Occurrence and human exposure assessment of organophosphate flame retardants in indoor dust from various microenvironments of the Rhine/Main region, Germany.

We analyzed organophosphate flame retardants (OPFRs) in 74 indoor dust samples collected from seven microenvironments (building material markets, private cars, daycare centers, private homes, floor/carpet stores, offices, and schools) in the Rhine/Main region of Germany. Ten of 11 target OPFRs were ubiquitously detected, some with more than 97% detection frequency, including tris(1,3-dichloroisopropyl)phosphate (TCIPP), tris(2-butoxyethyl)phosphate (TBOEP), triphenyl phosphate (TPHP), and tris(isobutyl) phosphate (TIBP). Total concentrations (∑OPFRs) ranged from 5.9 to 4800 µg/g, with TBOEP and TCIPP being the most abundant congeners. The ∑OPFRs in schools, private cars, offices, and daycare centers were significantly (P<.05) higher than in private homes. The ∑OPFRs for building material markets (19 µg/g) and floor/carpet stores (20 µg/g) showed no significant difference to the other microenvironments, likely because of forced ventilation. The profiles of OPFRs in dust samples from offices and private homes were highly similar, while profiles from the other five microenvironments were substantially different. Comparison of our results with previous studies indicates a significant global variation in OPFR concentrations and their profiles, reflecting distinct fire safety regulations in different countries and/or different sampling strategies. Dust ingestion constitutes the major exposure pathway to OPFRs for toddlers, while air inhalation is the major pathway for adults.

Source identification of high glyme concentrations in the Oder River.

The objective of the following study was to identify the source of high concentrations of glycol diethers (diglyme, triglyme, and tetraglyme) in the Oder River. Altogether four sampling campaigns were conducted and over 50 surface samples collected. During the first two samplings of the Oder River in the Oderbruch region (km 626-690), glymes were detected at concentrations reaching 0.065 µg L(-1) (diglyme), 0.54 µg L(-1) (triglyme) and 1.7 µg L(-1) (tetraglyme). The subsequent sampling of the Oder River, from the area close to the source to the Poland-Germany border (about 500 km) helped to identify the possible area of the dominating glyme entry into the river between km 310 and km 331. During that sampling, the maximum concentration of triglyme was 0.46 µg L(-1) and tetraglyme 2.2 µg L(-1); diglyme was not detected. The final sampling focused on the previously identified area of glyme entry, as well as on tributaries of the Oder River. Samples from Czarna Woda stream and Kaczawa River contained even higher concentrations of diglyme, triglyme, and tetraglyme, reaching 5.2 µg L(-1), 13 µg L(-1) and 81 µg L(-1), respectively. Finally, three water samples were analyzed from a wastewater treatment plant receiving influents from a Copper Smelter and Refinery; diglyme, triglyme, and tetraglyme were present at a maximum concentration of 1700 µg L(-1), 13,000 µg L(-1), and 190,000 µg L(-1), respectively. Further research helped to identify the source of glymes in the wastewater. The gas desulfurization process Solinox uses a mixture of glymes (Genosorb(®)1900) as a physical absorption medium to remove sulfur dioxide from off-gases from the power plant. The wastewater generated from the process and from the maintenance of the equipment is initially directed to the wastewater treatment plant where it undergoes mechanical and chemical treatment processes before being discharged to the tributaries of the Oder River. Although monoglyme was also analyzed, it was not detected in any of the water samples.

Behavior of organophosphates and hydrophilic ethers during bank filtration and their potential application as organic tracers. A field study from the Oderbruch, Germany.

