Quantification of bacterial lipopolysaccharides (endotoxin) by GC-MS determination of 3-hydroxy fatty acids

A GC-MS method for the quantification of bacterial lipopolysaccharides (LPS, endotoxin) is presented. After hydrolytic cleavage of 3-hydroxy fatty acids (3-OH FAs) from the lipid A region of LPS, derivatisation of both the hydroxyl and the carboxyl group was performed in one step with a mixture of methyl-bis(trifluoracetamide)(MBTFA) and N-methyl-N-(tert-butyldimethylsilyl)trifluoracetamide (MTBSTFA). Using GC-MS in the EI mode with selected ion monitoring (SIM) for analysis, baseline separation of 3-OH FAs (and of possibly interfering 2-OH FAs) was achieved. The sensitivity of the method (LOD 7-50 pg/injection for the different 3-OH FAs investigated) allows for the efficient quantification of LPS in occupational and environmental samples. Degradation of 3-OH FAs as well as of their derivatives during sample preparation and GC-MS separation as a possible source of errors in analytical methods based on 3-OH FA determination is reported for the first time. Thermal elimination of water from the underivatised 3-OH FAs and of trifluoroacetic acid from the derivatives was identified as the cause of degradation. The resulting alpha,beta-unsaturated compounds showing the same mass spectra as the 3-OH FA derivatives were detected as more or less prominent satellite peaks. By using alkaline instead of acidic hydrolysis and cool on-column instead of split/splitless injection, elimination was reduced to an acceptable level.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.     

Development and comparison of methods using MS scan and selective ion monitoring modes for a wide range of airborne VOCs

Adsorbent sampling with analysis by thermal desorption, gas chromatography and mass spectrometry (TD/GC/MS) offers many advantages for volatile organic compounds (VOCs) and thus is increasingly used in many applications. For environmental samples and other complex mixtures, the MS detector typically is operated in the scan mode to aid identification of co-eluting compounds. However, scan mode does not achieve the optimal sensitivity, thus compounds occurring at low concentrations may not be detected. This paper develops and evaluates the application of a more sensitive TD/GC/MS method using selective ion monitoring (SIM) that is applicable to VOC mixtures found in ambient and indoor air. Based on toxicity and prevalence, 94 VOCs (including terpenes, aromatic, halogenated and aliphatic compounds) were selected as target compounds. Two analytical methods were developed: a conventional full scan method for ions from 29 to 270 m/z; and a SIM method using 16 time windows and different ions selected for the compounds in each window. Both methods used the same Tenax GR adsorbent sampling tubes, TD and GC parameters, and target and qualifier ions. Laboratory tests determined calibrations, method detection limits (MDLs), precisions, recoveries and storage stability. Field tests compared scan and SIM mode analyses for duplicate samples of indoor air in 51 houses and outdoor air at 41 sites. Statistical analyses included the development of error/precision models. The laboratory tests showed that most compounds demonstrated excellent precision (<10% for concentrations exceeding approximately 0.5 microg m(-3)), good linearity, near identical calibrations for scan and SIM modes, a wide dynamic range (up to 1500 microg m(-3)), and negligible storage losses after 1 month (7 compounds showed moderate losses). SIM mode MDLs ranged from 0.004 to 0.27 microg m(-3), representing a modest (1.1 to 22-fold) improvement compared to scan mode. However, in field tests the SIM method detected significantly more compounds (e.g., styrene and chloroform). Error models fit most compounds and allow quantification of errors at selected percentiles. Overall, while the new SIM method is somewhat time-consuming to develop, it offers greater sensitivity and maintains the high selectivity of traditional scan methods.     

