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 PM10, PM2.5 and PM1 samples were collected along a busy road in Frankfurt am Main from July 2008 to April 2010. PM10 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 PM10 from Frankfurt (e.g. 12.4pg Pt/m3 (mean)), while the rural locations of Deuselbach and Neuglobsow exhibited the lowest levels (e.g. 2pg Pt/m3 (mean)). PGE concentrations were observed to decline with increasingly smaller PM size fractions from PM10 to PM1. All size fractions generally contained higher levels of Pd compared to Pt and Rh, an element of greater concern due to its solubility. PM2.5 collected in Frankfurt had a mean of 16.1pg Pd/m3, compared to 9.4pg/m3 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 PM10 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.
► Platinum group element (PGE) levels in airborne PM of human health concern have increased with time. ► Data on platinum (Pt), rhodium (Rh) and palladium (Pd) levels in PM1 reported for first time. ► PGE concentrations in rural areas of Germany do not reflect local emission sources. ► PGE are likely transported long-distances from urban to rural locations. ► PGE concentrations in airborne PM are higher in winter compared to summer.
The role of precipitation as an important source of, and entry pathway for, organophosphates (OPs) into the aquatic environment was investigated. Rainwater and snow samples (53 and 43, respectively) ...collected between November 2007 and April 2008 from urban and remote areas of middle Germany were analyzed for OPs by gas chromatography‐mass spectrometry (GC‐MS) after solid phase extraction (SPE). The analytes 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) were detected in almost all rain and snow samples. TCPP was the most abundant chlorinated alkyl‐phosphate ester in urban rainwater, with concentrations ranging from 46 to 2659 ng L–1. In general, concentrations of OPs in urban rainwater were 3 to 4 times higher than those at background monitoring stations, e. g., Schmücke and Thuringian Forest. Variable concentrations of chlorinated flame retardants were found in precipitation, but their occurrence was not correlated with air temperature. The results of the study indicate that volatilization of OPs from objects protected by flame retardants, including vehicles and buildings, causes these compounds to reach the aquatic environment via washout from the atmosphere, despite their reported short atmospheric half‐lives (< 24 h).
Research Article: The role of precipitation as an important entry pathway for organophosphorus flame retardants and plasticizers into the aquatic environment is investigated by analyzing rainwater and snow samples from urban and remote areas of middle Germany, using gas chromatography‐mass spectrometry after solid phase extraction.
Coals contain native polycyclic aromatic compounds (PACs), which include polycyclic aromatic hydrocarbons (PAHs), and heterocyclic aromatic compounds (NSO-PACs) in considerably varying amounts up to ...2500 mg/kg. Whereas PAC bioavailability and toxicity from coals are generally considered to be low, few studies have considered potential variations arising from the composition of different coal types including native PAC content. In the present study, fine particles of different coal types exhibiting variable properties were systematically investigated regarding their PAC bioavailability. PAH content reached up to 79 mg/kg EPA-PAH and 865 mg/kg total PAH. Determination of the toxic potential of extracted PACs in bioassays showed inhibition of Caenorhabditis elegans reproduction (up to 94%) and increased mortality of Danio rerio embryos (up to 100%) after exposure to extracts from lignite, sub-bituminous, and bituminous coals. Anthracite extracts showed no effects. Contact assays using whole coal samples revealed no toxicity to D. rerio embryos in any of the coal samples, suggesting low bioavailability of PACs. In contrast, C. elegans reproduction was inhibited by direct coal contact; however, the observed toxicity probably resulted from other coal effects. The results suggest that despite the high toxic potential of PACs present, their bioavailability from different coal types is very limited and independent of coal properties and native PAH content.
