Soil solution extraction techniques for microbial ecotoxicity testing: a comparative evaluation

The suitability of two different techniques (centrifugation and Rhizon sampler) for obtaining the interstitial pore water of soil (soil solution), integral to the ecotoxicity assessment of metal contaminated soil, were investigated by combining chemical analyses and a luminescence-based microbial biosensor. Two different techniques, centrifugation and Rhizon sampler, were used to extract the soil solution from Insch (a loamy sand) and Boyndie (a sandy loam) soils, which had been amended with different concentrations of Zn and Cd. The concentrations of dissolved organic carbon (DOC), major anions (F- , CI-, NO3, SO4(2-)) and major cations (K+, Mg2+, Ca2+) in the soil solutions varied depending on the extraction technique used. Overall, the concentrations of Zn and Cd were significantly higher in the soil solution extracted using the centrifugation technique compared with that extracted using the Rhizon sampler technique. Furthermore, the differences observed between the two extraction techniques depended on the type of soil from which the solution was being extracted. The luminescence-based biosensor Escherichia coli HB101 pUCD607 was shown to respond to the free metal concentrations in the soil solutions and showed that different toxicities were associated with each soil, depending on the technique used to extract the soil solution. This study highlights the need to characterise the type of extraction technique used to obtain the soil solution for ecotoxicity testing in order that a representative ecotoxicity assessment can be carried out.     

Evaluation of interactive toxicity of chlorophenols in water and soil using lux-marked biosensors

An assessment of the toxicity of three chlorophenol compounds (2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP)), individually and in combinations, was made in deionised water, soil extracts and soils using the lux-marked microbial biosensors: Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607. These biosensors responded to the bioavailable fraction of pollutants enabling a rapid and ecologically relevant toxicity test. Toxicity interaction responses of pollutant mixtures were predicted after individual compounds were assessed. Synergistic interactions were observed in the response of P. fluorescens to all combinations of chlorophenols tested, while the toxicity response of E. coli varied with the matrices tested. Soil characteristics influenced the toxicity response when compared with aqueous solutions. These results highlight the significance of interactive factors and physicochemical parameters when evaluating toxicity. To develop an understanding of pollution derived hazard assessment in soils we need to integrate a wide spectrum of parameters.     

Comparison of response of six different luminescent bacterial bioassays to bioremediation of five contrasting oils

The performance of six different bioluminescent bacteria for the assessment of oil bioremediation was compared. Three contained lux genes linked to promoters from hydrocarbon degradation pathways: Pseudomonas fluorescens HK44 (pUTK21), Escherichia coli HMS174 (pOS25) and E. coli DH5 alpha (pGEc74, pJAMA7), responding to naphthalene, isopropylbenzene and octane, respectively. The other three expressed lux constitutively: E. coli HB101 (pUCD607) and P. putida F1 (pUCD607) are genetically engineered, while Vibrio fischeri is naturally bioluminescent and was included to facilitate comparison with previous work. Five different oils (four crude oils plus diesel) were spiked into soil, and the progress of remediation was followed over a period of 119 d by monitoring both hydrocarbon disappearance and changes in the microbial response to soil extracts. The octane bioassay was the only one of the hydrocarbon-responsive bacterial assays to show any appreciable response, with up to 20-fold induction by light crude oils. Heavy crude oil and diesel elicited a much weaker response. The metabolic (lux constitutively expressed) bioassays showed that there was a general increase in toxicity over the course of the experiment, although toxicity to E. coli HB101 (pUCD607) appeared to be decreasing by the final sampling point. The metabolic bioassay response was much less variable between the different oils than for the first three, catabolic, strains.     

Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.     

Comparison of PoraPak Rxn RP and XAD-2 adsorbents for monitoring dissolved hydrophobic organic contaminants

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant’s hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.     

