Ecotoxicity and fate of a silver nanomaterial in an outdoor lysimeter study.

Sewage sludge is repeatedly applied as fertilizer on farmland due to its high nutrient content. This may lead to a significant increase of silver nanomaterials (AgNM) in soil over years. Therefore, our aim was to investigate the ecotoxicity and fate of AgNM under environmentally relevant conditions in outdoor lysimeters over 25 months. Two AgNM concentrations (1.7 and 8.0 mg/kg dry matter soil) were applied via sewage sludge into soil. In subsamples of the soil, incubated under laboratory conditions for 180 days, the comparability of outdoor and laboratory results regarding ecotoxicity was determined. The results from our long term lysimeter experiments show no detectable horizontal displacement in combination with very low remobilization to the percolate water. Thus, indicate that the sludge applied AgNM remains nearly immobile in the pathway between soils and leachate. However, Ag uptake to the roots of wheat and canola suggests that the chemical conditions in the rhizosphere induce AgNM remobilization from the incorporated sewage sludge even after two harvesting cycles. At the higher AgNM concentration a steady inhibition of the soil microflora was observed over 25 month in the lysimeter study, while there was no effect at the lower AgNM concentration. The results of the laboratory experiment reflect the findings of the lysimeter study and indicate that a risk assessment for AgNM based on data from laboratory tests is acceptable.

Interactions of ciprofloxacin (CIP), titanium dioxide (TiO2) nanoparticles and natural organic matter (NOM) in aqueous suspensions.

The aim of the present study was to investigate interactions of the antibiotic ciprofloxacin (CIP), titanium dioxide nanoparticles (TiO2 NP) and natural organic matter (NOM) in aqueous suspensions. The mean hydrodynamic diameter of particles of TiO2 NP and NOM in the suspensions ranged from 113 to 255nm. During batch experiments the radioactivity resulting from (14)CIP was determined in the filtrate (filter pore size 100nm) by scintillation measurements. Up to 72h, no significant sorption of NOM to TiO2 NP was observed at a TiO2 NP concentration of 5mg/L. When the concentration of TiO2 NP was increased to 500mg/L, a small amount of NOM of 9.5%±0.6% was sorbed at 72h. The low sorption affinity of NOM on TiO2 NP surfaces could be explained by the negative charge of both components in alkaline media or by the low hydrophobicity of the NOM contents. At a TiO2 NP concentration of 5mgL(-1), the sorption of CIP on TiO2 NP was insignificant (TiO2 NP/CIP ratio: 10). When the TiO2 NP/CIP ratio was increased to 1000, a significant amount of 53.6%±7.2% of CIP was sorbed on TiO2 NP under equilibrium conditions at 64h. In alkaline media, CIP is present mainly as zwitterions which have an affinity to sorb on negatively charged TiO2 NP surfaces. The sorption of CIP on TiO2 NP in the range of TiO2 NP concentrations currently estimated for municipal wastewater treatment plants is estimated to be rather low. The Freundlich sorption coefficients (KF) in the presence of NOM of 2167L(n)mgmg(-n)kg(-1) was about 10 times lower than in the absence of NOM. This is an indication that the particle fraction of NOM<100nm could play a role as a carrier for ionic organic micro-pollutants as CIP.

Occurrence and spatial distribution of microplastics in sediments from Norderney.

The spatial distribution of small potential microplastics (SPM) (<1 mm) in beach sediments was studied on a 500 m stretch of the North Sea island of Norderney. Their correlation with visible plastic debris (VPD) (>1 mm) was also examined. Small microparticles were extracted from 36 one kg sediment samples and analysed by visual microscopic inspection and partly by thermal desorption pyrolysis gas chromatography/mass spectrometry. The smallest particle size that could be analysed with this method was estimated to be 100 µm. The mean number of SPM at the three sampling sites (n = 12) was 1.7, 1.3 and 2.3 particles per kg dry sediment, respectively. SPM were identified as polypropylene, polyethylene, polyethylene terephthalate, polyvinylchloride, polystyrene and polyamide. The organic plastic additives found were benzophenone, 1,2-benzenedicarboxylic acid, dimethyl phthalate, diethylhexyl phthalate, dibutyl phthalate, diethyl phthalate, phenol and 2,4-di-tert-butylphenol. Particles were distributed rather homogenously and the occurrence of SPM did not correlate with that of VPD.

