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PubMed2002

Insecticide resistance in field populations of Frankliniella occidentalis (Pergande) in Murcia (south-east Spain).

Thirty-nine field populations of Frankliniella occidentalis (Pergande) were collected from different crops (sweet pepper, tomato, lettuce, artichoke, melon, cucumber, carnation, broad bean, peach and plum) in Murcia (south-east Spain). All populations were reared separately in the laboratory to obtain enough individuals for bioassays. Female thrips were bioassayed, using a standard topical application method, against methiocarb, methamidophos, acrinathrin, endosulfan, deltamethrin and formetanate. Methiocarb was the only insecticide that showed a high efficacy against F occidentalis at field dose rates. Acrinathrin and methamidophos were moderately effective, while endosulfan and deltamethrin were ineffective. Only moderate levels of resistance (Resistance Ratios at LC50 of 10-30) were detected for the selective insecticides methiocarb, formetanate and acrinathrin used against F occidentalis in crops where these insecticides are used intensively. This generalized and low level of resistance to these insecticides, coupled with a lack of efficacy for the three broad-spectrum insecticides, was observed even in intensively managed vegetable crops. Implementation of IPM strategies in Murcia has contributed to more successful insecticide anti-resistance management.

Animals↗
PubMed2004

In vitro sulfoxidation of thioether compounds by human cytochrome P450 and flavin-containing monooxygenase isoforms with particular reference to the CYP2C subfamily.

Cytochrome P450 (P450) and flavin-containing monooxygenase (FMO) enzymes are major catalysts involved in the metabolism of xenobiotics. The sulfoxidation of the thioether pesticides, phorate, disulfoton, sulprofos, and methiocarb, was investigated. Using pooled human liver microsomes (HLMs), thioether compounds displayed similar affinities; however, phorate and disulfoton displayed higher intrinsic clearance rates than either sulprofos or methiocarb. The sulfoxidation of thioethers by HLMs was found to be predominantly P450-driven (85-90%) compared with FMO (10-15%). Among 16 cDNA-expressed human P450 isoforms and 3 human FMO isoforms examined, the following isoforms and their polymorphisms had the highest rates for sulfoxidation, as follows: phorate, CYP1A2, 3A4, 2B6, 2C9*1, 2C18, 2C19, 2D6*1, and FMO1; disulfoton, CYP1A2, 3A4, 2B6, 2C9*1, 2C9*2, 2C18, 2C19, 2D6*1, and FMO1; sulprofos, CYP1A1, 1A2, 3A4, 2C9*1, 2C9*2, 2C9*3, 2C18, 2C19, 2D6*1, and FMO1; methiocarb, CYP1A1, 1A2, 3A4, 2B6, 2C9*1, 2C19, 2D6*1, and FMO1. Among these isoforms, members of the CYP2C subfamily often had the highest affinities and clearance rates. Moreover, sulfaphenazole, a CYP2C9 competitive inhibitor, inhibited disulfoton sulfoxidation by CYP2C9 (IC50 0.84 microM) as well as in HLMs. Ticlopidine, a CYP2C19 mechanism-based inhibitor, inhibited disulfoton sulfoxidation by CYP2C19 (IC50 after coincubation, 43.5 microM; IC50 after preincubation, 4.3 microM) and also in HLMs. Our results indicate that current models of the substrate binding site of the CYP2C subfamily would not effectively predict thioether pesticide metabolism. Thus, the substrate specificity of CYP2Cs is more extensive than is currently believed, and some reevaluation of structure-activity relationships may be required.

Aryl Hydrocarbon Hydroxylases↗
PubMed1989

Factors influencing discrimination between insecticide-treated and untreated foods by northern bobwhite.