Pesticide vapours in confined atmospheres. Determination of dichlorvos by SPME-GC-MS at the microg m(-3) level

A method based on SPME is described for assessing the gaseous dichlorvos concentration in confined atmospheres like a greenhouse after a pesticide application. Sampling was made by using SPME with PDMS fibres immersed into a 250 mL sampling flask into which air samples were dynamically pumped from the analysed atmosphere. Sampling duration was 40 min and samples were then analysed by GC-MS. Calibration was performed from a vapour saturated air sample and gas phase diluted samples, and this procedure afforded a curve with a regression coefficient (R2) higher than 0.98. The repeatability of these measurements was observed with an RSD of 2.5%. This analysis procedure was then applied for the determination of gaseous dichlorvos concentrations versus time, in the atmosphere of an experimental 8 m2 and 20 m3 greenhouse. The pesticide was sprayed according to real cultivation conditions and measurements were made from 2 up to 74 h after application affording observed concentrations in the range of decades and hundreds of microg m(-3) (corresponding limits of detection and quantification were found at the level of a few microg m(-3)).     

Development of a solid phase microextraction (SPME) method for the sampling of VOC traces in indoor air

Solid-phase microextraction (SPME) was studied for the measurement of volatile organic compounds (VOCs) in indoor air. An adsorptive PDMS/Carboxen fibre was used and an analytical methodology was developed in order to overcome competitive adsorption. Kinetics and adsorption isotherms were investigated for different sample volumes and model compounds. In order to evaluate competitive adsorption on the fibre, these compounds were studied alone and in mixture. From the results obtained, the operating conditions allowing co-adsorption of the target compounds were determined: the air sample is enclosed in a 250 mL glass bulb where the SPME fibre is exposed until adsorption equilibrium. This procedure was combined with GC/MS analysis for the identification and quantification of VOCs in indoor air. The performances were determined by using a standard gas containing 10 VOCs representative of indoor environments (acetaldehyde, acetone, BTX, alpha-pinene, trichloroethylene, alkanes). The detection limits were determined in single ion monitoring mode and for a signal to noise ratio of 3. Except acetaldehyde (6 microg m(-3)), they are all below 0.5 microg m(-3). Calibration curves are linear up to 10 micromol m(-3) for all the compounds with good correlation coefficients (above 0.99). The reproducibility ranges from 6 to 12% according to the compound. The methodology was then applied to the comparison of the VOCs content in classrooms of two different schools.     

Exposure to airborne isocyanates and other thermal degradation products at polyurethane-processing workplaces

The thermal degradation products of polyurethanes (PURs) and exposure to isocyanates were studied by stationary and personal measurements in five different occupational environments. Isocyanates were collected on glass fibre filters impregnated with 1-(2-methoxyphenyl)piperazine (2MP) and in impingers containing n-dibutylamine (DBA) in toluene. connected to a glass fibre postfilter. The derivatives formed were analysed by liquid chromatography: 2MP derivatives with UV and electrochemical detection and DBA derivatives with mass spectrometric detection. The release of aldehydes and other volatile organic compounds into the air was also studied. In a comparison of the two sampling methods, the 2MP method yielded about 20% lower concentrations for 4,4'-methylenediphenyl diisocyanate (MDI) than did the DBA method. In car repair shops, the median concentration of diisocyanates (given as NCO groups) in the breathing zone was 1.1 microg NCO m(-3) during grinding and 0.3 microg NCO m(-3) during welding, with highest concentrations of 1.7 and 16 pg NCO m(-3), respectively. High concentrations of MDI, up to 25 and 19 microg NCO m(-3), respectively, were also measured in the breathing zone during welding of district heating pipes and turning of a PUR-coated metal cylinder. During installation of PUR-coated floor covering, small amounts of aliphatic diisocyanates were detected in the air. A small-molecular monoisocyanate, methyl isocyanate, and isocyanic acid were detected only during welding and turning operations. The diisocyanate concentrations were in general higher near the emission source than in the workers' breathing zone. A sampling strategy to evaluate the risk of exposure to isocyanates is presented.     