Monitoring of the ecotoxicological hazard potential by polar organic micropollutants in sewage treatment plants and surface waters using a mode-of-action based test battery

We propose and evaluate a mode-of-action based test battery of low-complexity and in-vitro bioassays that can be used as a routine monitoring tool for sewage treatment efficiency and water quality assessment. The test battery comprises five bioassays covering five different modes of toxic action. The bioluminescence inhibition test with Vibrio fischeri and a growth rate inhibition test with the green algae Pseudokirchneriella subcapitata are measures of non-specific integrative effects. A second endpoint in the algae test, the specific inhibition of the efficiency of photosynthesis, gives an account of the presence of herbicides. An enzymatic assay covers an important aspect of insecticidal activity, the inhibition of the acetylcholine esterase activity. Estrogenic effects are assessed with the yeast estrogen screen (YES) and genotoxicity with the umuC test. Three field studies, each lasting six to seven consecutive days, were undertaken at a sewage treatment plant (STP) in Switzerland. Samples were collected in summer and late autumn, under dry and rainy conditions. None of the bioassays gave positive results with raw water in whole effluent toxicity testing. Therefore, water samples from various sites during wastewater treatment and from surface water were enriched with solid-phase extraction. The focus was on non-volatile compounds of average to moderate hydrophobicity, a range that includes most pesticides, biocides and pharmaceuticals. Various polar solid phases were evaluated for their extraction efficiency, disturbance by matrix components and overall performance. We finally selected a mixture of a polymeric sorbent and a C18-sorbent, Lichrolut EN and RP-18 or, alternatively, Empore SDB-RPS disks. All bioassays gave clear and robust responses with the SPE extracts. With the bioassay data the treatment efficiency of the STP can be assessed with respect to different modes of toxic action and accordingly different groups of micropollutants. Furthermore, the data allowed for a comparison between the effluent and the receiving river. In all bioassays the primary effluent had a strong effect and this effect was reduced after passing the STP. Treatment efficiency was high (typically over 90%) but varied from bioassay to bioassay, which is expected because each bioassay detects different types of micropollutants and therefore we cannot expect a common answer.     

Addressing analytical uncertainties in the determination of trichloroacetic acid in soil

Soil is an important compartment in the environmental cycling of trichloroacetic acid (TCA), but soil TCA concentration is a methodologically defined quantity; analytical methods either quantify TCA in an aqueous extract of the soil, or thermally decarboxylate TCA to chloroform in the whole soil sample. The former may underestimate the total soil TCA, whereas the latter may overestimate TCA if other soil components (e.g. humic material) liberate chloroform under the decarboxylation conditions. The aim of this work was to show that extraction and decarboxylation methods yield different TCA concentrations because the decarboxylation method can also determine "bound" TCA. Experiments with commercial humic acid solutions showed there was no additional chloroform formation under decarboxylation conditions, and that all TCA in a TCA-humic acid mixture could be quantitatively determined (108 +/- 13%). Anion exchange resin was used as a provider of solid-phase TCA binding; only 5 +/- 1% of a TCA solution mixed with the resin was present in the aqueous extract subsequently separated from the resin, yet the decarboxylation method yielded mass balance (123 +/- 22%) with TCA remaining in the resin. In aqueous extraction of a range of soil samples (with or without added TCA spike), the decarboxylation method was able to satisfactorily account for TCA in the extractant + residue post-extraction, compared with whole-soil TCA (+ spike) pre-extraction: e.g. mass balances for unspiked soil from Sikta spruce and larch forest were 99 +/- 8% and 93 +/- 6%, respectively, and for TCA-spiked forest and agricultural soils were 114 +/- 13% and 102 +/- 2%. In each case recovery of TCA in the extractant was substantially less than 100%(<20% for unspiked soils, <55% for spiked soils). Extraction efficiencies were generally lower in more organic soils. The results suggest that analytical methods which utilise aqueous extraction may underestimate whole-soil TCA concentrations. Application of both methodologies together may enhance insight into TCA behaviour in soil.     