Tests were conducted to determine at what dietary concentrations northern bobwhite (Colinus virginianus) chicks (14 days old) could discriminate between pesticide-treated and untreated food using an organophosphate (OP) insecticide, parathion, and two carbamates, carbofuran and methiocarb. Results from subacute dietary LC50 tests (one feeder of treated food per cage) were compared to tests where birds were presented with two feeders (one treated and one untreated, 1:1) or 10 feeders (five treated and five untreated, 5:5; or nine treated and one untreated, 9:1). The dietary concentration above which birds discriminate between feeders by consuming a greater proportion of untreated food is defined as the discrimination threshold (DT). The DT occurred at sublethal concentrations in all 1:1 tests, with little mortality or reduction in food consumption. Little or no discrimination was observed in 9:1 tests, with mortality similar to the LC50 tests. The discrimination response in 5:5 tests was similar to the 1:1 tests for parathion and methiocarb, but with carbofuran the DT was higher than in the 1:1 test and higher mortality was observed. In all tests, mortality was inversely related to total food consumption. No relationship was found between mortality and the amount of active ingredient ingested/bird-day. Consequently, mortality was more a function of ability to locate untreated feeders than amount of chemical ingested. When alternative food choices exist, vulnerability to poisoning can be influenced by the number and relative abundance of those choices, as well as the bird's ability to detect the chemical.

Animals↗
PubMed1987

Hydroperoxide-dependent sulfoxidation catalyzed by soybean microsomes.

The sulfoxidation of methiocarb, an aromatic-alkyl sulfide pesticide, catalyzed by soybean microsomes was found to be strongly stimulated in the presence of cumene and linoleic acid hydroperoxides. We have shown that this S-oxidation, which does not require cofactors such as NAD(P)H, is an hydroperoxide-dependent reaction: 18O2-labeling experiments demonstrated that the oxygen atom incorporated into the sulfoxide originated from hydroperoxides rather than from molecular oxygen. In the absence of exogenous hydroperoxides, soybean microsomes catalyzed methiocarb sulfoxide formation at a basal rate dependent on their endogenous hydroperoxides, especially those derived from free fatty acids. The nature of the sulfoxidase is discussed. Our results seem to rule out the participation of cytochrome P-450 in this oxidation, whereas the studied sulfoxidase presents some similarities to plant peroxygenase.

Benzene Derivatives↗
PubMed1986

Oxidation of an organosulfur xenobiotic by microsomes from soybean cotyledons.

Methiocarb, an aromatic-alkyl sulfide insecticide was enzymatically oxidized into its sulfoxide by microsomes from soybean cotyledons. No further oxidation into sulfone was detected. Distribution of the sulfoxidase activity was studied in soybean seedlings and found maximal in cotyledons. Subcellular fractionation of cotyledons homogenates indicated that the activity was almost entirely associated with the microsomal fraction. Sulfoxidation of methiocarb did not require cofactors such as NAD(P)H. Nevertheless, the sulfoxidase did not act as a peroxidase.

Insecticides↗
PubMedDate not supplied

Determination of pesticides in soy-based infant formula using liquid chromatography with electrospray ionization tandem mass spectrometry.

A sensitive method using liquid chromatography with electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) was developed and validated to quantify and confirm 13 pesticides, including aldicarb sulfoxide, aldicarb sulfone, oxamyl, methomyl, formetanate, 3-hydroxycarbofuran, carbendazim, thiabendazole, aldicarb, propoxur, carbofuran, carbaryl, and methiocarb, in soy-based infant formula. Data acquisition under MS/MS was achieved by applying multiple reaction monitoring of 2 fragment ion transitions to provide a high degree of sensitivity and selectivity for both quantitation and confirmation. Different approaches to constructing calibration curves were compared and discussed to address issues of the extraction efficiency or recovery, and matrix effects. Matrix-matched standard calibration curves with the use of isoprocarb as an internal standard were finally used to achieve the best accuracy of the method. Under most circumstances, recoveries of 13 pesticides, spiked at 5.0, 25.0, and 45.0 microg/kg, were close to 100%. The method detection limits (signal-to-noise ratio > or =3:1; microg/kg) of 13 pesticides were 0.2 for thiabendazole and methiocarb, 0.6 for aldicarb, and 0.1 for the others.

