Empore Disks Research Articles

Analysis of drug of abuse compounds using passive sampling and ultrahigh-liquid chromatography coupled to mass spectrometry

The present study proposes the monitoring of compounds of drugs of abuse through the use of passive samplers in water systems. Initially, four positive ion compounds of interest were determined according to national surveys, and then composite sampling and passive sampling were implemented using continuous-flow passive samplers containing two types of sorbents, the Empore disk and Gerstel Twister. Two study sites were established at the beginning and at the end of the middle Bogotá River basin. After 4 days, the sorbents were removed so that they could be desorbed and analyzed using UHPLC–MS in the laboratory. For the composite samples, the results were below the first calibration curve point (FCCP) of the chromatographic method, and for passive sampling, peaks of benzoylecgonine (BE) (21427.3 pg mL−1), methamphetamine (MET) (67101.5 pg mL−1), MDMA (ecstasy) (225844.8 pg mL−1) and 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) (15908.4 pg mL−1) were found. Therefore, passive sampling could be suggested as an alternative to composite sampling for the monitoring of compounds.

In situ calibration of three passive samplers for the monitoring of steroid hormones in wastewater

In situ extraction of steroid hormones from waste water using adsorption-based integrative passive samplers represents a promising approach for their monitoring in water at ultra-trace concentrations. Three passive samplers, namely a POCIS, a Chemcatcher fitted with an Empore SDB-RPS disk, and an Empore SDB-RPS disk-based sampler with enhanced water flow, were calibrated in situ in treated municipal wastewater for the purpose of monitoring five estrogens (17-β-estradiol, 17-α-estradiol, 17-α-ethinylestradiol, estrone and estriol) at sub ng per litre concentrations. Uptake of steroids to samplers during 14-day exposure in wastewater was compared with steroid concentrations in daily collected composite water samples. Sampling rates were obtained from a numerical solution of first order uptake kinetics equations describing the uptake of compounds into a passive sampler over time. Mass transfer of steroids in the Chemcatcher fitted with naked Empore disks was more than two times faster than in the POCIS sampler. The uptake capacity of the applied Empore disk was not sufficient for integrative uptake of all tested steroids during the entire 14-day exposure. Time-weighted average concentrations of steroids estimated at concentrations in units of ngL−1 using the in situ-calibrated samplers were within a factor of two from values obtained using composite water samples.

Limited reversibility of bioconcentration of hydrophobic organic chemicals in phytoplankton.

Aging, reversibility, and desorption rates for the binding of hydrophobic chemicals (HOC) to phytoplankton cells have not been directly measured. Here the effect of bioconcentration time on subsequent desorption of hexachlorobenzene (HCB) and polychlorinated biphenyls (PCBs) was studied for the alga Monoraphidium minutum. Cell suspensions were exposed to HCB and PCBs spanning a range of log Kow values of 5.7 to 8.2, for 0.13 to 14 d. Subsequently, reversibility and desorption rates were assessed by extracting the chemicals from the cells using infinite sink extractions with Tenax beads or Empore disks employed in the cell suspension. Uptake was biphasic with constant relative contributions of fast surface sorption. Desorption was biphasic too and well fitted to a first order two compartment model. Increasing exposure times resulted in increasing slowly desorbing chemical fractions and decreased desorption rates from these fractions. For the most hydrophobic PCBs, slowly desorbing fractions were >80–90%, whereas desorption half-lives from these fractions ranged up to 120 days. The slow desorption rates directly prove that bioconcentration to algae can be rate limited and imply that already after a few hours of exposure, HOCs may become practically unavailable for repartitioning.

A SILAC-based Approach Identifies Substrates of Caspase-dependent Cleavage upon TRAIL-induced Apoptosis