The behavior of organophosphates and ethers during riverbank filtration and groundwater flow was assessed to determine their suitability as organic tracers. Four sampling campaigns were conducted at the Oderbruch polder, Germany to establish the presence of chlorinated flame retardants (TCEP, TCPP, TDCP), non-chlorinated plasticizers (TBEP, TiBP, TnBP), and hydrophilic ethers (1,4-dioxane, monoglyme, diglyme, triglyme, tetraglyme) in the Oder River, main drainage ditch, and anoxic aquifer. Selected parameters were measured in order to determine the hydro-chemical composition of both, river water and groundwater. The results of the study confirm that organophosphates (OPs) are more readily attenuated during bank filtration compared to ethers. Both in the river and the groundwater, TCPP was the most abundant OP with concentrations in the main drainage ditch ranging between 105 and 958 ng L(-1). 1,4-dioxane, triglyme, and tetraglyme demonstrated persistent behavior during bank filtration and in the anoxic groundwater. In the drainage ditch concentrations of 1,4-dioxane, triglyme, and tetraglyme ranged between 1090 and 1467 ng L(-1), 37 and 149 ng L(-1), and 496 and 1403 ng L(-1), respectively. A positive correlation was found for the inorganic tracer chloride with 1,4-dioxane and tetraglyme. These results confirm the possible application of these ethers as environmental organic tracers. Both inorganic and organic compounds showed temporal variability in the surface- and groundwater. Discharge of the river water, concentrations of analytes at the time of infiltration and attenuation were identified as factors influencing the variable amounts of the analytes in the surface and groundwater. These findings are also of great importance for the production of drinking water via bank filtration and natural and artificial groundwater recharge as the physicochemical properties of ethers create challenges in their removal.

Simultaneous determination of six hydrophilic ethers at trace levels using coconut charcoal adsorbent and gas chromatography/mass spectrometry.

The main objective of the following study was to determine the efficiency of a method that uses coconut charcoal as a solid-phase extraction (SPE) adsorbent in order to simultaneously detect six hydrophilic ether species in water in the low microgram-per-liter range. The applied method was validated for quantification of ethyl tert-butyl ether, 1,4-dioxane, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) and tetraethylene glycol dimethyl ether (tetraglyme). SPE followed by gas chromatography/mass spectrometry of the extracts using the selected ion monitoring mode allowed for establishing low detection limits in the range of 0.007-0.018 µg/L in ultrapure water and 0.004-0.020 µg/L in environmental samples. Examination of the method accuracy and precision resulted in a recovery greater than 86.8 % for each compound with a relative standard deviation of less than 6.6 %. A stability study established a 5-day holding time for the unpreserved water samples and extracts. Finally, 27 samples obtained from surface water bodies in Germany were analyzed for the six hydrophilic ethers. Each analyte was detected in at least eight samples at concentrations reaching 2.0 µg/L. The results of this study emphasize the advantage of the method to simultaneously determine six hydrophilic ether compounds. The outcome of the surface water analyses augments a concern about their frequent and significant presence in surface water bodies in Germany.

Occurrence and distribution of organophosphorus flame retardants and plasticizers in anthropogenically affected groundwater.

Occurrence and distribution of chlorinated and non-chlorinated organophosphates in 72 groundwater samples from Germany under different recharge/infiltration conditions were investigated. Tris(2-chloro-1-methylethyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) were the most frequently detected organophosphates in groundwater samples. Highest individual organophosphate concentrations (>0.1 µg L(-1)) were determined in groundwater polluted by infiltrating leachate and groundwater recharged via riverbank filtration of organophosphate-loaded recipients. In samples from springs and deep groundwater monitoring wells that are not affected by surface waters, organophosphate concentrations were mostly below the limit of detection. The occurrence (3-9 ng L(-1)) of TCPP and TCEP in samples from aquifers with groundwater ages between 20 and 45 years indicates the persistence of both compounds within the aquifer. At urban sites organophosphate-loaded precipitation, surface runoff, and leakage of wastewater influenced groundwater quality. For rural sites, where groundwater recharge is only influenced by precipitation, organophosphates were very rarely detectable in groundwater.

Analysis of palladium concentrations in airborne particulate matter with reductive co-precipitation, He collision gas, and ID-ICP-Q-MS.