Prediction of PAH biodegradation in field contaminated soils using a cyclodextrin extraction technique

Biodegradation has been identified as a major loss process for organic contaminants in soils and, as a result, microbial strategies have been developed for the remediation of contaminated land. Prediction of the biodegradable fraction would be important for determining bioremediation end-points in the clean-up of contaminated land. The aim of this study was to investigate the ability of a cyclodextrin extraction to predict the extent to which polycyclic aromatic hydrocarbons (PAHs) would be degraded microbiologically in field contaminated soils; further testing the robustness and reproducibility of this extraction in chemically complex systems. Dichloromethane and hydroxypropyl-beta-cyclodextrin (HPCD) extractable fractions were measured together with the PAH biodegradable fraction in each of the six field contaminated soils. The amounts of PAHs degraded by the catabolic activity of the indigenous microflora in each of the soils were correlated with HPCD-extractable PAH concentrations. The regressions showed that the amounts of lower molecular weight PAHs extracted by the HPCD were not significantly (P > 0.05) different to the amounts that were degraded. However, higher molecular weight PAHs that were extracted by HPCD did differ significantly (P < 0.05) from the amounts degraded. Although the HPCD extraction did overestimate the microbially degradable fraction of the higher molecular weight PAHs, overall the correlations between the HPCD extractable fraction and the microbially degradable fraction were very close, with mean values of the slope of line for the six soils equalling 1. This study further describes the robust and reproducible nature of the aqueous-based soil extraction technique reliably measuring the extent to which PAHs will be microbially degraded in soil.     

离子色谱法测定土壤中草甘膦的提取溶液选择

以辽宁棕壤等10种土壤为样品,探讨了水和p H值=9.00~14.00的氢氧化钠(Na OH)作为提取液对草甘膦分析的影响。结果表明,以水为提取液,仅石灰性紫色土和灰钙土能获得较高的回收率,其他所测土壤尤其是p H值<8.00的土壤其回收率较低,提取效果受土壤理化性质影响明显。以p H值=9.00~14.00的Na OH为提取液,随着提取液p H值的提高,所测土壤的回收率均随之提高,达到一定的p H值后,回收率随之提高不明显,但干扰会增多。当已知土壤相关理化性质时,可以参考回收率相关性分析选择合适的提取液。     

In situ phytoremediation of a soil historically contaminated by metals, hydrocarbons and polychlorobiphenyls

In the past several years, industrial and agricultural activities have led to serious environmental pollution, resulting in a large number of contaminated sites. As a result, much recent research activity has focused on the application of bioremediation technologies as an environmentally friendly and economically feasible means for decontamination of polluted soil. In this study horse manure and Populus nigra (var. italica) (HM + P treatment) have been used, at real scale level, as an approach for bioremediation of a soil historically contaminated by metals (Pb, Cr, Cd, Zn, Cu and Ni) and organic contaminants, such as polychlorobiphenyls and petroleum hydrocarbon. After one year, the HM + P phytotreatment was effective in the reclamation of the polluted soil from both organic and inorganic contaminants. A reduction of about 80% in total petroleum hydrocarbon (TPH), and 60% in polychlorobiphenyls (PCBs) and total metals was observed in the HM + P treatment. In contrast, in the horse manure (HM) treatment, used as control, a reduction of only about 30% of TPH was obtained. In order to assess both effectiveness and evolution of the remediation system to a biologically active soil ecosystem, together with the pollution parameters, the parameters describing the evolution of the soil functionality (enzymatic activities and protein SDS-PAGE pattern) were investigated. A stimulation of the metabolic soil processes (increase in dehydrogenase activity) was observed in the HM + P compared to the HM treatment. Finally, preliminary protein SDS-PAGE results have permitted the identification of proteins that have been recovered in the HM + P soil with respect to the HM; this may become a basic tool for improving the biogeochemical status of soil during the decontamination through the identification of microbial populations that are active in soil decontamination.     