The extracellular ligand-induced extrinsic pathway of apoptosis is executed via caspase protease cascades that activate downstream effectors by means of site-directed proteolysis. Here we identify proteome changes upon the induction of apoptosis by the cytokine tumor necrosis factor–related apoptosis-inducing ligand (TRAIL) in a Jurkat T cell line. We detected caspase-dependent cleavage substrates by quantifying protein intensities before and after TRAIL induction in SDS gel slices. Apoptotic protein cleavage events are identified by a characteristic stable isotope labeling with amino acids in cell culture (SILAC) ratio pattern across gel slices that results from differential migration of the cleaved and uncleaved proteins. We applied a statistical test to define apoptotic substrates in the proteome. Our approach identified more than 650 of these cleaved proteins in response to TRAIL-induced apoptosis, including many previously unknown substrates and cleavage sites. Inhibitor treatment combined with triple SILAC demonstrated that the detected cleavage events were caspase dependent. Proteins located in the lumina of organelles such as mitochondria and endoplasmic reticulum were significantly underrepresented in the substrate population. Interestingly, caspase cleavage is generally observed in not only one but several members of stable complexes, but often with lower stoichiometry. For instance, all five proteins of the condensin I complex were cleaved upon TRAIL treatment. The apoptotic substrate proteome data can be accessed and visualized in the MaxQB database and might prove useful for basic and clinical research into TRAIL-induced apoptosis. The technology described here is extensible to a wide range of other proteolytic cleavage events.

Determination of Selected Nitropolycyclic Aromatic Hydrocarbons in Water Samples

A new method for the analysis of selected nitropolycyclic aromatic hydrocarbons (NPAHs) at ultra-trace levels in water samples is proposed. Particulate NPAHs were collected on a GC glass fiber filter. Soluble NPAHs were collected on a C18 Empore disk. After simple clean-up and concentration of NPAHs in both phases, the NPAHs were analyzed using HPLC equipped with clean-up, reducer, concentration and chemiluminescence detection units. The proposed method showed good linear calibration curves with correlation coefficients (r(2)) ranging from 0.9954 to 0.9998. The limits of detection ranged from 0.013 to 0.15 nmol/L (soluble NPAHs) and from 0.01 to 0.13 nmol/L (particulate NPAHs) for 5 NPAHs [(9-nitroanthracene, 1-nitropyrene, 6-nitrochrysene (6-NC), 7-nitrobenz[a]anthracene and 6-nitrobenzo[a]pyrene] having 3 to 5 rings analyzed, when 1.5 L of water sample was used. The repeatability for soluble NPAHs ranged between 4.2 and 6.8% (n=5), while for particulate NPAHs, it varied between 2.2 and 2.8% (n=5). The proposed method successfully determined the above NPAHs expect 6-NC in river water samples, suggesting that this method is suitable for the ultra-trace analysis of NPAHs in water samples.

Development of a Passive Sampler for Monitoring of Carbamate and s-Triazine Pesticides in Surface Waters

A new sampling system has been developed for the measurement of time-averaged concentrations (TWA) and diffusion coefficients of organic micropollutants in aquatic environments. The system is based on the diffusion of targeted organic compounds through a rate-limiting membrane and the subsequent accumulation of these species in a bound, hydrophobic solid-phase material. Two separate prototype systems are described. One is suitable for the sampling of carbamates such as carbaryl, carbofuran, 3-hydroxycarbofuran, baygon, propham, clorpropham, and the other one for s-triazines such as atrazine, prometryn, propazine, simazine, terbuthylazine, terbutryn, metribuzin, cyanazine, and metamitron pesticides. The systems use solid-phase material (47-mm C18 Empore disk) as the receiving phase but are fitted with rate-limiting membranes of either polysulfone or polycarbonate. For the two designs investigated, the cumulative uptake of all target analytes was considered over exposure periods of 7 days. The determined sampling rates ranged from 0.1323 to 0.0465 L day−1 with both membranes. The best system was the one with the polysulfone membrane allowing a better cumulative uptake.

Evaluation of Contaminant Removal of Reverse Osmosis and Advanced Oxidation in Full-Scale Operation by Combining Passive Sampling with Chemical Analysis and Bioanalytical Tools