Development and application of quantitative methods for monitoring dermal and inhalation exposure to propiconazole

Quantitative methods to measure dermal and inhalation exposure to the fungicide propiconazole were developed in the laboratory and applied in the occupational exposure setting for monitoring five farm workers' exposure during pesticide preparation and application to peach crops. Dermal exposure was measured with tape-strips applied to the skin, and the amount of propiconazole was normalized to keratin content in the tape-strip. Inhalation exposure was measured with an OVS tube placed in the worker's breathing-zone during pesticide handling. Samples were analyzed by GC-MS in EI+ mode (limit of detection 6 pg microl(-1)). Dermal exposure ranged from non-detectable to 32.1 +/- 22.6 ng per microg keratin while breathing-zone concentrations varied from 0.2 to 2.2 microg m(-3). A positive correlation was observed between breathing-zone concentrations and ambient air temperature (r2 = 0.87, p < 0.01). Breathing-zone concentrations did not correlate with dermal exposure levels (r2 = 0.11, p = 0.52). Propiconazole levels were below limit of detection when rubber gloves, coveralls, and full-face mask were used. The total-body propiconazole dose, determined for each worker by summing the estimated dermal dose and inhalation dose, ranged from 0.01 to 12 microg per kg body weight per day. Our results show that tape-stripping of the skin and the OVS can be effectively utilized to measure dermal and inhalation exposure to propiconazole, respectively, and that the dermal route of exposure contributed substantially more to the total dose than the inhalation route.     

Development of an integrative passive sampler for the monitoring of organic water pollutants

The development of convenient and competitive devices and methods for monitoring of organic pollutants in the aquatic environment is of increasing interest. An integrative passive sampling system has been developed which consists of a solid poly(dimethylsiloxane) (PDMS) material (tube or rod), acting as hydrophobic organic receiving phase, enclosed in a water-filled or an air-filled low-density polyethylene (LDPE) membrane tubing. These samplers enable the direct analysis of the pollutants accumulated during exposure in the receiving phase by thermodesorption-GC/MS, avoiding expensive sample preparation and cleanups. The capabilities of these sampling devices were studied for the sampling of 20 persistent organic pollutants (chlorobenzenes, hexachlorocyclohexanes, p,p'-DDE, PAHs, and PCBs) in laboratory exposure experiments. For the three sampler designs investigated the uptake of all target analytes was integrative over exposure periods up to 9 days (except PCB 101). The determined sampling rates range from 4 to 1340 microl h(-1) for the water-filled samplers and from 20 to 6360 microl h(-1) for the air-filled ones, respectively. The sampling rate of the analytes is dependent on their molecular weight, partition between water and sampler media (PDMS, polyethylene, water, air) and also of the sampler design. The passive samplers enable the estimation of time-weighted average (TWA) concentration of water pollutants in the lower ng l(-1) to pg l(-1) range.     

Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland)

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.     

The application of HPLC-F and GC-MS to the analysis of selected hydroxy polycyclic hydrocarbons in two certified fish bile reference materials

Four selected hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), 2-hydroxy-naphthalene (2-OH-NPH), 1-hydroxy-phenanthrene (1-OH-PHE), 1-hydroxy-pyrene (1-OH-PYR) and 3-hydroxy-benzo[a]pyrene (3-OH-BaP) have been analysed in two certified fish bile reference materials (CRMs) for exposure monitoring of PAHs in the aquatic environment. The two materials, BCR 720 and BCR 721, consist of bile from fish exposed to contaminated sediment and dispersed crude oil, respectively. Both bile samples have been analysed by two different analytical techniques, gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-F), and the separation performance, detection limits, recoveries and reproducibility for the four target compounds were evaluated. HPLC-F requires a simple sample preparation and the separation capacity is adequate for quantification of 1-OH-PYR and 3-OH-BaP. Detection limits are excellent for 1-OH-PYR (6 pg injected) and 3-OH-BaP (3 pg injected) and generally improved with increasing molecular size. Recoveries ranged from 48 to 99% for the four selected compounds, depending on compound and concentration. Sample preparation prior to GC-MS analysis was more demanding, as reflected by the obtained recoveries for 2-OH-NPH, 1-OH-PHE and 1-OH-PYR (35 to 61%). The sensitivity improved with decreasing molecular size, 2-OH-NPH (1.2 pg injected), 1-OH-PHE (2.4 pg injected) and 1-OH-PYR (6 pg injected). Because of the superior separation power of GC and the extra selectivity of MS detection, GC-MS was the method of choice for the determination of 2-OH-NPH and 1-OH-PHE in both CRMs. In fish bile samples these two compounds are more likely to suffer from chromatographic overlap, and HPLC-F was not sufficiently selective. Determination of 1-OH-PYR was performed with success by both methods, but HPLC-F would be preferred because of the simpler and less time-consuming sample preparation. Detectable concentrations of 3-OH-BaP were present in BCR 720 and could only be determined by HPLC-F. The present work aims to present HPLC-F and GC-MS as complementary methods for the quantitative analysis of OH-PAHs in fish bile.     