The concentration of platinum group elements (PGE) in the environment has increased significantly in the last 20 years mainly due to their use as catalysts in automotive catalytic converters. The quantitation of these metals in different environmental compartments is, however, challenging due to their very low concentrations and the presence of interfering matrix constituents when inductively coupled plasma-mass spectrometry (ICP-MS) is used for analysis. Previously, the research focus was on the analysis of platinum (Pt) and rhodium (Rh). However, due to the increasing use of palladium (Pd) in automotive catalytic converters, quantitation of this element in airborne particulate matter (PM) is also needed. Compared to Pt and Rh, measurements of Pd using ICP-MS are plagued by greater molecular interferences arising from elements such as copper (Cu), zinc (Zn) strontium (Sr), yttrium (Y), and zirconium (Zr). The aim of this study was to evaluate the applicability of reductive co-precipitation procedures using both mercury (Hg) and tellurium (Te) for the pre-concentration of Pd from airborne PM. Furthermore, helium (He) was tested as a collision gas for isotope dilution-inductively coupled plasma-quadrupole-mass spectrometry (ID-ICP-Q-MS) to measure Pd in the Hg and Te precipitates. Airborne PM samples (PM10) were collected from Neuglobsow (Brandenburg, north-eastern Germany) and Deuselbach (Rhineland-Palatinate, south-western Germany), considered to represent background levels, and from the city Frankfurt am Main (Hesse, Germany), a high-traffic area. Samples were first digested with aqua regia in a high-pressure asher (HPA) at 320 degrees C and 130 bar prior to the application of reductive co-precipitation procedures. The method was validated with road dust reference material BCR-723 and the CANMET-CCRMP reference material TDB-1 and WPR-1. In airborne PM collected at the background areas Neuglobsow and Deuselbach, Pd was detected with median concentrations values of 0.5 and 0.6 pg/m3, respectively. Much higher median concentration values of 14.8 pg Pd/m3 (detection limit = 0.01 pg Pd/m3) were detected in samples collected in the city of Frankfurt am Main. Results have shown that Hg co-precipitation depletes the concentrations of interfering matrix constituents by at least one order of magnitude more, compared to Te co-precipitation, making it a more effective method for the isolation and pre-enrichment of Pd from airborne PM prior to analysis. The use of a He gas flow of 120 ml/min in the plasma further minimized interferences, particularly those arising from CuAr+, YO+, and ZrO+ during the determination of Pd. The results demonstrate that Hg co-precipitation and the use of He collision gas, in combination with isotope dilution, are highly effective methods for the quantitation of Pd in airborne PM using ICP-MS.

Method for determination of methyl tert-butyl ether in gasoline by gas chromatography.

A simple method for the determination of methyl tert-butyl ether (MTBE) in gasoline has been developed. The separation of MTBE from other analytes was controlled by the use of gas chromatography-mass spectrometry in the full scan mode using the characteristic primary, secondary and tertiary ions m/z 73, 57 and 43. The sample mass spectrum did not show any superimposition of other analytes. The separation from the common gasoline component 2-methylpentane was sufficient for reliable quantitation. An application of the developed conditions using gas chromatography with flame ionization detection was performed by the analysis of regular, euro super, super premium unleaded and 'Optimax' gasoline from petrol stations in the area of Frankfurt/Main, Germany. Regular unleaded gasoline shows an average MTBE content of 0.4% (w/w), whereas the MTBE content in euro super gasoline varies between 0.4 and 4.2% (w/w). The blending of MTBE to super premium has increased from 8.2% (w/w) in 1998 to 9.8% (w/w) on average in 1999. The recently introduced gasoline 'Optimax' shows an average MTBE content of 11.9% (w/w). The presented method might also be used for the analysis of other ethers, such as ethyl tert-butyl ether, which requires the use of another internal standard.

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.

Sensitive method for determination of methyl tert-butyl ether (MTBE) in water by use of headspace-SPME/GC-MS.

A simple and rapid method for the determination of methyl tert-butyl ether (MTBE) in water by headspace-solid-phase microextraction (headspace-SPME) at sub-microg/L concentrations is described. On using a cooled SPME fiber coated with a 75-microm layer of poly(dimethylsiloxane)/carboxene and heating the sample to 35 degrees C, about 4 times more MTBE is extracted compared to SPME extraction with the fiber placed in the water sample. Stable analytical conditions with a detection limit of 10 ng/L are achieved. By use of a sample volume of 4 mL in a 10 mL vial, a sodium chloride content of 10% (w/w), and an extraction time of 30 min, the total time of an analytical cycle was optimized to 39 min. Precise linearity of R2>0.9991 and R2>0.9916 in the calibration range of 20-5000 ng/L and 20-100 ng/L, both in addition to blanks, respectively, and relative standard deviations of 10% (100 ng/L, long-term) and 11% (20 ng/L, short-term) are presented. The recovery is well within the accepted limits of 83-118% at a concentration of 100 ng/L and even close thereto at trace levels of 20 ng/L (96-125%). The data presented for a concentration of 100 ng/L are examined by statistical methods and show results for the T test at the 95% confidence level. Due to the large concentration range covered, the method is well suited for the monitoring of MTBE in the aquatic environment.