A new analytical approach for monitoring microplastics in marine sediments.

A two-step method was developed to extract microplastics from sediments. First, 1 kg sediments was pre-extracted using the air-induced overflow (AIO) method, based on fluidisation in a sodium chloride (NaCl) solution. The original sediment mass was reduced by up to 80%. As a consequence, it was possible to reduce the volume of sodium iodide (NaI) solution used for the subsequent flotation step. Recoveries of the whole procedure for polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polystyrene and polyurethane with sizes of approximately 1 mm were between 91 and 99%. After being stored for one week in a 35% H2O2 solution, 92% of selected biogenic material had dissolved completely or had lost its colour, whereas the tested polymers were resistant. Microplastics were extracted from three sediment samples collected from the North Sea island Norderney. Using pyrolysis gas chromatography/mass spectrometry, these microplastics were identified as PP, PVC and PET.

Microplastics in freshwater ecosystems: what we know and what we need to know.

BACKGROUND: While the use of plastic materials has generated huge societal benefits, the 'plastic age' comes with downsides: One issue of emerging concern is the accumulation of plastics in the aquatic environment. Here, so-called microplastics (MP), fragments smaller than 5 mm, are of special concern because they can be ingested throughout the food web more readily than larger particles. Focusing on freshwater MP, we briefly review the state of the science to identify gaps of knowledge and deduce research needs. STATE OF THE SCIENCE: Environmental scientists started investigating marine (micro)plastics in the early 2000s. Today, a wealth of studies demonstrates that MP have ubiquitously permeated the marine ecosystem, including the polar regions and the deep sea. MP ingestion has been documented for an increasing number of marine species. However, to date, only few studies investigate their biological effects. The majority of marine plastics are considered to originate from land-based sources, including surface waters. Although they may be important transport pathways of MP, data from freshwater ecosystems is scarce. So far, only few studies provide evidence for the presence of MP in rivers and lakes. Data on MP uptake by freshwater invertebrates and fish is very limited. KNOWLEDGE GAPS: While the research on marine MP is more advanced, there are immense gaps of knowledge regarding freshwater MP. Data on their abundance is fragmentary for large and absent for small surface waters. Likewise, relevant sources and the environmental fate remain to be investigated. Data on the biological effects of MP in freshwater species is completely lacking. The accumulation of other freshwater contaminants on MP is of special interest because ingestion might increase the chemical exposure. Again, data is unavailable on this important issue. CONCLUSIONS: MP represent freshwater contaminants of emerging concern. However, to assess the environmental risk associated with MP, comprehensive data on their abundance, fate, sources, and biological effects in freshwater ecosystems are needed. Establishing such data critically depends on a collaborative effort by environmental scientists from diverse disciplines (chemistry, hydrology, ecotoxicology, etc.) and, unsurprisingly, on the allocation of sufficient public funding.

Identification of polymer types and additives in marine microplastic particles using pyrolysis-GC/MS and scanning electron microscopy.