Parabens and sorbic acid are commonly used as food preservatives due to their antimicrobial effect. However, their use in foods for infants and young children is not permitted in the European Union. ...Previous studies found these compounds in some gel-filled baby teethers, whereby parabens, which are well-known as endocrine disruptors, were identified in the polymer-based chewing surface consisting of ethylene-vinyl acetate (EVA). To assess the exposure of infants and young children to these products, the application of parabens in teethers should be thoroughly investigated. Therefore, the present study aimed to apply a representative migration test procedure combined with an accurate analytical method to examine gel-filled baby teethers without elaborate sample preparation, high costs, and long processing times. Accordingly, solid-phase extraction (SPE), in combination with a stable isotope dilution assay (SIDA) and subsequent gas chromatography–mass spectrometry (GC–MS) for analysis of methyl-, ethyl-, and
n
-propylparaben (MeP, EtP, and
n
-PrP), was found to be well-suited, with recoveries ranging from 93 to 99%. The study compared the release of these parabens from intact teether surfaces into water and saliva simulant under real-life conditions, with total amounts of detected parabens found to be in the range of 101–162 µg 100 mL
−1
and 57–148 µg 100 mL
−1
, respectively. Furthermore, as a worst-case scenario, the release into water was examined using a long-term migration study.
Background
On Late Cretaceous Tethyan upwelling sediments from the Mishash/Ghareb Formation (Negev, Israel), bulk geochemical and biomarker analyses were performed to explain the high proportion of ...phosphates in the lower part and of organic matter (OM) preserved in upper parts of the studied section. The profile is composed of three facies types; the underlying Phosphate Member (PM), the Oil Shale Member (OSM) and the overlying Marl Member (MM).
Results
Total organic carbon (TOC) contents are highly variable over the whole profile reaching from 0.6% in the MM, to 24.5% in the OSM. Total iron (TFe) varies from 0.1% in the PM to 3.3% in the OSM. Total sulfur (TS) ranges between 0.1% in the MM and 3.4% in the OSM, resulting in a high C/S ratio of 6.5 in the OSM section. A mean proportion of 11.5% total phosphorus (TP) in the PM changed abruptly with the facies to a mean value of only 0.9% in the OSM and the MM.
The TOC/TOC
OR
ratios argue for a high bacterial sulfate reduction activity and in addition, results from fatty acid analyses indicate that the activity of sulfide-oxidizing activity of bacteria was high during deposition of the PM, while decreasing during the deposition of the OSM.
Conclusions
The upwelling conditions effected a high primary productivity and consequently the presence of abundant OM. This, in combination with high sulfate availability in the sediments of the PM resulted in a higher sulfide production due to the activity of sulfate-reducing bacteria. Iron availability was a limiting factor during the deposition of the whole section, affecting the incorporation of S into OM. This resulted in the preservation of a substantial part of OM against microbial degradation due to naturally-occurring sulfurization processes expressed by the high C/S ratio of 6.5 in the OSM.
Further, the abundant sulfide in the pore water supported the growth of sulfide-oxidizing bacteria promoting the deposition of P, which amounted to as much as 15% in the PM. These conditions changed drastically from the PM to the OSM, resulting in a significant reduction of the apatite precipitation and a high concentration of reactive S species reacting with the OM.
The sensitivity and precision of headspace solid-phase micro extraction (HS-SPME) at an analyte solution temperature (T as) of +35 °C and a fiber temperature (T fiber) of +5 °C were compared with ...those for HS-SPME at T as and T fiber of -20 °C for analysis of the volatile organic compounds benzene, 1,1,1-trichloroethane, trichloroethylene, toluene, o-xylene, ethylbenzene, m/p-xylene, and tetrachloroethylene in water samples. The effect of simultaneous fiber cooling and analyte solution freezing during extraction was studied. The compounds are of different hydrophobicity, with octanol/water partition coefficients (Kow) ranging from 126 and 2511. During a first set of experiments the polydimethylsiloxane (PDMS) SPME fiber was cooled to +5 °C with simultaneous heating of the aqueous analyte solution to +35 °C. During a second set of experiments, both SPME fiber holder and samples were placed in a deep freezer maintained at -20 °C for a total extraction time of 30 min. After approximately 2 min the analyte solution in the vial began to freeze from the side inwards and from the bottom upwards. After approximately 30 min the solution was completely frozen. Analysis of VOC was performed by coupling HS-SPME to gas chromatography-mass spectrometry (GC-MS). In general, i.e. except for tetrachloroethylene, the sensitivity of HS-SPME increased with increasing compound hydrophobicity at both analyte solution and fiber temperatures. At T as of +35 °C and T fiber of +5 °C detection limits of HS-SPME were 0.5 μg L-¹ for benzene, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene, 0.125 μg L-¹ for toluene, and 0.025 μg L-¹ for ethylbenzene, m/p-xylene, and o-xylene. In the experiments with T as and T fiber of -20 °C, detection limits were reduced for compounds of low hydrophobicity (Kow<501), for example benzene, toluene, 1,1,1-trichloroethane, and trichloroethylene. In the concentration range 0.5-62.5 μg L-¹, the sensitivity of HS-SPME was enhanced by a factor of approximately two for all compounds by performing the extraction at -20 °C. A possible explanation is that freezing of the water sample results in higher concentration of the target compounds in the residual liquid phase and gas phase (freezing-out), combined with enhanced adsorption of the compounds by the cooled fiber. The precision of HS-SPME, expressed as the relative standard deviation and the linearity of the regression lines, is increased for more hydrophobic compounds (Kow>501) by simultaneous direct fiber cooling and freezing of analyte solution. Background contamination during analysis is reduced significantly by avoiding the use of organic solvents.