Advanced water treatment of secondary treated effluent requires stringent quality control to achieve a water quality suitable for augmenting drinking water supplies. The removal of micropollutants such as pesticides, industrial chemicals, endocrine disrupting chemicals (EDC), pharmaceuticals, and personal care products (PPCP) is paramount. As the concentrations of individual contaminants are typically low, frequent analytical screening is both laborious and costly. We propose and validate an approach for continuous monitoring by applying passive sampling with Empore disks in vessels that were designed to slow down the water flow, and thus uptake kinetics, and ensure that the uptake is only marginally dependent on the chemicals' physicochemical properties over a relatively narrow molecular size range. This design not only assured integrative sampling over 27 days for a broad range of chemicals but also permitted the use of a suite of bioanalytical tools as sum parameters, representative of mixtures of chemicals with a common mode of toxic action. Bioassays proved to be more sensitive than chemical analysis to assess the removal of organic micropollutants by reverse osmosis, followed by UV/H₂O₂ treatment, as many individual compounds fell below the quantification limit of chemical analysis, yet still contributed to the observed mixture toxicity. Nonetheless in several cases, the responses in the bioassays were also below their quantification limits and therefore only three bioassays were evaluated here, representing nonspecific toxicity and two specific end points for estrogenicity and photosynthesis inhibition. Chemical analytical techniques were able to quantify 32 pesticides, 62 PCPPs, and 12 EDCs in reverse osmosis concentrate. However, these chemicals could explain only 1% of the nonspecific toxicity in the Microtox assay in the reverse osmosis concentrate and 0.0025% in the treated water. Likewise only 1% of the estrogenic effect in the E-SCREEN could be explained by the quantified EDCs after reverse osmosis. In comparison, >50% of the estrogenic effect can typically be explained in sewage. Herbicidal activity could be fully explained by chemical analysis as the sampling period coincided with an illegal discharge and two herbicides dominated the mixture effect. The mass balance of the reverse osmosis process matched theoretical expectations for both chemical analysis and bioanalytical tools. Overall the investigated treatment train removed >97% estrogenicity, >99% herbicidal activity, and >96% baseline toxicity, confirming the suitability of the treatment train for polishing water for indirect potable reuse. The product water was indistinguishable from local tap water in all three bioassays. This study demonstrates the suitability and robustness of passive sampling linked with bioanalytical tools for semicontinuous monitoring of advanced water treatment with respect to micropollutant removal.

Identification of miR-193b Targets in Breast Cancer Cells and Systems Biological Analysis of Their Functional Impact

Identification of protein targets for microRNAs (miRNAs) is a significant challenge due to the complexity of miRNA-mediated regulation. We have previously demonstrated that miR-193b targets estrogen receptor-α (ERα) and inhibits estrogen-induced growth of breast cancer cells. Here, we applied a high-throughput strategy using quantitative iTRAQ (isobaric tag for relative and absolute quantitation) reagents to identify other target proteins regulated by miR-193b in breast cancer cells. iTRAQ analysis of pre-miR-193b transfected MCF-7 cells resulted in identification of 743 unique proteins, of which 39 were down-regulated and 44 up-regulated as compared with negative control transfected cells. Computationally predicted targets of miR-193b were highly enriched (sevenfold) among the proteins whose level of expression decreased after miR-193b transfection. Only a minority of these (13%) showed similar effect at the mRNA level illustrating the importance of post-transcriptional regulation. The most significantly repressed proteins were selected for validation experiments. These data confirmed 14-3-3ζ (YWHAZ), serine hydroxyl transferase (SHMT2), and aldo-keto reductase family 1, member C2 (AKR1C2) as direct, previously uncharacterized, targets of miR-193b. Functional RNAi assays demonstrated that specific combinations of knockdowns of these target genes by siRNAs inhibited growth of MCF-7 cells, mimicking the effects of the miR-193b overexpression. Interestingly, the data imply that besides targeting ERα, the miR-193b effects include suppression of the local production of estrogens and other steroid hormones mediated by the AKR1C2 gene, thus provoking two separate molecular mechanisms inhibiting steroid-dependent growth of breast cancer cells. In conclusion, we present here a proteomic screen to identify targets of miR-193b, and a systems biological approach to mimic its effects at the level of cellular phenotypes. This led to the identification of multiple genes whose combinatorial knock-down likely mediates the strong anti-cancer effects observed for miR-193b in breast cancer cells.