Any assessment of plastic contamination in the marine environment requires knowledge of the polymer type and the additive content of microplastics. Sequential pyrolysis-gas chromatography coupled to mass spectrometry (Pyr-GC/MS) was applied to simultaneously identify polymer types of microplastic particles and associated organic plastic additives (OPAs). In addition, a scanning electron microscope equipped with an energy-dispersive X-ray microanalyser was used to identify the inorganic plastic additives (IPAs) contained in these particles. A total of ten particles, which were optically identified as potentially being plastics, were extracted from two sediment samples collected from Norderney, a North Sea island, by density separation in sodium chloride. The weights of these blue, white and transparent fragments varied between 10 and 350 µg. Polymer types were identified by comparing the resulting pyrograms with those obtained from the pyrolysis of selected standard polymers. The particles consisted of polyethylene (PE), polypropylene, polystyrene, polyamide, chlorinated PE and chlorosulfonated PE. The polymers contained diethylhexyl phthalate, dibutyl phthalate, diethyl phthalate, diisobutyl phthalate, dimethyl phthalate, benzaldehyde and 2,4-di-tert-butylphenol. Sequential Py-GC/MS was found to be an appropriate tool for identifying marine microplastics for polymer types and OPAs. The IPAs identified were titanium dioxide nanoparticles (TiO2-NPs), barium, sulphur and zinc. When polymer-TiO2 composites are degraded in the marine environment, TiO2-NPs are probably released. Thus, marine microplastics may act as a TiO2-NP source, which has not yet been considered.

New developments in the trace analysis of organic water pollutants.

Challenging tasks, increasing demands, and new generations of powerful analytical instruments initiated considerable progress in aquatic environmental analysis and led to a considerable improvement of analytical performance during the last few years. The ever growing number of emerging pollutants is tackled by specific and highly sensitive analytical methods with detection limits of a few nanogram per liter and even lower. Wide-scope monitoring techniques and multiclass and multiresidue analysis allow for the simultaneous determination of hundreds of compounds. The high mass resolution capability and mass accuracy of advanced mass spectrometric instruments, i.e., time-of-flight (TOF) MS or Fourier transform (FT)-Orbitrap MS, enable combined target and non-target analysis, including the identification of metabolites and abiotic degradation products. This minireview highlights some of the most recent developments in the trace analysis of important organic water pollutants and focuses on some specific groups of emerging contaminants, i.e., pharmaceuticals, flame retardants, disinfection by-products, surfactants, per- and polyfluorinated compounds, benzotriazoles, and benzothiazoles, as well as on the identification of transformation products and on non-target analysis. References were selected according to their exemplary and innovative character and to their practical relevance.

Seasonal source influence on river mass flows of benzotriazoles.

The anticorrosive agents 1H-benzotriazole (1H-BT), 4-methyl-1H-benzotriazole (4 Me-BT) and 5-methyl-1H-benzotriazole (5 Me-BT), which are usually added to dishwasher detergents, automotive antifreeze formulations and aircraft de-icing/anti-icing fluids (ADAFs), were measured in river water. Samples were collected from 15 sampling sites in the mainstream and selected tributaries of a medium-sized catchment area during summer and winter periods. The aim of this study was to assess a seasonal source influence on mass flows of benzotriazoles (BTs). The study area was representatively selected for an area with a possible influence of airport surface runoff. River discharge measurements were also performed. Moreover, BT concentrations were measured in an anti-icing and a de-icing fluid used at German airports as well as in several dishwasher detergents. The highest concentrations of all three compounds in river water were measured during the winter seasons. The maximum BT mass flows were calculated for all three substances in January when the mean monthly air temperature was the lowest; mass flows were the lowest in July when the mean monthly air temperature was the highest. A significant seasonal influence on BT mass flows in river water was observed for monitoring stations with a possible influence of airport surface runoff and for sampling locations where such an influence could be excluded. This indicates an input of BTs from other temperature-dependent applications, e.g. the use of antifreeze formulations in automotive windscreen wiper or cooling systems. 1H-BT was detected in two dishwasher tablets; 4 Me-BT and 5 Me-BT were not detected. BTs were measured in the anti-icing fluid with concentrations of 715 ng g(-1) (1H-BT), 1425 ng g(-1) (4 Me-BT) and 536 ng g(-1) (5 Me-BT); none of the BTs were detected in the de-icing fluid. Distribution patterns of BTs in ADAF and dishwasher detergents differed from those in river water.

Acute and chronic toxicity of benzotriazoles to aquatic organisms.