Classification of alluvial soils according to their potential environmental risk: a case study for Belgian catchments

Alluvial soils may represent important sinks of contaminants as a result of the deposition of contaminated sediments along the river by overbank flooding or after dredging. Because of the erosion of alluvial deposits or the release of contaminants from sediments, alluvial soils can also be a source of contamination. In this paper, a risk assessment for contaminated (alluvial) soils is presented. The approach, mainly based on physico-chemical soil characteristics, single extractions and leaching tests, is illustrated by means of a case study from four Belgian catchments. The extractions and leaching tests that were used have been validated by European testing programs and can provide valuable information for classifying the potential environmental risks of soils. Irrespective of the location, pH, organic carbon content and 'mobilisable' metal concentrations were the most important factors explaining 'mobile' metal concentrations in the alluvial soils. Additionally, the data of the physico-chemical soil characterization, extractions and leaching tests were combined with local and regional factors to classify the alluvial soils in different categories according to their actual and potential risk for the environment.     

Ecotoxicity monitoring of hydrocarbon-contaminated soil using earthworm (Eisenia foetida)

In order to assess the applicability of an earthworm bioassayas a technique for monitoring the soil flushing process, short-term and long-term toxicity tests were conducted on remediatedsoil using various pore volumes of surfactant solution. Resultsobtained on short-term toxicity testing indicated that biomassincreased as the soil flushing proceeded, and on diesel-contaminated soils this testing showed that the effect of dieselis lethal and that 25 pore volumes of soil surfactant were notsufficient to abrogate the toxic effect of diesel. These short-term tests also showed strong sublethal relationships between the development of biomass, and the concentrations of toxic chemicals in the soil. Although relationships between contaminants and the various bioassay parameters examined werenot significant in long-term testing, an increase in the numberof juveniles was observed over time, which may have been a consequence of a reduction in toxicity associated with the flushing process.     

A small subsurface ion mobility spectrometer sensor for detecting environmental soil-gas contaminants

A small subsurface ion mobility spectrometer (SS-IMS) was constructed and tested with several environmental contaminants to determine its potential for monitoring gaseous volatile organic compounds in the vadose zone. Trichloroethylene (TCE) and tetrachloroethylene (PCE) were detected and separated in IMS for the first time. Detection limits as low as 1 part per billion volume-to-volume (ppb(v)) were observed. Reduced mobility (K(0)) values were reported for 11 environmental contaminants. These data demonstrated the potential of ion mobility spectrometry as a viable technology for detecting and separating environmental soil-gas contaminants in the field, which may lead to a practical and simple approach for long-term monitoring of contaminated soils.     

土壤中石油类有机污染物检测方法研究进展

在系统地归纳总结了国内外研究者所采用的各种分析方法基础上,指出了现有实验分析中存在的问题及发展趋势。主张尽量使用和开发仪器分析检测方法,并建议尽快规范土壤中石油类有机污染物的定性定量分析方法,尽早解决目前常用分析方法中存在的各种问题,为土壤石油污染防治提供有效保障。     

Assessment of cyclodextrin-enhanced extraction of crude oil from contaminated porous media

The purpose of this study was to evaluate the effects of cyclodextrin (CD) on the extraction of Macondo well oil from contaminated porous media over a range of hydroxypropyl-β-CD (HPβCD) concentrations. To our knowledge, this is the first dataset on this type of CD yet assembled for an actual crude oil. The results showed that HPβCD can significantly increase oil extraction efficiency, demonstrated by increasing concentrations of all tested normal alkanes (nC(15)-nC(35)) and polyaromatic hydrocarbons (PAHs) in the aqueous phase with increasing CD concentration. A linear relationship between the extraction enhancement effect and CD concentration were verified experimentally and high correlation coefficients for total PAHs (R(2) = 0.82) and alkanes (R(2) = 0.99) were determined. For a 20% CD solution, 3.13 wt% of alkanes and 32.12 wt% of total PAHs were extracted to the aqueous phase, which was significantly more than what was extracted with water only (0.04% and 0.21% for alkanes and PAHs, respectively). This result shows that the remediation of oil contaminated media can be significantly enhanced through the use of HPβCD solutions in flushing or pump and treat operations to remove sorbed oil. The CD extraction enhancement effect decreases with increasing n-alkane chain length for the carbon number range tested. CD significantly enhanced PAH extraction from sand and the enhancement effect increased in the order of parent compounds < C-1 substituted < C-2 substituted < C-3 substituted for most PAHs tested. This study provides important information to assess the feasibility of using CD as a near-shore agent to enhance the cleanup of oil contaminated porous media.     