Determination of deployment specific chemical uptake rates for SDB-RPD Empore disk using a passive flow monitor (PFM)

The use of the adsorbent styrenedivinylbenzene-reverse phase sulfonated (SDB-RPD) Empore disk in a chemcatcher type passive sampler is routinely applied in Australia when monitoring herbicides in aquatic environments. One key challenge in the use of passive samplers is mitigating the potentially confounding effects of varying flow conditions on chemical uptake by the passive sampler. Performance reference compounds (PRCs) may be applied to correct sampling rates ( R s ) for site specific changed in flow and temperature however evidence suggests the use of PRCs is unreliable when applied to adsorbent passive samplers. The use of the passive flow monitor (PFM) has been introduced for the assessment of site-specific changes in water flow. In the presented study we have demonstrated that the R s at which both atrazine and prometryn are accumulated within the SDB-RPD-Empore disk is dependent on the flow conditions. Further, the calibration of the measured R s for chemical uptake by the SDB-RPD-Empore disk to the mass lost from the PFM has shown that the PFM provides an accurate measure of R s for flow velocities from 0 to 16 cm s −1. Notably, for flow rates >16 cm s −1, a non linear increase in the R s of both herbicides was observed which indicates that the key resistance to uptake into the SDB-RPD Empore disk is associated with the diffusion through the overlying diffusion limiting membrane. Overall the greatest uncertainty remains at very low flow conditions, which are unlikely to often occur in surface waters. Validation of the PFM use has also been undertaken in a limited field study.

Estimation of In Situ Sediment-to-Water Fluxes of Polycyclic Aromatic Hydrocarbons, Polychlorobiphenyls and Polybrominated Diphenylethers

Sediment-water fluxes of hydrophobic organic chemicals (HOC) may affect the quality of surface waters. Here, we present an approach to derive such fluxes from (a) in situ HOC concentration gradients measured with passive samplers and (b) mass transfer coefficients measured with a novel flux method using Empore disks. For eight undisturbed sediments, this method identified whether the sediment acted as a source or as a sink for HOCs. The analysis also identified which type of transport resistance governed sediment water exchange. For seven inland locations, exchange was limited by benthic boundary layer transport, showing no dependencies on sediment or chemical properties other than concentration. For one river mouth location, exchange was limited by slow in-bed intraparticle diffusion. A biphasic dual compartment radial diffusion model adequately described the data for this location. Fast desorption was interpreted as molecular diffusion retarded by microscale dual domain sorption to amorphous as well as black carbon (BC). Slow desorption was invariant with LogK(ow) and consistent with intraorganic matter diffusion through BC particles. Finally, it is discussed how these findings can be translated into a general framework for flux based exposure assessment.

Event monitoring of herbicides with naked and membrane-covered Empore disk integrative passive sampling devices

Subsequent to an initial wet season flood event in the Brisbane River, Australia, both fast (naked disk) and slow (membrane-covered) variants of SDB–RPS Empore disk passive sampling devices were deployed with an automated grab sampling program. A trend increase in the aquatic dissolved concentrations of diuron and simazine was observed over a 10-day period. Kinetic and equilibrium parameters for each sampler were calculated based on the dynamic concentration. Absolute percent difference for duplicate passive samples was <10% in the fast and <25% in the slow samplers. For kinetic sampling, significantly shortened integrative periods are available with the fast compared with the slow variant, with higher sampling rates offering improved detection limits. The study demonstrates a method for determining kinetic parameters of passive samplers in a variable concentration field deployment, and illustrates the differences in quality between active and passive data, in terms of capturing changes in concentration associated with rainfall events.

Time Integrative Passive Sampling: How Well Do Chemcatchers Integrate Fluctuating Pollutant Concentrations?

Many environments are subject to periodic fluctuations in pollutant concentrations. Passive samplers, which can provide time weighted average concentrations integrated over the period of deployment, are ideally suited as monitoring tools for these environments. However, the potential for fluctuating concentrations to limit the integrative period of sampling needs to be investigated before sampling data from these environments can be interpreted with confidence. In this study, Chemcatchers using SDB-RPS Empore disks as the sorbent phase were exposed to herbicides for 28 days in a calibration chamber. A pulsed event of 10-fold greater concentrations was introduced on day 5 and returned to background concentrations over a period of 3 days. Observed uptake was compared with that predicted by a first order uptake model and by the reduced form of this model describing a strictly integrative response for samplers deployed with two surfaces exposed (two-sided naked), with one surface exposed (one-sided naked) and with a polyethersulfone membrane. Membrane covered samplers predicted time weighted average water concentrations within a factor 0.7-1.2 after 28 days exposure, while one- and two-sided naked samplers under predicted the average by a factor 1.9-2.2 and 2.4-3.2, respectively. First order modeling predicted uptake in membrane covered and one-sided naked samplers and was therefore applied to predict sampler response to several fluctuating concentration event scenarios.