PURPOSE: Resulting from their intensive use as corrosion inhibitors in aircraft deicing and anti-icing fluids (ADAF) and for silver protection in dishwasher detergents benzotriazoles (BTs) are widespread in European surface waters. The current study aimed on an ecotoxicological characterization of 1H-benzotriazole (1H-BT) and 5-methyl-1H-benzotriazole (5MBT). METHODS: Acute and chronic OECD guideline tests were conducted with primary producers (Desmodesmus subspicatus, Lemna minor) and two daphnia species (Daphnia magna, Daphnia galeata) to characterize the hazard of these chemicals. Additionally, the estrogenic activity of both BTs was analyzed in vitro using a recombinant yeast estrogen screen (YES). RESULTS: Both BTs revealed significant effects in acute and chronic experiments, but exhibited no estrogenic activity in the YES. The algal growth test displayed an inhibited cell number increase with effect concentration (EC) values of EC(10) 1.18 and 2.86 mg l(-1) for 1H-BT and 5MBT, respectively. In the Lemna test, EC(10) values were 3.94 mg l(-1) (1H-BT) and 2.11 mg l(-1) (5MBT). D. magna was also affected with EC(50) (48 h) values of 107 mg l(-1) for 1H-BT and 51.6 mg l(-1) for 5MBT. D. galeata was more sensitive with an EC(50) (48 h) of 14.7 mg 1H-BT l(-1) and 8.13 mg 5MBT l(-1). In the 21-day reproduction tests with D. magna, the EC(10) for 5MBT was 5.93 mg l(-1) while 1H-BT showed no adverse effects. D. galeata turned out to be more sensitive in the chronic study with EC(10) values of 0.97 mg l(-1) for 1H-BT and 0.40 mg l(-1) for 5 MBT. CONCLUSION: Because BTs are regularly found in the aquatic environment at lower µg l(-1) concentrations reflecting their persistence and poor elimination during wastewater treatment processes, a preliminary risk assessment was conducted. There is little indication that BTs pose a risk for aquatic ecosystems at current exposure levels during most of the year. However, it cannot be excluded that in winter with a higher usage of ADAFs environmental concentrations may well exceed the level that is considered safe for aquatic organisms.

Sorption of polycyclic aromatic hydrocarbons (PAHs) to low and high density polyethylene (PE).

BACKGROUND, AIM, AND SCOPE: According to their high sorption capacity polyethylene (PE) passive samplers are often used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in the aquatic environment. PE is also one of the primary synthetic polymers found in oceans, and sorption of PAHs to marine PE debris may determine PAH exposure and therefore hazards in marine ecosystems. Thus, an understanding of the sorption process is of great importance. In the present study, the sorption of several PAHs with different polarities to low density polyethylene (LDPE) and high density polyethylene (HDPE) was studied in order to improve our understanding of the influence of material properties on the Fickian diffusion of PAHs into PE. MATERIALS AND METHODS: Batch sorption experiments were performed with aqueous solutions containing acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and LPDE or HDPE pellets. Samples were shaken in the dark at 20 ± 1°C for 16 time intervals within one week. Concentrations of PAHs were determined in the aqueous samples using solid-phase microextraction coupled with gas chromatography-mass spectrometry. The distribution coefficients (K (PE)) between PE and water were estimated from different models reported in the literature. Kinetic sorption of the PAHs into the plastic pellets was described by a diffusion model based on Fick's second law in spherical coordinates. RESULTS AND DISCUSSION: A comparison between different models describing the equilibrium distribution of PAHs between PE and water revealed that the sorption equilibrium seemed to be driven by parameters other than, or in addition to, organic carbon. For both plastic types, diffusion coefficients decreased while the molecular weight of the PAHs increased which indicates a hindered diffusion through the matrix as a result of a larger molecule size. Higher diffusion coefficients were derived for LPDE than for HDPE indicating a greater sorption velocity for LPDE according to the lower polymer density. CONCLUSIONS: Our results revealed that equilibrium time could be shortened during passive sampling as polymer membranes of lower density are used. In some areas, marine ecosystems may not be in equilibrium with respect to concentrations of organic contaminants and abundance of marine plastic debris. In such cases, different polymer densities should be taken into account in risk assessments.