Aldicarb↗
PubMed2007

Synergism studies with binary mixtures of pyrethroid, carbamate and organophosphate insecticides on Frankliniella occidentalis (Pergande).

The major mechanism of resistance to most insecticides in Frankliniella occidentalis (Pergande) is metabolic, piperonyl butoxide (PBO) suppressible, mediated by cytochrome-P450 monooxygenases and conferring cross-resistance among insecticide classes. The efficacy of insecticide mixtures of acrinathrin, methiocarb, formetanate and chlorpyrifos was studied by topical exposure in strains of F. occidentalis selected for resistance to each insecticide. The method consisted in combining increasing concentrations of one insecticide with a constant low rate of the second one as synergist. Acrinathrin activity against F. occidentalis was enhanced by carbamate insecticides, methiocarb being a much better synergist than formetanate. Monooxygenase action on the carbamates would prevent degradation of the pyrethroid, hence providing a level of synergism by competitive substrate inhibition. However, the number of insecticides registered for control of F. occidentalis is very limited, and they are needed for antiresistance strategies such as mosaics and rotations. Therefore, a study was made of the synergist effect of other carbamates not used against thrips, such as carbofuran and carbosulfan, against a susceptible strain and a field strain. Neither carbamate showed synergism to acrinathrin in the susceptible strain, but both did in the field strain, carbosulfan being a better synergist than carbofuran. The data obtained indicate that low rates of carbamates could be used as synergists to restore some pyrethroid susceptibility in F. occidentalis.

Animals↗
PubMed2001

Evaluation of medium treatments for management of Frankliniella occidentalis (Thripidae: Thysanoptera) and Bradysia coprophila (Diptera: Sciaridae).

Two greenhouse experiments, each comprising two trials, were conducted to evaluate medium drenches of insect growth regulators and conventional insecticides to reduce emergence of adult western flower thrips, Frankliniella occidentalis (Pergande), and fungus gnats, Bradysia coprophila (Lintner) from the medium. In the insect growth regulator trials, diflubenzuron and pyriproxyfen provided the greatest reduction in thrips emergence, and fenoxycarb, pyriproxyfen and azadirachtin resulted in the most significant reduction of fungus gnat emergence. Treatments with the contact insecticides, methiocarb and chlorpyrifos, resulted in the greatest reduction of thrips and fungus gnat populations. These data suggest that fungus gnats are susceptible to many compounds used in commercial greenhouse production. Even though medium drenches are not currently used for thrips management, drenches with diflubenzuron, pyriproxyfen, methiocarb and chlorpyrifos could aid in reducing thrips populations in greenhouse management programs.

Animals↗
PubMed2002

Effects of currently used pesticides in assays for estrogenicity, androgenicity, and aromatase activity in vitro.

Twenty-four pesticides were tested for interactions with the estrogen receptor (ER) and the androgen receptor (AR) in transactivation assays. Estrogen-like effects on MCF-7 cell proliferation and effects on CYP19 aromatase activity in human placental microsomes were also investigated. Pesticides (endosulfan, methiocarb, methomyl, pirimicarb, propamocarb, deltamethrin, fenpropathrin, dimethoate, chlorpyriphos, dichlorvos, tolchlofos-methyl, vinclozolin, iprodion, fenarimol, prochloraz, fosetyl-aluminum, chlorothalonil, daminozid, paclobutrazol, chlormequat chlorid, and ethephon) were selected according to their frequent use in Danish greenhouses. In addition, the metabolite mercaptodimethur sulfoxide, the herbicide tribenuron-methyl, and the organochlorine dieldrin, were included. Several of the pesticides, dieldrin, endosulfan, methiocarb, and fenarimol, acted both as estrogen agonists and androgen antagonists. Prochloraz reacted as both an estrogen and an androgen antagonist. Furthermore, fenarimol and prochloraz were potent aromatase inhibitors while endosulfan was a weak inhibitor. Hence, these three pesticides possess at least three different ways to potentially disturb sex hormone actions. In addition, chlorpyrifos, deltamethrin, tolclofos-methyl, and tribenuron-methyl induced weak responses in one or both estrogenicity assays. Upon cotreatment with 17beta-estradiol, the response was potentiated by endosulfan in the proliferation assay and by pirimicarb, propamocarb, and daminozid in the ER transactivation assay. Vinclozolin reacted as a potent AR antagonist and dichlorvos as a very weak one. Methomyl, pirimicarb, propamocarb, and iprodion weakly stimulated aromatase activity. Although the potencies of the pesticides to react as hormone agonists or antagonists are low compared to the natural ligands, the integrated response in the organism might be amplified by the ability of the pesticides to act via several mechanism and the frequent simultaneous exposure to several pesticides.

