Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.     

Immersed solid phase microextraction to measure chemical activity of lipophilic organic contaminants in fatty tissue samples

It is known that solid phase microextraction (SPME) fibers can be equilibrated directly within environmental matrices such as water, sediment and soil slurries. Here it is shown that this method can also be applied to biological tissue. SPME extraction of biological matrices reportedly causes lipophilic fouling of the fiber. However, we found no significant measurement bias when combining equilibrium sampling with fiber surface cleaning. The uptake of lipophilic organic pollutants from the tissue and into the SPME fiber coating was characterized by fast equilibrium partitioning without sample depletion and without impacting the sorptive properties of the fiber. The precision of the method when applied to hexachlorobenzene and several PCB congeners in harbor porpoise blubber was 15%, which includes the variation between SPME samplings, manual injections and the instrumental analysis. A good correlation (r(2)=0.95) was obtained between SPME measurements of PCB 153 in blubber and concentrations obtained via a traditional analytical approach. These results indicate that SPME is a promising technique for measuring chemical activity in biological tissue, which would make it a useful tool for studying chemical distribution in organisms as well as biodilution and biomagnification phenomena.     

Bioavailability of PCBs from field-collected sediments: application of Tenax extraction and matrix-SPME techniques

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.     

Pesticide contamination profiles of water, sediment and aquatic organisms in the effluent of Gaobeidian wastewater treatment plant

Organochlorine pesticides (OCPs, including DDT, HCH and HCB) and six indicator polychlorinated biphenyls (PCB 28, 52, 101, 138, 153, and 180) were measured in water, sediment, zooplankton, fish and Chinese softshell turtle (Pelodiscus sinensis) from Gaobeidian Lake, which is located in the effluent of Gaobeidian wastewater treatment plant (WWTP) in Beijing, China. DDTs were dominant except for in water. In water, the concentrations of DDTs (6.22 ng l(-1)) and HCHs (18.0 ng l(-1)) were less than the limits (l000 ng l(-1) for DDTs and 5000 ng l(-1) for HCHs). However, PCBs concentration (20.8 ng l(-1)) exceeded the limit (14 ng l(-1)) suggested by the United States Environmental Protection Agency (USEPA). The high ratio of p,p'-DDT/DDTs (0.80) in water suggested that DDTs had recently been discharged into the ambient environment despite a longtime ban in China. For fish and Pelodiscus sinensis, the accumulation patterns of OCPs and PCBs were different in muscle and liver. And HCB and PCB 153 were significant different in different species (p<0.05). PCBs were dominated by PCB 52 in zooplankton, but by PCB 138 and 153 in Pelodiscus sinensis. The highest food web magnification factor (FWMF) was 4.83 for p,p'-DDT and the second highest was 4.36 for PCB 101 in Gaobeidian Lake. As compared with the other studies, biomagnification in the present study was not obvious. Trophic levels and age were two important factors that might contribute to the bioaccumulation in the present study.     

Levels of polychlorinated biphenyls and organochlorine pesticides in serum samples of Egyptian Vulture (Neophron percnopterus) from Spain

Concentrations of 23 polychlorinated biphenyls (PCBs), p,p'-DDT and two of its metabolites, p,p'-DDE and p,p'-TDE have been measured in serum samples of up to 1 ml of Egyptian Vulture (Neophron percnopterus) gathered from five populations in Spain. SigmaPCB concentrations were found to be in the range 3.2-97 ng/ml, while those of SigmaDDTs ranged from 0.93 to 38 ng/ml. p,p'-DDT/p,p'-DDE ratios higher than one were only found in the Segovia population, which could be an indication of recent use of p,p'-DDT in the area. In all cases, PCB profiles were dominated by congeners 52, 132 + 105, 138, 153 and 180. However, some differences among the five populations studied became evident when their profiles were compared with those of technical PCB mixtures by principal components analysis. The DDT and PCB levels detected in the serums analysed were lower than those previously reported for similar avian species and those reported to have deleterious effects on survival or reproduction of birds.     