Occurrence and distribution of benzothiazole in the Schwarzbach watershed (Germany).

This study quantifies the regional distribution of the micropollutant benzothiazole (BT) in river water by sampling 15 river sites in the Schwarzbach watershed (about 400 km(2)) from November 2008 to February 2010. Additionally, wastewater samples from three municipal wastewater treatment plants (WWTPs) in Germany were analyzed. BT was detected in all wastewater influent and effluent samples as well as in all river water samples collected downstream of wastewater discharge. This corroborates the ubiquitous occurrence of BT in the aqueous environment. Concentrations were between 58 and 856 ng L(-1) in the river water. The observed mean concentration at the outlet of the investigated catchment was 109 ng L(-1). With only a few exceptions, temporal and spatial variations of BT concentrations in river water were low. Rather similar BT concentrations over a wide range of river discharge indicate that dilution along the mainstream is negligible and, thus, supports the hypothesis that paved surface runoff during rain events is an important BT source not only for wastewater influent but also for river water. This was supported by detecting the highest BT concentrations at sampling locations close to the dense highway network around the city of Frankfurt. Since BT was also detected in river water collected from locations that were clearly unaffected by wastewater effluent discharge, surface runoff must be considered as a diffuse source of BT in river water.

Pollution of soils with organophosphorus flame retardants and plasticizers.

The detection of the three organophosphate esters TCEP, TCPP and TBEP in soil samples indicates that pollution of soils from diffuse atmospheric sources has to be considered in risk assessments.

Determination of benzothiazole in untreated wastewater using polar-phase stir bar sorptive extraction and gas chromatography-mass spectrometry.

Stir bar sorptive extraction (SBSE) was applied to extract benzothiazole (BT) from untreated wastewater using a novel polyacrylate (PA)-coated stir bar (PA Twister(®)). After extraction, BT was desorbed in a thermal desorption system (TDS) and analysed by GC-MS (gas chromatography-mass spectrometry). The sample contained 30% (w/w) NaCl, the sample temperature was 30°C and the extraction time was 240 min. Since no filtering or clean-up steps or solvents were necessary SBSE clearly performs better than all previously used extractions techniques for analysing BT in untreated wastewater in terms of easy use, sample throughput and analytical costs. In addition, matrix effects were small. The calibration curve resulting from the standard addition method was linear with a value of the stability index (R(2)) of 0.999 (n=3). A good inter-day repeatability of the method was observed with a relative standard deviation (RSD) of 9.8% (n=6). A low limit of detection (LOD) of 0.256 µg L(-1) was achieved using only a small sample volume of 18 mL. Small sample volumes significantly reduce sample transport costs. The concentration of BT in untreated wastewater was determined to be 1.04 µg L(-1).

Application of Twisselmann extraction, SPME, and GC-MS to assess input sources for organophosphate esters into soil.

Although the ubiquitous distribution of organophosphate esters (OPEs) in the environment has been documented very thoroughly, data on their occurrence in soil is so far sparse. In this study, an analytical method was developed to determine six OPEs in soil. The method consists of a combination of Twisselmann extraction and solid-phase microextraction (SPME), followed by gas chromatography-mass spectrometry (GC-MS). To develop the method, spiked soil was extracted using a Twisselmann extractor after freeze-drying. The extract was evaporated to dryness, redissolved, and filtered. A volume of 7 mL was then analyzed by SPME, followed by GC-MS. The effects of different parameters on analyte recoveries during sample preparation, e.g., solvent for Twisselmann extraction, solvent for redissolving the extract, addition of copper, and filtration of the extract, were systematically investigated. Under optimum conditions, 10 g soil samples were extracted using toluene, and the extract was redissolved in methanol/water (1:14) and filtered. It was not necessary to add copper. For TnBP, TBEP, TCPP, and TCEP, recoveries ranged from 77.0% to 89.6%. Those for TPP and TDCP were much lower, at 31.5% and 42.0%, respectively (addition level 22.9-45.8 ng g(-1)). The variability of recoveries under these conditions was between 0.3 and 16.2% (n = 3). Limits of detection (LOD) were 0.002-3 ng g(-1). When ultrasonication was used in place of Twisselmann extraction in the developed method, recoveries were three to four times lower (27.4% to 30.6%), but the variability of recoveries was below 3% (n = 3). The method was applied to quantify OPEs in soil collected from the university campus in Osnabrueck (Germany). Average concentrations (n = 6) in soil samples ranged from 1.23 ng g(-1) to 4.96 ng g(-1) (dry weight) for TCPP, TPP, and TCEP. The results demonstrate for the first time that atmospheric deposition leads to soil contamination by OPEs.