Solid-phase extraction followed by liquid chromatography-time-of-flight-mass spectrometry to evaluate pharmaceuticals in effluents. A pilot monitoring study

The present work provides a multi-residue analytical method for determining a selection of 20 pharmaceuticals from diverse therapeutical classes in hospital effluent wastewater. The method is based on the simultaneous extraction of the target compounds by solid phase extraction (SPE), followed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) analysis. Using TOF-MS, accurate mass measurements within 2 ppm error were obtained for most of the pharmaceuticals studied. Empirical formula information can be obtained by this method, allowing the unequivocal identification of the target compounds in the samples. Validation studies showed that LC-TOF-MS analysis is a valuable new tool for identification and quantification of pharmaceuticals in wastewater. Recoveries, using Oasis HLB cartridges at pH 7, were higher than 75% for all pharmaceuticals, except for ranitidine, 4-methylaminoantipyrine (4-MAA), cefotaxime and omeprazole, which needed specific pH conditions for their extraction. Linearity of response over two orders of magnitude was demonstrated (r > 0.99). Matrix effects resulting in suppression of the response were observed. For most of the compounds ion suppression was less than 39%, except for metronidazole, carbamazepine 10,11-epoxide, naproxen and erythromycin, where the signal suppression was 42%, 59%, 46% and 95%, respectively. A simple and effective approach to minimize or avoid matrix interferences was the 1 : 4 dilution of the SPE extracts. Method detection limits (MDLs) and quantification limits (MQLs) ranged between 4-115 ng l(-1) and 14-384 ng l(-1), respectively. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1.1-19.8% and 1.7-21.7% for intra- and inter-day, respectively. The developed analytical method was applied to the analysis of hospital effluent wastewater during a survey study. 18 of the 20 pharmaceuticals studied were detected at concentration levels of microg l(-1), reaching in some cases concentrations over 100 microg l(-1), and in the case of the analgesic and antipyretic dipyrone metabolite, higher than 1000 microg l(-1).     

Bio-analytical and chemical characterisation of offshore produced water effluents for estrogen receptor (ER) agonists

The in vitro estrogen receptor (ER) agonist potency and C1 to C9 alkyl substituted phenol content of offshore produced water effluents collected from the UK sector of the North Sea were determined using a combination of bio-analytical and chemical analysis techniques. An in vitro reporter gene assay was used to determine ER agonist potency, whilst gas chromatography coupled to mass spectrometry (GC-MS) was used to quantify the concentration of alkylphenols. The in vitro ER agonist potency was highly variable and ranged from less than the limit of detection (theoretically 0.03 ng 17beta-estradiol (E2) l(-1)) to 91 ng E2 l(-1). C1 to C5 alkylphenol concentrations were also highly variable ranging from 5 to 1600 microg l(-1) with a median concentration of 206 microg l(-1). These data reflect the highly variable composition of produced water discharges from different fields. The observed poor correlation of the alkylphenol isomer content and ER agonist activity suggests that other compounds present in the produced water discharges may be responsible for the ER agonist activity observed. It is recommended that further work be performed to characterise the full range of ER agonists present in offshore produced water discharges.     