Genotoxicity assessment of soils from wastewater irrigation areas and bioremediation sites using the Vicia faba root tip micronucleus assay

Genotoxicity potential of soils taken from wastewater irrigation areas and bioremediation sites was assessed using the Vicia faba root tip micronucleus assay. Twenty five soils were tested, of which 8 were uncontaminated soils and taken as the control to examine the influence of soil properties; 6 soils were obtained from paddy rice fields with a history of long-term wastewater irrigation; 6 soils were obtained from bioremediation sites to examine effects of bioremediation; and 5 PAH-contaminated soils were used to examine methodological effects between direct soil exposure and exposure to aqueous soil extracts on micronuclei (MN) frequency ( per thousand) in the V. faba root tips. Results indicate that soil properties had no significant influences on MN frequencies (p > 0.05) when soil pH varied between 3.4 to 7.6 and organic carbon between 0.4% and 18.6%. The MN frequency measured in these control soils ranged from 1.6 per thousand to 5.8 per thousand. MN frequencies in soils from wastewater irrigation areas showed 2- to 48-fold increase as compared with the control. Soils from bioremediation sites showed a mixed picture: MN frequencies in some soils decreased after bioremediation, possibly due to detoxification; whereas in other cases remediated soils induced higher MN frequencies, suggesting that genotoxic substances might be produced during bioremediation. Exposure to aqueous soil extracts gave a higher MN frequency than direct exposure in 3 soils. However, the opposite was observed in the other two soils, suggesting that both exposure routes should be tested in case of negative results from one route. Data obtained from this study indicate that the MN assay is a sensitive assay suitable for evaluating genotoxicity of soils.     

A novel passive water sampler for in situ sampling of antibiotics

Passive water sampling has several advantages over active methods; it provides time-integrated data, can save on time and cost compared to active methods, and yield high spatial resolution data through co-deployment of simple, cheap units. However, one problem with many sampler designs in current use is that their uptake rates for trace substances of interest are flow-rate dependent, thereby requiring calibration data and other information to enable water concentrations to be derived from the mass per sampler. However, the 'family' of samplers employing the principle of diffusive gradients in thin films (DGT) provides an in situ means of quantitatively measuring labile species in aquatic systems without field calibration. So far, this technique has only been tested and applied in inorganic substances: metals, radionuclides, nutrients, etc. Design and applications of DGT to trace organic contaminants ('o-DGT') would be of widespread interest. This study describes the laboratory testing and performance characteristics of o-DGT, with the antibiotic sulfamethoxazole (SMX) as a model compound and XAD18 as the novel binding agent. o-DGT uptake of SMX increased with time and decreased with diffusion layer thickness, confirming the principle for SMX. XAD18 showed sufficiently high capacity for SMX for routine field applications. o-DGT measurement of SMX was independent of pH (6-9) and ionic strength (0.001-0.1 M) and not affected by flow rate once above static conditions. The diffusion coefficient of SMX in the sampler was measured using an independent diffusion cell and information is presented to allow temperature correction and derivation of aqueous concentrations from deployed samplers. The potential use of o-DGT for in situ measurement of pharmaceutical antibiotics is confirmed by this study and applications are briefly discussed.     