Animals↗
PubMed2004

The combined antiandrogenic effects of five commonly used pesticides.

In this study, mixture effects of five dissimilarly acting pesticides were analyzed for antiandrogenic effects in vitro and in vivo. Deltamethrin, methiocarb, prochloraz, simazine, and tribenuron-methyl are all commonly used for agricultural and horticultural purposes. Concentration-response curves for the inhibition of R1881-induced transcriptional activity of the androgen receptor (AR) in vitro of each pesticide alone and in an equimolar mixture were obtained. The IC25 values for deltamethrin, methiocarb, prochloraz, and the mixture were 5.8, 5.8, 3.5, and 7.5 microM, respectively. Simazine and tribenuron-methyl were ineffective. Applying the isobole method resulted in an isobole coefficient of 0.94 at IC25 for the effect of the mixture, indicating additive effects of the compounds. Comparison of observed effects and effects calculated by assuming additivity also strongly indicated additive effects of the pesticides in vitro. In vivo, each of the five pesticides and a mixture of the pesticides were tested for antiandrogenic effects in castrated testosterone-treated Wistar rats. The mixture induced a significant change of weights of the levator ani/bulbocavernosus muscle and adrenal glands. Changes in gene expression in ventral prostates were observed as distinct effects on levels of ornithin decarboxylase (ODC) mRNA and effects on levels of prostate binding protein subunit C3 (PBP C3) mRNA. No pesticide-induced effect on the level of testosterone-repressed prostatic message 2 (TRPM-2) mRNA was observed, whereas flutamide increased TRPM-2 levels. In conclusion, the pesticides were found to act additively in vitro. In vivo, the organ weight changes indicated that the pesticides had an accumulating effect that was not observed for the individual pesticides. Several pesticide-induced gene expression changes were observed, indicating that these are either very sensitive antiandrogenic end-points or that these changes are induced by a pathway not related to AR.

Androgen Antagonists↗
PubMed2001

Stability studies of carbamate pesticides and analysis by gas chromatography with flame ionization and nitrogen-phosphorus detection.

As a result of thermal stability studies of carbamate pesticides, a method has been proposed for their direct determination by gas chromatography in the ranges 1-20 and 0.1-1 mg l(-1), using flame ionization and nitrogen-phosphorus detection, respectively. The method allows the determination of propham, propoxur, carbofuran, carbaryl, methiocarb, isopropoxyphenol and naphthol in powdered potato samples. The analytes were previously extracted with a light petroleum-dichloromethane (1:1, v/v) mixture and preconcentred by solid-phase extraction through a C8 cartridge. The recoveries obtained from spiked potato samples (n=4 replicates) at two concentration levels, 10 and 0.5 mg of pesticide per kg of sample, were in the ranges 72-115 and 50-73%, with relative standard deviations of 2-7 and 5-8%, respectively. The detection limits were 50-210 and 41-53 microg kg(-1) with flame ionization and nitrogen-phosphorus detection, respectively, and reaching the maximum residue levels, 0.05 mg kg(-1) for methiocarb and propoxur, set by the Real Decreto 280/1994 (based on the European directive).