Solid phase microextraction as a tool to predict internal concentrations of soil contaminants in terrestrial organisms after exposure to a laboratory standard soil

Uptake and accumulation of three chlorobenzenes was studied in both biota (Enchytraeus crypticus) and 30 mum polydimethylsiloxane (PDMS) solid phase microextraction (SPME) fibers after exposure to spiked OECD soil. The OECD soil was spiked with three different concentrations of all contaminants. Uptake of all three chlorobenzenes in E. crypticus was fast and steady state levels were reached within 2-4 days. Also in the PDMS-SPME fibers uptake was very fast for all three compounds, with steady state levels reached after 1 day. Comparison of steady state levels in biota and in the PDMS-SPME fibers showed a relationship which was consistent over the range of concentrations of chlorobenzenes in soil and the difference in logKow. This shows that measuring the concentrations of hydrophobic chemicals in a hydrophobic phase such as PDMS can be used as a simple tool to estimate internal concentrations of these chemicals in biota exposed to complex matrices such as soil.     

A comparison of exposure methods for SPME-based bioavailability estimates

The ability of polydimethlysiloxane coated solid phase microextraction (SPME) fibers to predict bioavailability has been documented for a number of species and compounds. There are also a variety of established methods for establishing SPME-based bioavailability estimates; however, factors such as time until equilibrium and exposure regimen could affect fiber concentrations and have not yet been thoroughly tested. Exposure time may influence SPME fiber concentrations at equilibrium. Co-exposure of the fibers with different animals or the invertebrate species used could yield different estimates than those acquired using a shaker table system to achieve equilibrium between the sediment and SPME fibers. The current study examined the effects of time and exposure method (shaker table versus co-exposure with test species) on SPME fiber concentrations for two hydrophobic compounds: permethrin and p,p′-dichlorodiphenyldichloroethylene (DDE). An additional experiment with permethrin determined whether animal densities or fiber number influenced fiber concentrations. There were significant differences between the time required for SPME fibers to reach equilibrium when co-exposed with different species or separately, but fiber concentrations at equilibrium among treatments for both compounds were similar. Furthermore, among the 12 variations in species and fiber densities, there were no significant differences among treatments indicating that neither the route of exposure, animal density, nor fiber volume influenced SPME fiber estimates. This demonstrated that SPME fiber concentrations at equilibrium were not affected by exposure conditions, increasing their versatility in environmental assessments.     

PCBs and other organochlorines in human tissue samples from the Welsh population: II--Milk

Polychlorinated biphenyl (PCB) and SigmaDDT (i.e. p,p'-DDT + p,p'-DDE = p,p'-DDD) concentrations were determined from the analysis of 115 Welsh breast milk samples collected in 1990 and 1991. Fifty PCB congeners were screened, of which 24 were identified in most samples. The PCB congener pattern was consistent between individual milk samples, with IUPAC congeners 28, 138, 153 and 180 being the most abundant and accounting for an average of 50% of the SigmaPCB concentrations determined. PCB concentrations varied between 2 and 70 ng g(-1) whole milk, were positively correlated with age, and negatively correlated with the total lactation period and with the percent lipid content of the milk. PCB pattern distributions differed between milk and adipose tissue samples. Human milk had a higher proportion of tri- (18 and 28), tetra- (44, 52 and 66) and pentachlorinated biphenyls (101) compared to human adipose tissue. SigmaDDT concentrations ranged from 0.3 to 71 ng g(-1) of whole milk, with p,p'-DDE contributing towards an average of 92% of the SigmaDDT concentrations. SigmaDDT levels were also positively correlated with age and negatively associated with the lactation period, though these correlations were rather weak. No significant differences in the SigmaPCB and SigmaDDT concentrations were noted between milk samples from donors living in rural and urban locations, or between the subjects' body weight, smoking habits or diet.     