Organic and inorganic diffuse contamination in urban soils: the case of Torino (Italy)

Soils in urban parks are useful tracers of diffuse contamination and could represent a potential health risk for citizens. Soils in the parks of Torino, Italy, were sampled and analysed for a broad range of organic and inorganic contaminants. Concentrations of potentially toxic elements, PAHs, PCBs and polychlorinated dibenzo-p-dioxins and dibenzofurans were often above national legislation limits, and higher than surrounding rural areas or than other cities. Mean concentrations were 233 mg kg(-1) for Cr, 164 mg kg(-1) for Ni, 124 mg kg(-1) for Pb and 170 mg kg(-1) for Zn. Other inorganic contaminants such as Cd, As, and Hg showed high concentrations in some soils. Organic contaminants were also found to be enriched in the sampled parks (e.g. maximum concentrations of PCDDs/DFs and PCBs were 12.6 ng kg(-1) and 0.310 mg kg(-1), respectively). Data from this study reveal an important enrichment of parks for some contaminants, reflecting the intensity of phenomena of diffuse contamination. Historical parks presented the highest degree of contamination, suggesting that the age of soils rather than their proximity to sources of emissions is a key factor in determining soil contamination. Data obtained in this study could be of help in the investigation and remediation practices of urban contaminated sites within large cities.     

Kinetic of Biomarker Responses in Juveniles of the Fish Sparus aurata Exposed to Contaminated Sediments

Sediments in the National Park of the Atlantic Islands (Galicia, Spain) were affected by the spill of the tanker Prestige (November, 2002) and still present high levels of Polycyclic aromatic hydrocarbons. The adverse effects associated with the contaminants in sediments were tested using a chronic bioassay, exposing juveniles of the fish Sparus aurata (seabream). A toxicokinetic approach is proposed to evaluate sediment quality by linking chemical and ecotoxicological data along the time. Sediment samples were physicochemically characterized and the concentration of contaminants (Polycyclic aromatic hydrocarbons – PAHs – and metals) was measured. Fishes were exposed to contaminated sediments, and samples from different tissues were collected every 15 days throughout the 60 days that lasted the experiment. A biomarker of exposure (ethoxyresorufin O-deethylase activity – EROD activity) and a biomarker of effect (histopathology) were analyzed during the exposure period. Results show a relationship between the biomarkers and the concentrations in sediments of polycyclic aromatic hydrocarbons—PAHs. Besides, the toxicokinetic approach links biomarkers response providing information about the relationship between the detoxification process and the damages observed in the different tissues. The frequency of the histological damage is highest when the EROD activity slightly decreases in accordance with the mechanism of detoxification of this enzymatic system against PAHs and other organic contaminants.     

Method for the determination of sub-ppm concentrations of perfluoroalkylsulfonate anions in water

The determination of sub-ppm concentrations of aqueous perfluoroalkylsulfonate (PFSt) anions, including perfluorooctylsulfonate (PFOS), has been accomplished with a relatively simple mass spectrometric procedure that does not require extraction of the analytes into an organic solvent or a chromatographic separation prior to injection into the negative-ion electrospray ionization mass spectrometer. Sample pretreatment was minimized and consisted of dilution of the aqueous samples of groundwater, surface water, tap water, and distilled water with acetonitrile, addition of dodecylsulfate (DDS) as an internal standard, and, in some cases, addition of known amounts of perfluorobutylsulfonate (PFBS) or PFOS for standard-addition experiments. The linear-response range for PFOS is 25.0 microg L(-1) to 2.5 mg L(-1). The lower limit of this range is three orders of magnitude lower than an equally straightforward chromatographic method. The relative errors for standard aqueous solutions containing only 25.0 microg L(-1) and 2.5 mg L(-1) PFOS are +/- 14% and +/- 7%, respectively, with 133 microg L(-1) DDS as the internal standard. The detection limit and quantification limit for PFOS in these standards are 5.0 microg L(-1) and 25.0 microg L(-1), respectively. Six different PFS anions, containing three to eight carbon atoms, were identified and quantified in an aqueous film-forming foam (AFFF) formulation using the method of standard additions. Two alkylsulfate anions and two perfluoroalkylcarboxylate anions were also identified in the AFFF formulation.