic transformation of the pharmaceuticals lidocaine (LDC), tramadol (TRA) and venlafaxine (VEN), and of the metabolites O-desmethyltramadol (ODT) and O-desmethylvenlafaxine (ODV) in the aquatic environmental have been investigated. Photodegradation experiments were carried out using a medium pressure Hg lamp (laboratory experiments) and natural sunlight (field experiments). Degradation of the target compounds followed a first-order kinetic model. Rates of direct photodegradation (light absorption by the compounds itself) at pH 6.9 were very low for all of the target analytes (⩽0.0059h−1 using a Hg lamp and ⩽0.0027h−1 using natural sunlight), while rates of indirect photodegradation (degradation of the compounds through photosensitizers) in river water at pH 7.5 were approximately 59 (LDC), 5 (TRA), 8 (VEN), 15 (ODT) and 13 times (ODV) higher than the rates obtained from the experiments in ultrapure water. The accelerated photodegradation of the target compounds in natural water is attributed mainly to the formation of hydroxyl radicals through photochemical reactions. Biotic (microbial) degradation of the target compounds in surface water has been shown to occur at very low rates (⩽0.00029h−1). The half-life times determined from the field experiments were 31 (LDC), 73 (TRA), 51 (VEN), 21 (ODT) and 18h (ODV) considering all possible mechanisms of degradation for the target compounds in river water (direct photodegradation, indirect photodegradation and biotic degradation).
Three different lithotypes (xylitic, gelified and matrix) of Pliocene lignite from the Velenje Basin, Slovenia, were investigated to establish the variations of biomarker compositions in solvent ...extracts and the stable isotope (carbon and nitrogen) compositions of bulk material. From the biomarker results, the xylitic lithotype almost exclusively originates from gymnosperms (conifers such as Taxodiaceae), as indicated by the very high contents of sesquiterpenoids and diterpenoids but very low abundances of n-alkanes and non-hopanoid triterpenoids. The relative proportion of gymnosperms to angiosperms in the paleomire is reflected by the ratio of diterpenoids to the sum of diterpenoids and non-hopanoid triterpenoids (Di-/(Di-+Tri-terpenoids)), which is close to 1 (av. 0.99) in the xylitic lithotype. The predominance of diterpenoids from conifers in the xylitic lithotype is associated with high C/N ratios and intermediate total sulfur (TS). The very low abundance of hop-17(21)-ene and the absence of further hopanoids in the xylitic lithotype indicate a restricted influence of bacterial degradation under relatively dry conditions in the paleomire. The matrix lithotype also originated preferentially from gymnosperms under dry depositional conditions, as indicated by the high Di-/(Di-+Tri-terpenoids) ratio (0.95), low amounts of hopanoids and low TS content. The gelified lithotype is characterized by a high content of n-alkanes and wide variation of the Di-/(Di-+Tri-terpenoids) ratio (0.13–0.88), indicating a fluctuating contribution of angiosperms to the plant community in the paleomire during formation of this lithotype. In addition, the high abundance of hop-17(21)-ene and TS in the gelified lithotype compared with the other two lithotypes suggests the effect of bacterial activity under relatively wet/humid conditions during formation of the gelified lithotype, which is also supported by the considerable content of mid-chain n-alkanes.
The high correlation between the δ13C and δ15N values (R2 = 0.68) indicates that the stable carbon and nitrogen isotope composition in the Velenje lignites were probably influenced by the same factors (e.g. precursor plants and/or microbial activity). The stable carbon isotopic values (av. −25.44‰) and nitrogen isotopic values (av. 2.15‰) of the xylitic lithotype are higher than those of the gelified lithotype (av. δ13C = −27.48‰, δ15N = 1.37‰) and the matrix lithotype (av. δ13C = −27.09‰, δ15N = 1.10‰). The relatively high correlation between the diterpenoid content and both δ13C and δ15N values suggests that the stable carbon and nitrogen isotopic composition of the three lithotypes might reflect the composition of the original plant material in the paleomire. The dominance of conifers as precursor plants in the xylitic lithotype might be the main reason for the higher δ13C values and probably also the higher δ15N values. The relatively higher δ15N values in the xylitic lithotype than in the other types could be explained by the high amount of decay-resistant xylem and low mineral (e.g. clay) content in the xylitic lithotype. The slightly lower δ13C but higher δ15N values in the gelified lithotype than in the matrix lithotype can be explained by variation of parent plant materials and the influence of bacterial activity.
•Different lithotypes (xylitic, gelified and matrix) of Pliocene lignite from the Velenje Basin, Slovenia, were analyzed for biomarkers and stable isotope (C and N) compositions.•The ratio of diterpenoids/(diterpenoids + triterpenoids) reflects the relative proportions of gymnosperms and angiosperms.•Xylitic and matrix lithotypes originate from gymnosperms, while gelified lithotypes are characterized by a fluctuating contribution of angiosperms.•The highest δ13C and δ15N values were measured in xylitic lithotype samples.•The δ13C and δ15N composition is preferentially influenced by the composition of the precursor plants community.
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