Contamination of human milk in Middle Hesse, Germany--a cross-sectional study on the changing levels of chlorinated pesticides, PCB congeners and recent levels of nitro musks

Human milk samples from women in Middle Hesse, Germany were chemically analyzed for contamination levels of alpha-, beta- and gamma-HCH, HCB, p,p'-DDE and p,p'-DDT as well as the PCB-congeners no. 28, 31, 49, 52, 101, 118, 138, 153, 156, 170 and 180. Changes in concentrations of these compounds in human milk over an extended time period were studied by comparing samples from 1984/85, 1990/91 and 1995. In addition, concentrations of the nitro-aromatic compounds musk xylene and musk ketone were determined in the 1995 samples. The study showed statistically highly significant (p<0.001) reductions in levels of beta- and gamma-HCH, HCB, p,p'-DDE and p,p'-DDT, in human milk from 1995 compared to samples from 1984/85. A weakly significant reduction (p<0.05) of alpha-HCH was also observed. For low-chlorinated PCB congeners, on the other hand, a highly significant increase of PCB no. 28 was detected and concentrations of congeners no. 31, 49 and 52 remained unchanged. Concentrations of the high-chlorinated congeners no. 101, 138, 153 and 180 dropped (highly significant). A highly significant reduction of PCB no. 118 and 156 occurred between 1990/91 and 1995, but a highly significant increase was found for no. 170. Lower levels of hydrocarbon contamination of human milk samples from 1995 than were found in samples from 1984/85 and 1990/91 can be seen to result partially from voluntary reductions, but primarily reflect restrictive environmental legislation in the Federal Republic of Germany. Mean concentrations of musk xylene and musk ketone in samples from 1995 were 41 microg/kg and 10 microg/kg milk fat, respectively.     

Sociodemographic, reproductive and dietary predictors of organochlorine compounds levels in pregnant women in Spain

Organochlorine pesticides and polychlorinated biphenyls (PCBs) are consistently found in human tissues. Serum levels of organochlorine compounds (OC) in pregnant women in particular have raised concern about possible harm to humans in the early phases of physical and behavioural development. The objective of the present study was to evaluate the association between concentration of OCs in serum of two cohorts of pregnant women from Gipuzkoa and Sabadell in Spain and socioeconomic, reproductive and dietary variables. Concentration of polychlorinated biphenyls (PCBs: 28, 52, 101, 118, 138, 153 and 180), hexachlorobenzene (HCB), beta and gamma-hexachlorocyclohexane (β-HCH and γ-HCH), heptachlor epoxide, dichlorodiphenyl dichloroethylene (p,p'-DDE) and dichlorodiphenyl trichloroethane (p,p'-DDT) were measured in the serum of 1259 pregnant women. Associations between OCs and potential predictor variables were assessed using linear regression models adjusted for potential confounders. The compounds most commonly found in the serum were p,p'-DDE (99% of the samples) and PCB-153 (95% of the samples). Geometric means of serum concentrations (ng g?1 lipid) of organochlorine pesticides were 110.0, 19.1, and 33.5 for p,p'-DDE, β-HCH, and HCB respectively, while the geometric means of PCBs were 21.8, 38.9 and 26.9 for PCB 138, 153, and 180 respectively. The levels of all OCs increased with age. BMI was positively associated with the concentration of organochlorine pesticides but inversely related to PCB concentrations. The serum levels of OCs fell only after a cumulative period of breastfeeding of over a year. Levels of PCBs were related to fish intake, but in general dietary factors did not improve the explained variability of the concentrations of OCs. Overall, the levels of OCs found in the study are at the lower end of the range reported in Spain and other countries.     