Chloroacetic acids in European soils and vegetation

Trichloroacetic acid (TCA) and dichloroacetic acid (DCA) are possible minor atmospheric degradation products of perchloroethylene and trichloroethylene, respectively. These acids may be wet- or dry-deposited from the atmosphere to land surfaces and hence possibly affect plant growth. However, the existing database on TCA levels in soil is limited to a few studies carried out in the late 1980's and the early to mid-1990's and it was concluded that there is a need for further measurements of concentrations of TCA and DCA in soils. In this study soil samples from 10 locations in 5 European countries, as well as vegetation samples, and a limited number of rainwater and air samples were collected and analysed for DCA and TCA to determine the concentrations of these compounds. An isotope dilution method using GC-MS was used for the determination of these acids in the samples. The method was briefly validated and the performance characteristics are presented. The results of the analysis of the soil samples show that the DCA and TCA concentrations in soil from different sites in Europe are more or less comparable, with the exception of Germany, especially Freudenstadt, where significantly higher TCA concentrations (up to 12 microg kg(-1) dw) were found. The average DCA and TCA concentrations in soil in this study were 0.25 +/- 0.12 and 0.64 +/- 1.40 microg kg(-1) dw, respectively. Generally, the concentration in soils from forest areas are about twice those from open-land areas. The DCA and TCA concentrations in vegetation samples ranged from 2.1 to 73 microg kg(-1) dw for DCA and from 4.7 to 17 microg kg(-1) dw for TCA. Thus, the concentrations in vegetation samples are 10-20 times higher than the soil concentrations. DCA and TCA concentrations in wet deposition samples and air samples collected in The Netherlands were 0.14 and 0.15 microg l(-1) for wet deposition samples and <0.5 and 0.7 ng m(-3) for air samples respectively. For these samples taken in The Netherlands, the estimated values for soil and air concentrations calculated from the wet deposition concentrations are in agreement with the concentrations measured in this study.     

A remote in situ monitor based on continuous flow analysis for the quantitation of sub-micromolar levels of hexavalent chromium in natural waters

We describe the design, optimization, and application of a small, lightweight, deployable monitoring instrument for accurately measuring parts-per-billion levels of hexavalent Cr in surface waters at hourly intervals. The monitor quantifies Cr(vi) using a standard molecular absorbance spectroscopic method, i.e. by formation of a complex with 1,5-diphenylcarbazide (DPC). The continuous flow analysis (CFA) design uses narrow conduits (0.90 mm) that are hot-forged onto poly(methyl methacrylate) ('Plexiglas') plates based on the method of Jannasch et al.(Anal. Chem., 1994, 66, 3352). The sample stream is drawn through the manifold at 25 microl min(-1) using a mini-peristaltic pump; osmotic pumps (10 microl h(-1)) are used to continuously inject reagent (2.0 mM DPC, 0.60 M HNO(3), 5.0% w/v acetone, and 0.10% w/v Brij-35) and to periodically introduce quality control standards and a cleaning solution (0.50 M HNO(3)). The 'Z-type' optical cell uses a liquid-core waveguide (10 mm) to collimate the light-emitting diode source beam (lambda(max) 574 nm) to a broadband photodiode detector. Figures of merit are: 7 min cycle time, response within 28 min and clear-down within 31 min, low waste generation (<40 ml d(-1)), detection limit (3sigma) of 48.4 microg l(-1) as Cr(vi) or 0.411 microM as chromic acid, 1.54% relative standard deviation at 100 microg l(-1), and selectivity for dissolved Cr(vi) in authentic surface water samples containing moderate levels (>0.21% w/v) of total particulate matter. Using a test chamber containing Milwaukee Harbor water that was periodically fortified with Cr(vi) standards, continuous testing over a 15 day period (354 h) yielded results that were in excellent agreement (<5% variation) with measurements made using an ICP-MS reference method. Drift in the calibration model over the test period was 1.23% and the variation in a 0.50 mg l(-1) Cr(vi) standard was 3.8%(n= 11). Known interferences to the DPC chemistry (Mo, V, and Hg at >5 mg l(-1)) were undetected in the harbor water by ICP-MS.     