Carbon isotope analyses of terrigenous organic matter are often used to reconstruct changes in the isotopic composition of upper ocean and atmospheric carbon reservoirs. Carbon isotope values from ...tree-rings, fossil wood, and coal matrices have been related to climatic change (e.g. temperature, humidity) via water-use efficiency of land plants. In this study, we report on carbon isotope analyses on low-rank coal deposits of the Alpine Realm and Middle German Lignite District covering the Early Eocene to Pliocene time interval.
Fossil wood and extracted wood cellulose from gymnosperms and angiosperms, respectively, are used for paleoenvironmental reconstructions. The trend in δ
13C is parallel to the carbon isotope record obtained from benthic foraminifera, because both data sets sample a common reservoir in the atmosphere.
The evaluation of the magnitudes of δ
13C variations of coal caused by environmental change, requires the correction of the δ
13C data due to the effects of different contents of lipids in the organic matter, differences in biogeochemical carbon cycling, varying contributions of gymnosperms versus angiosperms to peat formation, and differences in δ
13C of atmospheric CO
2. The resulting carbon isotope record of coal generally co-varies with the estimated variability in mean annual temperatures during the Tertiary, based on paleobotanical data. Changes in humidity and
pCO
2 may be responsible for deviations between the isotopic trend and the paleotemperature curve during the Miocene. The obtained temperature coefficient for δ
13C of C3 plants of about 0.3‰/°C is in agreement with the results of previous studies.
The behavior of anthropogenic polar organic compounds in ground water during infiltration of river water to ground water was studied at the Oderbruch area on the eastern border of Germany. ...Additionally, waste water sewage treatment works (STWs) discharging their treated waste water into the Oder River and rain water precipitation from the Oderbruch area were investigated. The study was carried out from March 2000 to July 2001 to investigate seasonal variations of the target analytes. Samples were collected from four sites along the Oder River, from 24 ground water monitoring wells located close to the Oder, from one rain water collection station, from two roof runoffs, and from four STWs upstream of the Oderbruch. Results of the investigations of the antioxidant 3,5-di-
tert-butyl-4-hydroxy-toluene (BHT) and its degradation product 3,5-di-
tert-butyl-4-hydroxy-benzaldehyde (BHT-CHO) are presented. BHT and BHT-CHO were detected in all samples of the Oder River with mean concentrations of 178 and 102 ng
l
−1, respectively. BHT and BHT-CHO were also detected in effluent waste water samples from municipal STWs at mean concentrations of 132 and 70 ng
l
−1, respectively. Both compounds are discharged into river water directly via treated waste water. In the rain water sample, 308 ng
l
−1 of BHT and 155 ng
l
−1 of BHT-CHO were measured. Both compounds were detected in roof runoff with mean concentrations of 92 ng
l
−1 for BHT and 138 ng
l
−1 for BHT-CHO. The median values of BHT and BHT-CHO in ground water samples were 132 and 84 ng
l
−1, respectively. The chemical composition of ground water from parts of the aquifer located less than 4.5 m distant from the river are greatly influenced by bank filtration. However, wet deposition followed by seepage of rain water into the aquifer is also a source of BHT and BHT-CHO in ground water.