Persistent organic pollutants (POPs) in antarctic fish: levels,patterns, changes

Organochlorine compounds were analysed in three fish species of different feeding types from the area of Elephant Island in the Antarctic. In 1996, hexachlorobenzene (HCB) (means: 15-20 ng/g lipid), p,p'-DDE (5-13 ng/g lipid) and mirex (1-7 ng/g lipid) predominated, while PCBs were minor components (PCB 153: 0.4-2 ng/g lipid). Concentration patterns were species-dependent: PCB 180, PCB 153, mirex, nonachlor III, trans-nonachlor and the toxaphene compound B8-1413 were highest in the bottom invertebrate feeder Gobionotothen gibberifrons and lowest in the krill feeder Champsocephalus gunnari. Levels of p,p'-DDE, PCB 138 and heptachloro-1'-methyl-1,2'-bipyrrole (Q1), a natural bioaccumulative product, were highest in the fish feeder Chaenocephalus aceratus, whereas HCB was present in about equal concentrations in all species. Most compounds were taken up preferentially via the benthic food chain, the chlorinated bipyrrole via the pelagic food chain and HCB from the water. In antarctic fish, biomagnification was generally more important than bioconcentration. Between 1987 and 1996, most persistent organic pollutant (POP) levels showed significant increases in the benthos feeder and the fish feeder, while they remained nearly constant or increased less in the krill feeder. Hence, the former species represent indicator species for changing POP levels in Antarctica. Ratios (1996/1987) of average concentrations in G. gibberifrons were: PCB 138 0.7, HCB 0.8, B8-1413 1.5, PCB 180 1.7, PCB 153 1.8, p,p'-DDE 2.0, nonachlor III 2.9, trans-nonachlor 3.3, mirex 6.7. By comparison with trends in the northern hemisphere it is concluded that global distribution of HCB is close to equilibrium. Changing levels of other POPs reflect global redistribution and increasing transfer to antarctic waters probably due to recent usage in the southern hemisphere and climate changes.     

A numerical study on the seasonal variability of polychlorinated biphenyls from the atmosphere in the East China Sea

A three-dimensional/high-resolution transport model for persistent organic pollutants (POPs) has been developed for the East China Sea (ECS). The POPs model has four compartments (gaseous, dissolved, phytoplankton-bound, and detritus-bound phases) and includes processes for diffusive air-water exchange, phytoplankton uptake/depuration to POPs, decomposition of dissolved phase, vertical sinking of phytoplankton, detritus production by phytoplankton mortality, and vertical sinking and decomposition of detritus. The POPs model is coupled with an ocean circulation model that can reproduce the seasonal variation in physical variables to represent the advection and diffusion of POPs. We applied the POPs model to the polychlorinated biphenyl congener 153 (PCB 153) from the atmosphere and examined the behavior of PCB 153 in the ocean. The model showed a remarkable seasonal variability of PCB 153. Concentrations in the dissolved and particulate phases are high in winter (January-March) and low in summer (July-September). In coastal regions, where chlorophyll a concentration is high, horizontal and vertical distributions in the dissolved and particulate PCB 153 concentrations are strongly affected by phytoplankton uptake. The sensitivity experiments on the dynamics of PCB 153 suggested that a change of Henry’s law constant associated with water temperature is the major factor controlling the seasonal variability of PCB 153. The model-based yearly mass balance of PCB 153 in the ECS indicated that most of the atmospheric input (35.5 kg year⁻¹) is removed by the horizontal advection outside the ECS (19.0 kg year⁻¹) and accumulates to the sea bottom by vertical sinking (15.7 kg year⁻¹). For comparison with PCB 153, we also conducted simulations for PCB 52, 101, and 180. The seasonal variations are similar to that of PCB 153. The mass balance of PCB 52 that has short half-life time and less hydrophobic property shows the different results compared with PCB 101, 153, and 180.     

Association between biomarkers of exposure to persistent organochlorine compounds (POCs)

Serum concentrations of CB-153 and p,p'-DDE were assessed for 354 men and women from the Swedish Fishermen's Families Cohort, and were found to correlate very well (Pearson's r=0.72). In this particular cohort the main source of exposure to persistent organochlorine compounds are consumption of contaminated fatty fish. High correlations between total PCB/CB-153 and p,p'-DDE have also been found in other population with similar exposure, but not in populations whose major source of exposure to persistent organochlorine compounds is not necessarily through the consumption of contaminated sea food. The authors suggest that when investigating a possible relation between exposure to persistent organochlorine compounds and different health outcomes in populations with exposure similar to the Swedish Fishermen's Families Cohort, there may be no need to analyze more than either CB-153 or p,p'-DDE.     

