Elke Fries

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.

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.

Analysis of the antioxidant butylated hydroxytoluene (BHT) in water by means of solid phase extraction combined with GC/MS

The antioxidant 3,5-di-tert-butyl-4-hydroxy-toluene (BHT) is widely used as an additive to increase the tenability of food and plastics. BHT is degraded to 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO) in mammals, as well as in the natural environment such as in water and soils. BHT-CHO has been studied extensively in terms of their potential toxicities. The present investigation was carried out to quantify BHT and BHT-CHO in river, ground, rain and drinking water obtained from several locations in Germany. Apart from the compounds mentioned above, 1,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane (2-BHT), which is a dimer of BHT, was also detected in the extracts of some ground water samples. The applied analytical method is based on solid phase extraction (SPE) to concentrate trace compounds from water samples followed by gas chromatography/mass spectrometry (GC/MS) of the extracts. A total of 51 of the respective water samples were used for extraction purposes and analyte recoveries were all > or = 80%. The determination limit for BHT was 5 ng l(-1) and for BHT-CHO 16 ng l(-1). The standard deviations for the analytical procedure were 6% for BHT and 10% for BHT-CHO. The use of the antioxidant BHT in Germany has resulted in water concentrations of 7-791 ng l(-1) in the rivers Rhine, Elbe, Main, Oder, Nidda and Schwarzbach. The degradation product BHT-CHO was also detected in the river water samples at concentrations between 29 and 223 ng l(-1). The concentrations of BHT measured in German rivers are lower compared to values measured in the USA and Japan 20 years ago. In ground water, levels for BHT varied from non-detectable up to 2156 ng l(-1) and for BHT-CHO from non-detectable up to 674 ng l(-1). Both compounds were also detected in rain water in Frankfurt/Main at a concentration of 1797 ng l(-1) for BHT and 59 ng l(-1) for BHT-CHO.

Occurrence and behaviour of 4-nonylphenol in river water of Germany

An analytical method composed of solid-phase-extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed to investigate the occurrence and the behaviour of the endocrine disruptor 4-nonylphenol (4-NP) in river water of Germany. 16 Para-isomers of the complex mixture of 4-NP isomers have been resolved in the SPE-extracts of river water samples. The mass spectra indicate the presence of four distinct groups of isomers. The different groups are characterised by different base peaks of the mass spectra dependent on the substitution of the alpha-carbon on the alkyl chain. The different isomers show (i) alpha-methyl, alpha-ethyl (base peak 149), (ii) alpha-dimethyl (base peak 135), (iii) alpha-methyl, alpha-propyl, alpha-butyl (base peak 121) and (iv) alpha-methyl, alpha-propyl, alpha-butyl (base peak 107) configuration of the alkyl chain. The recovery of the unbranched compound 4-n-NP was > or = 90%. Detection limit and determination limit of the whole analytical procedure were 6 ng L(-1) and 25 ng L(-1), respectively with a relative standard deviation of 11.7%. The concentration of the sum of the 4-NP isomers in all samples of river water ranged from 28 ng L(-1) (Elbe River) to 1220 ng L(-1)(Oder River). In a period of a higher river water level, a higher amount of 4-NP was detected in the Oder River than in a period of a lower water level. Therefore dilution was not the determinant factor of the 4-NP concentration in river water. The diurnal dynamics of the sewage treatment works (STWs) have to be considered as an influencing factor for the presence of 4-NP in river water.

Monitoring of the antioxidant BHT and its metabolite BHT-CHO in German river water and ground water.

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 ngl(-1), respectively. BHT and BHT-CHO were also detected in effluent waste water samples from municipal STWs at mean concentrations of 132 and 70 ngl(-1), respectively. Both compounds are discharged into river water directly via treated waste water. In the rain water sample, 308 ngl(-1) of BHT and 155 ngl(-1) of BHT-CHO were measured. Both compounds were detected in roof runoff with mean concentrations of 92 ngl(-1) for BHT and 138 ngl(-1) for BHT-CHO. The median values of BHT and BHT-CHO in ground water samples were 132 and 84 ngl(-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.

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).

Carbon stocks and greenhouse gas balance of harvested wood products: focus on the Asia-Pacific Partnership countries vis-à-vis the European Union

With the analytical tool, Frankfurt Harvested Wood Products Model, FPM, the carbon stocks and carbon stock changes of Harvested Wood Products, HWP, either in USE or in LANDFILLS L-F, have been evaluated, each separately, from the readily available statistical data base of the FAO, FAOSTAT, on the wood commodities: “Sawnwood and Wood-based Panels, SWP” and the paper commodities, “Paper and Paperboard, PAP”. The focus was on the newly founded Asia-Pacific Partnership countries for Clean Development and Climate (in short AP6), including Canada, which wants to join the AP6, in relation to the countries of the European Union EU-25. It could be shown that the stocks and stock changes of the HWP in USE follow a simple algorithm of the annual consumption or production and their mean annual growth, for the categories SWP and PAP, provided the mean residence times of the HWP in USE can be estimated. With the information on the fraction of residues entering the landfills and their estimated residence times an equivalent simple expression has been derived for stocks and stock changes of the HWP in LANDFILLS L-F. Their values have been calculated to be approximately 0.5 to 0.7 times smaller than those of the HWP in USE. Still, all stock changes of the HWP in L-F were positive and thus accumulating carbon. However, when methane outgasing within the HWP in L-F had been considered, the calculated Greenhouse Gas Balance was zero or negative under the estimated parameters thus to at least partly compensate the positive storage of carbon in HWP in USE. The percentage of CO2 removed by the HWP in USE in comparison to the annual greenhouse gas emissions varied from 0.3 to 1.7%, with a mean value of 0.8% for the AP6 countries including Canada, in contrast to 1.0% of the EU-25 countries. Despite of the relative small magnitude in relation to the total emission of all GHG this contribution should not be neglected in the GHG Budget of a country.

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.