Investigation of partitioning mechanism for volatile organic compounds in a multiphase system.

Laboratory experiments were performed to investigate the partitioning behavior of a set of diverse volatile organic compounds (VOCs). After equilibration at a temperature of 25°C, the VOC concentrations were measured by headspace method in combination with gas chromatography/mass spectrometry (GC/MS). The obtained data were used to determine the partition coefficients (K(P)) of VOCs in a gas-liguid-solid system. The results have shown that the presence and nature of solid materials in the working solution control the air-water partitioning of dissolved VOCs. The air/solution partitioning of BTEX and C(9)-C(10) aldehydes was most affected in the presence of diesel soot. K(P) values decreased by a factor ranging from 1.5 for toluene to 3.0 for ethylbenzene. The addition of mineral dust in the working solution exhibited greater influence on the partitioning of short aldehydes. K(P) values decreased by a factor of 1.8. The experimental partition coefficients were used to develop a predictive model for partitioning of BTEX and n-aldehydes between air, water and solid phases.

Occurrence of benzotriazoles in the rivers Main, Hengstbach, and Hegbach (Germany).

BACKGROUND, AIM, AND SCOPE: Benzotriazoles (BT) as 1H-benzotriazole (1H-BT), 5-methyl-1H-benzotriazole (5Me-BT), and 4-methyl-1H-benzotriazole (4Me-BT) are frequently used as corrosion inhibitors in dish washer detergents, aircraft de-icing/anti-icing fluids (ADAF), automotive antifreeze formulations, brake fluids, fluids for industrial cooling systems, metal-cutting fluids, and in solid cooling lubricants. Discharge of treated municipal waste water and controlled over-runs of combined waste water sewers are potential point sources for BT in rivers. The aim of this monitoring study was to yield an overview on exposure concentrations and loads of BT in the German rivers Main, Hengstbach, and Hegbach. MATERIALS AND METHODS: Concentrations of 1H-BT, 5Me-BT, and 4Me-BT were determined in grab samples collected from different sampling points in the rivers Main, Hengstbach, and Hegbach at four different sampling times. Main and Hengstbach rivers were sampled close to Frankfurt International Airport. Both rivers receive domestic waste water effluents. BT were extracted from 2.5 L of river water by solid phase extraction using Bond Elut ppl cartridges (200 mg/3 mL). The extracts were analyzed by gas chromatography/mass spectrometry in full scan mode. Mass flows of BT were calculated by concentrations multiplied by mean daily river flow rates. Median concentrations and mass flows were compared for different rivers. Mass flows were also compared for selected sampling points at different sampling times. RESULTS: 1H-BT, 5Me-BT, and 4Me-BT were detected in Main and Hengstbach rivers. 1H-BT and 5Me-BT were also detected in Hegbach River. Concentrations ranged from 38 to 1,474 ng/L for 1H-BT, from 25 to 281 ng/L for 5Me-BT, and from 25 to 952 ng/L for 4Me-BT. Median concentrations of 1H-BT, 5Me-BT, and 4Me-BT were lower in Main than in Hengstbach River. Much higher median mass flows of all BT were calculated for Main than for Hengstbach River. At sampling points P9 (Main) and P5 (Hengstbach) concentrations of 4Me-BT and 5Me-BT increased from March 29, 2008 to May 1, 2008 to June 22, 2008 whereas daily mean river flow rate decreased simultaneously. However, concentration of 1H-BT in Main and Hengstbach River increased from March 29, 2008 to May 1, 2008 and decreased again on June 22, 2008. In the Main River, lowest and highest mass