Human biomonitoring of polychlorinated biphenyls and polychlorinated dibenzodioxins and dibenzofuranes in teachers working in a PCB-contaminated school

Eighteen teachers from a highly contaminated school and 11 teachers from a control school participated in this study. Total polychlorinated biphenyl (PCB) indoor air concentration (six indicator congeners x 5) was beyond 12000 ng/m3 in some rooms of the contaminated school. PCB 28 and PCB 52 were the prevailing congeners. Whole blood was taken from each participant by the local health authority, pooled in two groups and analysed for the six PCB indicator congeners, non-ortho PCBs and polychlorinated dibenzodioxins (PCDD)/polychlorinated dibenzofurans (PCDF). Blood analysis showed elevated mean PCB 28 and PCB 52 levels for the exposed group, however the two groups were almost identical with regard to PCB 101, 138, 153 and 180. Moreover no difference can be observed for the concentration of non-ortho PCBs and PCDD/PCDF. The data support the finding, that heavy indoor air contamination with low chlorinated PCBs causes an increase of PCB 28 and PCB 52 blood levels. However, this increment was small compared to their total PCB load.     

Seasonal fluxes and temperature-dependent accumulation of persistent organic pollutants in lakes: The role of internal biogeochemical cycling

A dynamic flux model for lakes taking into account the interactions between atmospheric depositional and biogeochemical processes (BIODEP model) was used to assess the importance of internal cycling and biogeochemical processes with respect to accumulation of four different polychlorinated biphenyls (PCBs) (congeners 28, 52, 101 and 153) in Lake Redo, a high-altitude lake in the Spanish Pyrenees. To investigate the effect of temperature on sediment accumulation, the model was run at different temperatures and corresponding sediment inventories were plotted vs. reciprocal temperature. In line with measurements from a previous study looking at sediment inventories of 19 European high-altitude lakes (MOLAR study), we found a stronger temperature dependence of lake sediment concentrations for the less volatile/less soluble PCBs. Seasonal and annual mass balances were investigated and highlighted the importance of internal lake processes controlling the differences in sediment accumulation for the different PCB congeners. For example, the higher temperature dependence of sediment inventories for the high chlorinated congeners is due to the fast dynamics of water-to-sediment transport in comparison to atmospheric deposition processes.     

Identification of dimethylchloroarsine near a former herbicide factory by headspace solid-phase microextraction gas chromatography-mass spectrometry

The application of an improved method based on multidetector gas chromatography to the determination of trace levels of organoarsines in complex matrices is described. The method using headspace-mode solid-phase microextraction (SPME) was applied to a carefully sampled and preserved freshwater sediment core obtained from central Green Bay, Lake Michigan. The sediment core was collected and fractionated in an inert atmosphere. A carboxen/ polydimethylsiloxane-coated SPME fiber (85 microm film thickness) was equilibrated (n = 4) for 60 min at 25 degrees C in the headspace of the sample vessel before introduction to the chromatograph. Conventional quadrupole ion trap mass spectrometry (electron impact ionization), electron capture detection, and pulsed flame photometric detection (arsenic mode) were employed for structure elucidation. A heretofore unidentified species in this region, dimethylchloroarsine (DMCA). was identified. The mass spectrum for DMCA is interpreted based on the observed fragmentation pattern. A bimodal vertical distribution of DMCA in the sediment core sample was observed and its interpretation based on Pb-210 dating is reported.     

Serum concentrations of indicator PCB congeners in the Czech adult population

In 2006, levels of seven indicator polychlorinated biphenyl congeners (PCB28, 52, 101, 118, 138, 153, and 180) in blood serum of 202 blood donors residing for more than 2 years in five urban areas included in the Czech Human Biomonitoring project were measured by GC/MS/MS method. PCB congeners 138, 153 and 180 accounted for about 97% of the sum of the indicator congeners analyzed. Overall, the median and 95th percentile of the most abundant congener PCB 153 were 438 ng/g lipid and 1079 ng/g lipid, respectively. The highest median levels were found in Uherské Hradiste (669 ng/g lipid) and Ostrava (672 ng/g lipid in males compared to 341 ng/g lipid in females). Serum PCB concentrations were significantly associated with age, gender, place of residence and smoking habit, but not with body mass index and education. The results suggest the importance of PCB body burden in the Czech general population and the existence of hot spots.     

Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China

Tonghui River, a typical river in Beijing, People's Republic of China, was studied for its water and sediment quality, by determining the levels of 16 polycyclic aromatic hydrocarbons (PAHs), 12 polychlorinated biphenyls (PCBs) and 18 organochlorine pesticides in water and sediment samples. Total PAHs, PCBs and organochlorine pesticides concentrations in water varied from 192.5 to 2651 ng/l, 31.58-344.9 ng/l and 134.9-3788 ng/l, respectively. The total PAHs, PCBs and organochlorine pesticides concentrations in surficial sediments were 127-928 ng/g, 0.78-8.47 ng/g and 1.79-13.98 ng/g dry weight, respectively. The results showed that the concentration of these selected organic pollutants in sediment was higher than those in surface water. It may be due to the fact that organic hydrophobic pollutants tend to stay in the sediments. The PAHs were dominated by 2-, 3-ring components in water samples and by 3- and 4-ring compounds in sediment. For organochlorines, alpha-HCH, delta-HCH, Heptachlor, Endosulfan II, DDT are the major organochlorine pesticides in water while Heptachlor, Dieldrin and DDE composed of 95% of total organochlorine pesticides in sediment. For HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH), the predominance of alpha-HCH of total HCHs were clearly observed in water and sediment. PCB18, PCB31 and PCB52 were predominant in water, on average these compounds collectively accounted for 67% of total PCBs. But in sediment, the predominant compounds were PCB28, PCB31 and PCB153, which accounted for 71% of total PCBs in sediment. The levels of micro pollutants in our study areas were compared with other studies.     

Gas chromatographic analysis of organic marker compounds in fine particulate matter using solid-phase microextraction

A gas chromatographic method that uses solid-phase microextraction for analysis of organic marker compounds in fine particulate matter (PM2.5) is reported. The target marker compounds were selected for specificity toward emission from wood smoke, diesel or gasoline combustion, or meat cooking. Temperature-programmed volatilization analysis was used to characterize the thermal stabilities and volatile properties of the compounds of interest. The compounds were thermally evaporated from a quartz filter, sorbed to a solid phase microextraction (SPME) fiber, and thermally desorbed at 280 degrees C in a gas chromatograph injection port connected via a DB 1701 capillary separating column. Various experimental parameters (fiber type, time, and temperature of sorption) were optimized. It was found that high extraction yield could be achieved using a polyacrylate fiber for polar substances, such as levoglucosan, and a 7-microm polydimethylsiloxane (PDMS)-coated fiber for nonpolar compounds, such as hopanes and polyaromatic hydrocarbon. A compromise was made by selecting a carboxen/PDMS fiber, which can simultaneously extract all of the analytes of interest with moderate-to-high efficiency at 180 degrees C within a 30-min accumulation period. The optimized method was applied to the determination of levoglucosan in pine wood combustion emissions. The simplicity, rapidity, and selectivity of sample collection with a polymer-coated SPME coupled to capillary gas chromatography (GC) made this method potentially useful for atmospheric chemistry studies.     

Comparison between solid-phase extraction methods for the chromatographic determination of organophosphorus pesticides in water

A solid-phase microextraction (SPME) procedure has been developed to extract eight organophosphorus pesticides (OPs) in water and the method was compared with a conventional solid phase extraction (SPE) technique. The extracted OPs were analyzed by gas chromatography using thermionic specific detection. Both extraction methods presented linear calibration at least over the concentration range investigated (100 to 1000 ng x mL(-1) for SPE and 1 to 100 ng x mL(-1) for SPME). SPME method presented higher sensitivity than SPE. The quantitation limits were between 0.1 to 1.0 ng x mL(-1) for SPME depending upon the analyte, and 100 ng x mL(-1) for SPE. The precision, as measured by the standard deviations (RSD), were in the range 3.6% to 5.8% for SPME and 2.4% to 9.2% for SPE. Along with the feature of being a solvent - free sampling technique, SPME offers additional benefits due to its high sensitivity, simplicity, and small size sample required (typically: SPE - 500 mL, SPME - 5 mL).