Calibration↗
PubMed2003

Optimization of microwave-assisted extraction and supercritical fluid extraction of carbamate pesticides in soil by experimental design methodology.

Orthogonal array design (OAD) was applied for the first time to optimize microwave-assisted extraction (MAE) and supercritical fluid extraction (SFE) conditions for the analysis of four carbamates (propoxur, propham, methiocarb, chlorpropham) from soil. The theory and methodology of a new OA16 (4(4)) matrix derived from a OA16 (2(15)) matrix were developed during the MAE optimization. An analysis of variance technique was employed as the data analysis strategy in this study. Determinations of analytes were completed using high-performance liquid chromatography (HPLC) with UV detection. Four carbamates were successfully extracted from soil with recoveries ranging from 85 to 105% with good reproducibility (approximately 4.9% RSD) under the optimum MAE conditions: 30 ml methanol, 80 degrees C extraction temperature, and 6-min microwave heating. An OA8 (2(7)) matrix was employed for the SFE optimization. The average recoveries and RSD of the analytes from spiked soil by SFE were 92 and 5.5%, respectively except for propham (66.3+/-7.9%), under the following conditions: heating for 30 min at 60 degrees C under supercritical CO2 at 300 kg/cm2 modified with 10% (v/v) methanol. The composition of the supercritical fluid was demonstrated to be a crucial factor in the extraction. The addition of a small volume (10%) of methanol to CO2 greatly enhanced the recoveries of carbamates. A comparison of MAE with SFE was also conducted. The results indicated that >85% average recoveries were obtained by both optimized extraction techniques, and slightly higher recoveries of three carbamates (propoxur, propham and methiocarb) were achieved using MAE. SFE showed slightly higher recovery for chlorpropham (93 vs. 87% for MAE). The effects of time-aged soil on the extraction of analytes were examined and the results obtained by both methods were also compared.

Carbamates↗
PubMed2001

Presence of carbamate pesticides in environmental waters from the northwest of Mexico: determination by liquid chromatography.

A study on the presence of carbamate pesticides, namely aldicarb, aldicarb sulfoxide, baygon, benthiocarb, carbofuran, 3-hydroxycarbofuran, carbaryl, desmedipham, methiocarb, methomyl, thiodicarb, oxamyl, and propham was made in ground and surface waters from an agricultural zone of the Yaqui Valley located in northwest Mexico. Trace determinations were made by liquid chromatography (LC) with post-column fluorescence detection (EPA method 531.1) or LC-diode array UV detection coupled on-line to a solid-phase extraction (SPE) system and using a 13 x 4.6 mm i.d. precolumn and a 150 x 4.6 mm i.d. analytical column, both packed with a C18 silica. Results indicated that the level of contamination with methiocarb was 5.4 micrograms/L in a groundwater sample and that for 3-hydroxycarbofuran was 18 micrograms/L in a surface water sample. This study provides the basis for a future monitoring program.

Agriculture↗
PubMed2003

Survival tests with Chironomus riparius exposed to spiked sediments can profit from DEBtox model.

DEBtox model is a biologically based model used to analyse aquatic toxicity data (The analysis of aquatic toxicity data, VU University Press, Amsterdam, The Netherlands, 1996, 149pp.). To date, it has not been used to analyse sediment survival tests, mainly because this would require daily counting of survivors, which is difficult for benthic organisms. In the present study, we adapted survival toxicity tests with the midge Chironomus riparius to permit survival data analysis with DEBtox. To validate the adaptation proposed, we exposed organisms to two chemicals, copper and methiocarb. We exposed larvae of second, third and fourth instar to different concentrations of the tested compounds and two different diets to assess the influence of diet and instar on DEBtox parameter estimates. Daily counting of organisms did not affect survival and did not lead to much more effort when compared to usual tests. Moreover, the analysis profited much from use of the DEBtox model. It was possible, with only survival data to estimate and validate the kinetics of the compounds, to predict survival during the recovery of exposed organisms and to assess the influence of food availability on toxicity. Food availability did not influence methiocarb toxicity, but copper was more toxic to food-limited organisms when a threshold concentration was exceeded. Comparison of parameters estimate also helped in understanding the differences in toxicity responses between instars. For the two compounds we studied, the difference was entirely explained by differences in threshold values.