Capillary microextraction for simultaneous analysis of multi-residual semivolatile organic compounds in water

Capillary microextractor (CME) in combination with a gas chromatograph-mass spectrometer (GC-MS) was employed for the determination of trace priority hazardous substances in water. Three groups of semivolatile organic compounds (SVOCs), i.e., chlorinated hydrocarbons, pesticides and polycyclic aromatic hydrocarbons (PAHs), were simultaneously determined. SVOCs were extracted from 7 mL of water samples on a 100 cm commercial gas chromatographic column (0.32 mm id x film thickness 0.25 microm, HP-5 capillary column) and eluted with only 3 microL of acetonitrile. The extractant was analyzed by GC-MS in the selected ion monitoring mode. The method showed good linearity over the concentration range 10 ng L(-1) to 3.0 mg L(-1) with correlation coefficients (r) greater than 0.99 and low limits of detection ranged from 10 ng L(-1) to 1.0 mg L(-1). High recovery (more than 80%) was obtained with relative standard deviation less than 10%. The method was successfully applied for trace level analyses of SVOCs in water samples.     

Atmospheric transport of persistent organic pollutants (POPs) to Bjørnøya (Bear island)

A first medium term monitoring of atmospheric transport and distribution for persistent organic pollutants (POPs) in Bj?rn?ya (Bear island) air samples has been performed in the period between week 51/1999 and week 28/2003. A total of 50 single compounds consisting of polychlorinated biphenyls (33 congeners), hexachlorobenzene (HCB), hexachlorocyclohexane isomers (alpha-, beta-, gamma-HCH), alpha-endosulfan, cyclodiene pesticides (chlordanes, nonachlor-isomers, oxy-chlordane, heptachlor and chlordane) as well as dichlorodiphenyltrichloroethane (DDT) derivatives were analysed and quantified. Atmospheric transport of POPs was identified as an important contamination source for the island. PCBs, HCB and HCH isomers were the predominant POP groups, contributing with 70-90% to the overall POP burden quantified in the Bj?rn?ya air samples. The highest concentration levels for a single compound were found for HCB (25-35 pg m(-3)). However, the sum of 33 PCB congeners was found to be in the same concentration range (annual means between 15 and 30 pg m(-3)). Cyclodiene pesticides, DDT derivatives and alpha-endosulfan were identified as minor contaminants. Several atmospheric long-range transport episodes were identified and characterised. Indications for industrial emissions as well as agricultural sources were found for the respective atmospheric transport episodes. A first simple statistical correlation assessment showed that for long-range transport of pollution, the local meteorological situation is not as important as the air mass properties integrated over the time period of the transport event. The local weather situation, on the other hand, is important when investigating deposition rates and up-take/accumulation properties in the local ecosystem. Based upon chemical data interpretation, valuable information about the influence of primary and secondary sources on the air mass contamination with chlorinated insecticides (e.g., HCHs) was found and discussed. The interdisciplinary interpretation of contaminant data using statistical methods, chemical analysis, meteorological modelling and classical meteorological information for a comprehensive evaluation of atmospheric long range transport into the European Arctic (Bj?rn?ya) has proven to be a highly versatile tool not only for atmospheric scientists but also with strong potential for regulatory purposes.     