One-Step Procedure for Peptide Extraction from In-Gel Digestion Sample for Mass Spectrometric Analysis

Protein identification from samples resolved by one-dimensional and two-dimensional gel electrophoresis is highly dependent on the recovery of trypsin-digested peptides prior to mass spectrometric analysis. The commonly used two-step protocol for extracting tryptic peptides, involving high-volume organic solvent extraction and cleanup via microscale reversed-phase micropipet tip or microcolumn is not only limited by significant sample loss but is also costly and very labor-intensive. We report here a simple one-step procedure for simultaneous peptide extraction and cleanup by incubating a small piece of C18 Empore Disk (3M) with the in-gel digested solution. We show that the direct Empore Disk-based peptide extraction procedure is convenient, economical, and has higher efficiency as compared with the commonly used two-step protocol for peptide preparation prior to MS analysis.

Aquatic passive sampling of a short-term thiacloprid pulse with the Chemcatcher: Impact of biofouling and use of a diffusion-limiting membrane on the sampling rate

We examined the performance of the Chemcatcher (University Portsmouth, UK) in two different configurations when used for the aquatic passive sampling of a 1-day pulse contamination with thiacloprid under field-relevant conditions. The configuration without diffusion-limiting membrane led to biofouling of the Empore disk receiving phase resulting in a fourfold reduction in analyte uptake compared to unfouled passive samplers. The sampling rate for the configuration with diffusion-limiting polyethersulfone membrane was also much lower than in a long-term exposure scenario, although no biofouling occurred. Both configurations of the Chemcatcher exhibited high variation in analyte uptake with up to 100% RSD. Short-term contamination events may be underestimated in passive sampling when the receiving phase is biofouled or a diffusion-limiting membrane is employed.

Calibration of the Chemcatcher® passive sampler for monitoring selected polar and semi-polar pesticides in surface water

Passive sampling is a powerful method for continuous pollution monitoring, but calibration experiments are still needed to generate sampling rates in order to estimate water concentrations for polar compounds. We calibrated the Chemcatcher device with an uncovered SDB-XC Empore disk as receiving phase for 12 polar and semi-polar pesticides in aquatic environments in flow-through tank experiments at two water flow velocities (0.135 m/s and 0.4 m/s). In the 14-day period of exposure the uptake of test substances in the sampler remained linear, and all derived sampling rates R(s) were in the range of 0.1 to 0.5 L/day. By additionally monitoring the release of two preloaded polar pesticides from the SDB-XC disks over time, very high variation in release kinetics was found, which calls into question the applicability of performance reference compounds. Our study expands the applicability of the Chemcatcher for monitoring trace concentrations of pesticides with frequent occurrence in water.

Salicylic acid and derivatives anchored on poly(styrene- co-divinylbenzene) resin and membrane via a diazo bridge: Synthesis, characterisation and application to metal extraction

New materials for chelating solid-phase extraction have been prepared by grafting of salicylic acid and derivatives on poly(styrene- co-divinylbenzene) based sorbents. These sorbents are either resin bead-shaped Amberlite ® XAD-4 or membrane disk-shaped Empore™ SDB-XC. Grafting has been achieved via –N N– spacer. The grafted ligands are salicylic acid (SA), its dimer form methylenedisalicylic acid (MDSA) and trimer form aurintricarboxylic form (ATA) in order to study the influence of multi-functionalization on chelating properties. Grafting scheme was validated on a model molecule (4-ethylaniline) for optimisation of experimental conditions. The resulting sorbents have been characterised by FTIR, Py-GC/MS analysis and 13 C CP-MAS NMR. Grafting rates are higher for SA (25–38%) than for MDSA (16–17%) and ATA (9%), still the number of SA entities remains almost constant. Metallic sorption abilities of the two new sorbents – determined by ICP-AES – have been succcessfully assessed by means of flow-through experiments with synthetic solution of multielement cations (Cd 2+, Co 2+, Cu 2+, Mn 2+, Ni 2+, Pb 2+, Zn 2+, Fe 2+ and Al 3+). It evidenced the influence of the PTFE matrix, contained in Empore disks, for acidic pH. Finally, complexing capacities for Fe(III) were found to be higher for membranes (13.4 ± 0.7 for SA) than for resins (11.6 ± 0.6): this allows to consider grafted polymer membranes as competitive materials for SPE applications.