Animals↗
PubMed2006

Survey of carbamate and organophosphorous pesticide export from a south Florida (U.S.A.) agricultural watershed: implications of sampling frequency on ecological risk estimation.

The objectives of the present study were to characterize the presence of selected carbamate and organophosphorous pesticides in Ten Mile Creek (Fort Pierce, FL, U.S.A.) and to evaluate the implications of sampling frequency on ecological risk estimates. Ten Mile Creek originates in a predominately agricultural watershed that is drained by an extensive network of cross-linked canals. Water samples were collected daily or every other day and were analyzed for azinphos-methyl, chlorpyrifos, diazinon, dimethoate, ethion, fenamiphos, malathion, methidathion, carbaryl, carbofuran, 3-hydroxycarbofuran, methiocarb, methomyl, oxamyl, and propoxur. A total of 457 samples were analyzed for the carbamate suite, and a total of 332 samples were analyzed for the organophosphorous suite. Carbaryl was detected in eight samples; half of these detections occurred on four consecutive days (October 26-29, 2001) at concentrations ranging from 0.33 to 0.95 microg/L. Methomyl was detected in samples collected on five consecutive days (March 30-April 3, 2002) at concentrations ranging from 1.0 to 2.2 microg/L. Oxamyl was detected in four samples, three of which occurred on three consecutive days (February 17-19, 2002) at concentrations ranging from 6.2 to 6.8 microg/L. The carbamates propoxur, 3-hydroxycarbofuran, carbofuran, and methiocarb were not detected. Diazinon and ethion were the only organophosphorous pesticides detected. Diazinon was detected at 0.9 and 0.7 microg/L on January 5, 2002, and on January 6, 2002, respectively. Ethion was detected in 18 consecutive samples (August 3-20, 2001). The mean, maximum, minimum, and median detected concentrations were 0.38, 0.61, 0.30, and 0.33 microg/L, respectively. Results indicate that frequent sampling is necessary to characterize the presence of these pesticides in this intensively drained watershed. This conclusion also may apply to similar canalized watersheds.

Agriculture↗
PubMedDate not supplied

Liquid chromatographic determination of N-methylcarbamate insecticides and metabolites in crops. II. Analytical characteristics and residue findings.

Four laboratories obtained 177 carbamate recovery values using a liquid chromatographic method. The average recovery of 11 carbamates (aldicarb, aldicarb sulfone, bufencarb, carbaryl, carbofuran, 3-hydroxy carbofuran, 3-keto carbofuran, methiocarb, methiocarb sulfoxide, methomyl, and oxamyl) from 14 crops was 99% with a coefficient of variation of 8% (0.03-1.8 ppm fortification levels). No statistical difference in recovery was found between oxime and phenyl carbamates, or between parent and metabolite carbamates. Average recovery of aldicarb sulfoxide was 59% due to loss in the liquid-liquid partitioning because of the polarity of this compound. A fifth laboratory contributed 34 carbamate recoveries (average 99%) on table-ready food products for 4 carbamates. Bendiocarb, dioxacarb, isoprocarb, and propoxur are also quantitatively recovered through the method. Previously reported carbamate and noncarbamate recovery data are also discussed. In the Food and Drug Administration's (FDA) analysis of 319 samples (mainly crops), 86 (27%) were found to contain residues of carbamate insecticides and/or toxic carbamate metabolites. Carbaryl and methomyl were the most common carbamate residues found on the food products excluding the aldicarb sulfone and sulfoxide residues found on potatoes. In one FDA Total Diet Program "market basket", 11 of 69 table-ready food commodities contained from 0.005 to 0.094 ppm carbamate residues. Carbaryl was the most prevalent residue. Several laboratories reported adverse effects on the determinative system when inadequately purified reagents were used.