flows for all BT were calculated on June 22, 2008 and May 1, 2008, respectively. In the Hengstbach River lowest and highest mass flows for 1H-BT and 4Me-BT were also calculated on June 22, 2008 and May 1, 2008, respectively. However, mass flows of 5Me-BT in Hengstbach River were rather similar at all three sampling times. In all grab samples, 1H-BT was more abundant than 5Me-BT and 4Me-BT in Main and Hengstbach River, except on June 22, 2008. Ratios of 1H-BT/(5Me-BT + 4Me-BT) determined on March 15, 2008, March 29, 2008, and May 1, 2008 varied between 1.6 and 9.0 with a median value of 1.9 (n = 9) whereas on June 22, 2008 the ratios varied between 0.4 and 0.7 with a median value of 0.6 (n = 5). DISCUSSION: Due to the absence of waste water effluents in the Hegbach River, other input sources as controlled over-runs of combined waste water sewers and/or atmospheric deposition of BT must be regarded as possible input sources. Exfiltration of ground water containing BT to Hegbach River must be also regarded, especially when considering the high polarity of BT. Median concentrations of BT in Main River were much lower than in Hengstbach River due to dilution. However, median mass flows were higher in the Main River than in the Hengstbach River. Higher mass flows could be attributed to higher source strengths and/or numerous emissions sources in the Main River. Mass flows determined on June 22, 2008 in Main and Hengstbach rivers probably reflect emissions of BT only from dishwasher detergents since de-icing operations were unlikely at that time. Emissions of BT from dish washer detergents are rather constant without any seasonal variations. Assuming the absence of additional input sources and constant in-stream removal processes, mass flows calculated for all other sampling times must be nearly similar to mass flows for June 22, 2009 as it was only observed for 5Me-BT in Hengstbach River. The higher mass flows for 1H-BT and 4Me-BT in March and May in both rivers could be an indication for temporal variations of emission pattern and/or of in-stream removal processes. 1H-BT/(4Me-BT + 5Me-BT) ratios above one in March and May and below one in June could be also an indication for temporal variations of input and/or removal processes. CONCLUSIONS: 1H-BT, 5Me-BT, and 4Me-BT used as corrosion inhibitors in many applications were detected in the rivers Main, Hengstbach, and Hegbach with relative high temporal and spatial concentration variations. Dilution is a dominant factor that influences exposure concentrations of BT in the studied rivers. We conclude that, especially in smaller rivers (as Hengstbach River), the hydrological situation has to be regarded when predicting exposure concentrations of BT. Characteristic emission strength and in-stream removal processes must be known to relate loads of BT in river water to different sources. The ratio of 1H-BT/(4Me-BT + 5Me-BT) could be possibly used for source apportionment. RECOMMENDATIONS AND PERSPECTIVES: Time series analyses of BT in composite river water samples collected at two river sites of the Hengstbach/Schwarzbach catchment area, without any waste water effluents in between, are recommended to study in-stream removal of BT. In addition, exposure modeling is recommended of BT, regarding all input sources and in-stream removal processes to predict exposure concentrations of BT in rivers. In order to calibrate and validate the model, additional monitoring data are required.

Analysis of potassium formate in airport storm water runoff by headspace solid-phase microextraction and gas chromatography-mass spectrometry.