Determination of CH4, CO2 and N2O in air samples and soil atmosphere by gas chromatography mass spectrometry, GC-MS

A method for determination of the climate gases CH4, CO2 and N2O in air samples and soil atmosphere was developed using GC-MS. The method uses straightforward gas chromatography (separation of the gases) with a mass spectrometric detector in single ion mode (specific determination). The gases were determined with high sensitivity and high sample throughput (18 samples h(-1)). The LOD (3sigma) for the gases were 0.10 micro L L(-1) for CH4, 20 microL L(-1) for CO2 and 0.02 microL L(-1) for N2O. The linear range (R2 = 0.999) was up to 500 microL L(-1) for CH4, 4000 microL L(-1) for CO2 and 80 microL L(-1) for N2O. The samples were collected in 10 mL vials and a 5 microL aliquot was injected on column. The method was tested against certified gas references, the analytical data gave an accuracy within +/-5% and a precision of +/-3%. The presence of < or = 10% by volume of C2H2 (often used experimentally to prevent N2 formation from N2O) did not interfere with detection for the targeted trace gases.     

Observation of volatile and semi-volatile carbonyls in an Algerian urban environment using dinitrophenylhydrazine/silica-HPLC and pentafluorophenylhydrazine/silica-GC-MS

Lower carbonyls and n-alkanals from C5 to C10 were measured from late autumn 2000 to summer 2001 in two urban areas in the Algerian territory: Algiers and Ouargla. They were collected on silica cartridges coated with dinitrophenylhydrazine (DNPH) and pentafluorophenylhydrazine (PFPH), which were analysed by HPLC-UV and high-resolution GC-MS. respectively. The two methods were used in parallel samplings in a suburban Algiers site and provided consistent results for semi-volatile congeners, as differences in the concentration data did not exceed 21% on average for individual carbonyl levels ranging from 0.0 to 0.5-2.6 microg m(-3). Concentrations of formaldehyde up to 27 and 5 microg m(-3) were monitored during 10 h samplings in the daytime in Algiers and Ouargla, respectively; acetaldehyde reached values of 13 and 5 microg m(-3), whilst acetone was the most abundant ketone with peak levels of 14 and 4 microg m(-3), respectively. High night-time levels of lower carbonyls were also measured at both locations. Among the semi-volatile alkanals, the highest levels were observed in suburban Algiers for hexanal and nonanal (2.2 microg m(-3)) and in downtown Algiers for valeraldehyde (2.6 microg m(-3)), whilst in Ouargla only hexanal and nonanal levels within the C5-C10 fraction exceeded 1 microg m(-3). Moreover, benzaldehyde concentrations as high as 5 microg m(-3) were measured in the centre of Algiers. Algiers data are comparable with those found in photochemically polluted urban areas of Europe and the USA. Strong correlations between formaldehyde and acetaldehyde and between formaldehyde and benzaldehyde were observed; by contrast, acetone did not show any correlation with the lower aldehydes, suggesting the existence of carbonyl sources other than vehicular traffic. Diurnal variations of almost all carbonyls suggested that motor vehicles were the most important source in the winter, whereas photochemical production appeared to predominate during the summer.     

Solid-phase microextraction to monitor the sonochemical degradation of polycyclic aromatic hydrocarbons in water

Solid-phase microextraction (SPME) coupled with GC-MS has been used to monitor the degradation of polycyclic aromatic hydrocarbons (PAHs) by ultrasound treatment. Immersion SPME sampling enabled the fast and solventless extraction of target contaminants at the low microg l(-1) concentration level. The developed protocol was found to be linear in the concentration range from 0.1 to 50 microg l(-1) for most target analytes, with the limits of detection ranging between 0.01 and 0.70 microg l(-1) and the relative standard deviations between 4.31 and 27%. The developed SPME protocol was used to follow concentration profiles of aqueous solutions containing 16 PAHs, which were subject to low frequency ultrasonic irradiation. At the conditions employed in this study (80 kHz of ultrasound frequency, 130 W l(-1) of applied electric power density, 30 microg l(-1) of initial concentration for each of the 16 PAHs), sonochemical treatment was found capable of destroying the lower molecular weight PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) within 120-180 min of irradiation. The higher molecular weight PAHs were more recalcitrant to ultrasound treatment.