Carbamates↗
PubMedDate not supplied

Automated sample preparation for monitoring groundwater pollution by carbamate insecticides and their transformation products.

We investigated automated on-line solid-phase extraction (SPE) followed by liquid chromatographic (LC) techniques for monitoring carbamates and their transformation products. Analytical determinations were performed by LC with UV or postcolumn fluorescence detection (U.S. Environmental Protection Agency Method 531.1 for carbamate insecticides) after preconcentration with on-line SPE using C18 Empore extraction disks. On-line SPE/LC/thermospray mass spectrometry with time-scheduled selected-ion monitoring was used as confirmatory method. The method was used to determine pesticide traces in well waters of a typical aquifer in the Almeria area (Andalucia, south of Spain) from March 1993 to February 1994. The major pollutants, found in highest amounts, were carbofuran, methiocarb, and methomyl, at levels of 0.32, 0.3, and 0.8 micrograms/L, respectively. According to results of seasonal variation studies, pollution by carbamate insecticides is sporadic and exceeds the limit of 0.5 micrograms/L for total pesticides allowed by the European Economic Community Drinking Water Directive only twice a year. 3-Hydroxycarbofuran and methiocarb sulfone also were detected, showing the importance of including the main toxic break-down products of carbamate insecticides in future monitoring programs.

Autoanalysis↗
PubMed1996

Solid-phase extraction of polar pesticides from environmental water samples on graphitized carbon and Empore-activated carbon disks and on-line coupling to octadecyl-bonded silica analytical columns.

The suitability of Empore-activated carbon disks (EACD), Envi-Carb graphitized carbon black (GCB) and CPP-50 graphitized carbon for the trace enrichment of polar pesticides from water samples was studied by means of off-line and on-line solid-phase extraction (SPE). In the off-line procedure, 0.5-2 l samples spiked with a test mixture of oxamyl, methomyl and aldicarb sulfoxide were enriched on EnviCarb SPE cartridges or 47 mm diameter EACD and eluted with dichloromethane-methanol. After evaporation, a sample was injected onto a C18-bonded silica column and analysed by liquid chromatography with ultraviolet (LC-UV) detection. EACD performed better than EnviCarb cartridges in terms of breakthrough volumes (> 2 l for all test analytes), reproducibility (R.S.D. of recoveries, 4-8%, n = 3) and sampling speed (100 ml/min); detection limits in drinking water were 0.05-0.16 microgram/l. In the on-line experiments, 4.6 mm diameter pieces cut from original EACD and stacked onto each other in a 9 mm long precolumn, and EnviCarb and CPP-50 packed in 10 x 2.0 mm I.D. precolumn, were tested, and 50-200 ml spiked water samples were preconcentrated. Because of the peak broadening caused by the strong sorption of the analytes on carbon, the carbon-packed precolumns were eluted by a separate stream of 0.1 ml/min acetonitrile which was mixed with the gradient LC eluent in front of the C18 analytical column. The final on-line procedure was also applied for the less polar propoxur, carbaryl and methiocarb. EnviCarb could not be used due to its poor pressure resistance. CPP-50 provided less peak broadening than EACD: peak widths were 0.1-0.3 min and R.S.D. of peak heights 4-14% (n = 3). In terms of analyte trapping efficiency on-line SPE-LC-UV with a CPP-50 precolumn also showed better performance than when Bondesil C18/OH or polymeric PLRP-S was used, but chromatographic resolution was similar. With the CPP-50-based system, detection limits of the test compounds were 0.05-1 microgram/l in surface water.

Adsorption↗