Calibration of a passive sampling device for time‐integrated sampling of hydrophilic herbicides in aquatic environments

Two types of solid-phase materials, a styrenedivinylbenzene copolymer sorbent (embedded in a SDB-XC Empore disk) and a styrenedivinylbenzene copolymer sorbent modified with sulfonic acid functional groups (embedded in a SDB-RPS Empore disk), were compared as a receiving phase in a passive sampling device for monitoring polar pesticides. The SDB-XC Empore disk was selected for further evaluation, overlayed with either a polysulfone or a polyethersulfone diffusion membrane. The target herbicides included five nonionized herbicides (simazine, atrazine, diuron, clomazone, and metolachlor) and four phenoxy acid herbicides (dicamba, (2,4-dichlorophenoxy)acetic acid [2,4-D], (4-chloro-2-methylphenoxy)acetic acid [MCPA], and triclopyr) with log octanol/water partition coefficient (log K(OW)) values of less than three in water. Uptake of these herbicides generally was higher into a device constructed of a SDB-XC Empore disk as a receiving phase covered with a polyethersulfone membrane compared to a similar device covered with a polysulfone membrane. Using the device with a SDB-XC Empore disk covered with a polyethersulfone membrane, linear uptake of simazine, atrazine, diuron, clomazone, and metolachlor was observed for up to 21 d, and daily sampling rates of the herbicides from water in a laboratory flow-through system were determined. The uptake rate of each nonionized herbicide by the Empore disk-based passive sampler was linearly proportional to its concentration in the water, and the sampling rate was independent of the water concentrations over the 21-d period. Uptake of the phenoxy acid herbicides (2,4-D, MCPA, and triclopyr) obeyed first-order kinetics and rapidly reached equilibrium in the passive sampler after approximately 12 d of exposure. The Empore disk-based passive sampler displayed isotropic kinetics, with a release half-life for triclopyr of approximately 6 d.

Preparation of trioctylamine-impregnated polystyrene–divinylbenzene porous resins for the collection of precious metals from water

A water-insoluble extracting solvent, trioctylamine (TOA), was solubilized in the aqueous micellar solution of a polyoxyethylene-type nonionic surfactant, polyethyleneglycol (10)-mono-4-nonylphenyl ether (PONPE-10). By mixing the solution and a polystyrene–divinylbenzene porous resin (Amberlite XAD-4), TOA was successfully impregnated into the resin. Gold(III), platinum(II), and palladium(II) were well extracted from hydrochloric acid to the TOA-impregnated resins. The extents of the extraction of platinum(II) and palladium(II) increased with increasing the amount of TOA impregnated. The TOA-impregnated filter disk was also prepared by passing aqueous mixture of PONPE-10 and TOA through an Empore disk involving polystyrene–divinylbenzene. The disk was useful for concentrating precious metals in water prior to their graphite furnace atomic absorption spectrometric analysis.

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.

Stability of Pesticides on Solid-Phase Extraction Disks After Incubation at Various Temperatures and for Various Time Intervals: Interlaboratory Study

An interlaboratory study was conducted at 8 locations to assess the stability of pesticides on solid-phase extraction (SPE) disks after incubation at various temperatures and for various time intervals. Deionized water fortified with selected pesticides was extracted by using 2 types of SPE filtration disks (Empore C18 and Speedisk C18XF), and after extraction, the disks were incubated at 3 temperatures (25, 40, and 55 degrees C) and for 2 time intervals (4 and 14 days). Deionized water was fortified with atrazine, carbofuran, and chlorpyrifos by all participating laboratories. In addition, some of the laboratories included 2 of the following pesticides: metolachlor, metribuzin, simazine, chlorothalonil, and malathion. Concurrently, fortified water samples were extracted with the incubated samples by using each disk type at 4 and 14 days. Pesticides had equivalent or greater stability on > or = 1 of the C18 disk types, compared with storage in water. The lowest recoveries of carbofuran (6%) and chlorpyrifos (7%) were obtained at 55 degrees C after storage for 14 days in incubated water. At 55 degrees C after 14 days, the lowest recovery for atrazine was 65% obtained by using Empore disks. Pesticide-specific losses occurred on the C18 disks in this study, underlining the importance of temperature and time interval when water is extracted at remote field locations and the SPE disks containing the extracted pesticides are transported or shipped to a laboratory for elution and analysis.