The distributions of organophosphate flame retardants (OPFRs) in various size fractions of indoor dust samples from homes (H; n = 18) and building material markets (B; n = 7) in the Rhine/Main region ...of Germany were investigated. Three particle size fractions (F1: 150–200 μm, F2: 63–150 μm, and F3: <63 μm) and bulk dust (BD) subsamples (<200 μm) of each sample were analyzed for 10 OPFRs. On average, the total OPFR concentrations (∑10OPFR) in bulk dust and all three size fractions from building material markets were 133, 153, 196, and 88.0 μg/g in subsamples B-BD, B-F1, B-F2, and B-F3. These concentrations were at least five times higher than those in bulk dust and all three size fractions from homes, with values of 19.3, 17.2, 19.5, and 18.7 μg/g for subsamples H-BD, H-F1, H-F2, and H-F3, respectively. Tris(2-chloroisopropyl)phosphate (TCIPP) was the dominant congener in dust from building material markets, contributing over 91% to the ∑10OPFR of B-BD and all particle size fractions. Meanwhile, both tris(2-butoxyethyl)phosphate (TBOEP) and TCIPP were abundant in dust from homes, respectively contributing 28%–41% and 31%–43% to the ∑10OPFR of H-BD and all particle size fractions. Most of the OPFR concentrations showed no consistent trend with particle size. However, TCIPP was more likely to be enriched in F2. Microscopic examination indicated that TCIPP in indoor dust mainly originated from abraded fragments of commercial products. In contrast, TBOEP accumulated in F3, related to direct transfer of floor-care products to fine dust particles. The concentrations of OPFRs were not significantly correlated with total organic carbon contents in any particle size fraction. However, evaluation of their mass contributions showed that more than 85% of OPFRs accumulated in particles smaller than 150 μm, indicating that this particle size fraction is most suitable for monitoring of OPFRs.
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•OPFR concentrations in dust from homes and building material markets were compared.•Building material markets had higher OPFR levels than private homes.•TCIPP was typically enriched in the intermediate dust fraction F2 (63–150 μm in size).•TBOEP tended to accumulate in the finest dust fraction F3 (<63 μm in size).•Monitoring of OPFRs in indoor dust particles < 150 μm in size is recommended.
This study explores the contribution of different dust size fractions to OPFR contamination in homes and building material markets.
Mercury (Hg) is still a focus of environmental research, since its levels in fish frequently exceed the Environmental Quality Standard (EQS) of 20 µg/kg for biota defined by the European Water ...Framework Directive (Directive 2008/105/EC). Current Hg levels in Abramis brama from German rivers are in the range of 73–346 µg/kg wet weight (2009) and exceed the EQS by a factor of 3.7–17.3. Therefore, it is important to identify the sources of Hg pollution in the aquatic environment and to develop effective strategies for reducing the input into associated river systems. The aim of the present study was to analyze Hg in the urban water cycle of the city of Frankfurt am Main, Germany. Samples were taken from the river Main crosscutting the city and its tributaries. In addition, precipitation, stormwater runoff, effluents of two municipal WWTPs, and stormwater management structures such as combined sewer overflows and stormwater retention basins have been analyzed. Loads of Hg have been determined based on the measured concentrations and a Hg mass balance for the aquatic system was created. A total of 160 water samples were analyzed by cold vapor atomic fluorescence spectroscopy (CVAFS) according to US EPA Method 1631. Results from the mass balance have shown that approximately 5 kg Hg/a enter and 15 kg Hg/a leave the study area of Frankfurt am Main via the river Main. The largest amount of Hg (24.58 kg/a) throughout the urban water cycle of Frankfurt am Main is transported via wastewater. However, municipal WWTPs in Frankfurt am Main have been identified as the largest Hg sink, since 99.7% (24.5 kg/a) of the Hg is shifted from the sewage water and stormwater during treatment into the sewage sludge. Thus, the increase of the Hg load in the river Main from 5 to 15 kg/a has to be attributed to other sources such as 3 industrial WWTPs, groundwater and non-treated stormwater runoff during heavy rain events.
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