Potassium formate was extracted from airport storm water runoff by headspace solid-phase microextraction (HS-SPME) and analyzed by GC-MS. Formate was transformed to formic acid by adding phosphoric acid. Subsequently, formic acid was derivatized to methyl formate by adding methanol. Using sodium [(2)H]formate (formate-d) as an internal standard, the relative standard deviation of the peak area ratio of formate (m/z 60) and formate-d (m/z 61) was 0.6% at a concentration of 208.5 mg L(-1). Calibration was linear in the range of 0.5-208.5 mg L(-1). The detection limit calculated considering the blank value was 0.176 mg L(-1). The mean concentration of potassium formate in airport storm water runoff collected after surface de-icing operations was 86.9 mg L(-1) (n=11) with concentrations ranging from 15.1 mg L(-1) to 228.6 mg L(-1).

Benzene, alkylated benzenes, chlorinated hydrocarbons and monoterpenes in snow/ice at Jungfraujoch (46.6 degrees N, 8.0 degrees E) during CLACE 4 and 5.

Benzene, alkylated benzenes, chlorinated hydrocarbons and monoterpenes were measured in snow/ice collected directly in-cloud at Jungfraujoch (3580 m asl) in February and March 2005 and 2006 during the CLoud and Aerosol Characterization Experiments CLACE 4 and CLACE 5. Melted snow/ice samples were analyzed by headspace-solid-phase-dynamic-extraction (HS-SPDE) followed by gas chromatography/mass spectrometry (GC/MS). Generally, there was a tendency in the results that higher concentrations were found after longer precipitation-free periods, suggesting that higher concentrations in snow/ice may be caused by the washout effect of precipitation. High concentration variations in snow/ice samples taken at the same time at the same place highlight the heterogeneous nature of snow/ice. Air concentrations calculated by scavenging ratios and measured snow/ice values markedly exceed the typically reported concentrations of benzene and alkylbenzenes in air (Li Y, Campana M, Reimann S, Schaub KS, Staehlin J, Peter T. Hydrocarbon concentrations at the alpine mountain sites Jungfraujoch and Arosa. Atmos Environ 2005;39:1113-27). This argues for an efficient snow/ice scavenging of those compounds from the atmosphere during precipitation formation.

Analysis of benzene, toluene, ethylbenzene, xylenes and n-aldehydes in melted snow water via solid-phase dynamic extraction combined with gas chromatography/mass spectrometry.

The present study describes a method based on headspace-solid-phase dynamic extraction (HS-SPDE) followed by GC/MS for the qualitative and quantitative analysis of benzene, toluene, ethylbenzene, o-, m- and p-xylene (BTEX), and n-aldehydes (C(6)-C(10)) in water. To enhance the extraction capability of the HS-SPDE a new cooling device was tested that controls the temperature of the SPDE needle during extraction. Extraction and desorption parameters such as the number of extraction cycles, extraction temperature, desorption volume and desorption flow rate have been optimized. Detection limits for BTEX ranged from 19 ng/L (benzene) to 30 ng/L (m/p-xylene), while those for n-aldehydes ranged from 21 ng/L (n-heptanal) to 63 ng/L (n-hexanal). At a concentration level of 2 microg/L, the relative standard deviations (RSDs) for BTEX ranged from 3.9% (benzene) to 15.3% (ethylbenzene), while RSDs for n-aldehydes were between 6.1% (n-octanal) and 16.5% (n-hexanal) (n=7). Best results were obtained when the analyzed water samples were heated to 50 degrees C. At a water temperature of 70 degrees C GC responses decreased for all analyzed compounds. At a defined water temperature, a significant improvement of the GC response was achieved by cooling of the SPDE fiber during water extraction in comparison to an extraction keeping the fiber at room temperature. Evaluating the extraction cycles, for BTEX, the sensitivity was almost similar using 20, 40 and 60 extraction cycles. In contrast, the highest GC responses for n-aldehydes were achieved by the use of 60 extraction cycles. Optimizing the desorption parameters, best results were achieved using the smallest technical available desorption volume of 500 microL and the highest technical desorption flow rate of 50 microL/s. The method was applied to the analysis of melted snow samples taken from the Jungfraujoch, Switzerland (3580 m asl), revealing the presence of BTEX and aldehydes in snow.