Matrix solid phase dispersion (MSPD) extraction and gas chromatographic screening of nine chlorinated pesticides in beef fat

A multiresidue technique is presented for the extraction and quantitative gas chromatographic screening of 9 insecticides (lindane, heptachlor, aldrin, heptachlor epoxide, p,p'-DDE, dieldrin, endrin, p,p'-TDE, and p,p'-DDT) as residues in beef fat. Beef fat was fortified by adding the 9 insecticides, plus dibutyl chlorendate as internal standard, to 0.5 g portions of beef fat and blending with 2 g C18 (octadecylsilyl)-derivatized silica. The C18/fat matrix blend was fashioned into a column by adding the blend to a 10 mL syringe barrel containing 2 g activated Florisil. The insecticides were then eluted from the column with 8 mL acetonitrile, and a 2 microL portion of the acetonitrile eluate was then directly analyzed by gas chromatography with electron capture detection. Unfortified blank controls were treated similarly. The acetonitrile eluate contained all of the pesticide analytes (31.25-500 ng/g) and was free of interfering co-extractants. Correlation coefficients for the 9 extracted pesticide standard curves (linear regression analysis, n = 5) ranged from 0.9969 (+/- 0.0021) to 0.9999 (+/- 0.0001). Average relative percentage recoveries (85 +/- 3.4% to 102 +/- 5.0%, n = 25 for each insecticide), inter-assay variability (6.0 +/- 1.0% to 14.0 +/- 6.7%, n = 25 for each insecticide), and intra-assay variability (2.5-5.1% n = 5 for each insecticide) indicated that the methodology is acceptable for the extraction, determination, and screening of these residues in beef fat.     

Multiresidue gas chromatographic method for determining organochlorine pesticides in meats: validation study for swine and beef fats

A validation of a previously studied method for determining organochlorine residues in poultry fat was conducted to extend the usefulness of the method to beef and swine fats. The validation samples consisted of 16 materials all analyzed in duplicate. Fortification levels ranged from 0.02 to 1.2 ppm for alpha-BHC, lindane, cis- and trans-chlordane, octachlor epoxide, o,p'- and p,p'-DDT, p,p'-DDE, p,p'-TDE, hexachlorobenzene, heptachlor epoxide, dieldrin, endrin, methoxychlor, mirex, and toxaphene. The average recovery was 101% with a range of 79-113%, not including toxaphene. The ranges of coefficients of variation were CVo = 0-23.37% and CVx = 3.74-26.19%. The results were comparable to the previous collaborative study of the same method for poultry fat. The extended method has been adopted official first action.     

Multiresidue matrix solid phase dispersion (MSPD) extraction and gas chromatographic screening of nine chlorinated pesticides in catfish (Ictalurus punctatus) muscle tissue

A multiresidue technique for extraction and gas chromatographic screening of 9 insecticide (lindane, heptachlor, aldrin, heptachlor epoxide, p,p'-DDE, dieldrin, endrin, p,p'-TDE, and p,p'-DDT) residues in catfish (Ictalurus punctatus) muscle tissue is presented. The 9 insecticides, plus dibutyl chlorendate internal standard, were fortified into catfish muscle tissue (0.5 g) and blended with 2 g C18 (octadecylsilyl derivatized silica reverse-phase material). The C18/muscle tissue matrix blend was fashioned into a column by adding the blend to a 10 mL syringe barrel containing 2 g activated Florisil. The insecticides were then eluted from the column with acetonitrile (8 mL), and a portion (2 microL) of the acetonitrile eluate was then directly analyzed by gas chromatography with electron capture detection. Unfortified blank controls were treated similarly. The resultant extracts contained pesticide analytes (31.25-500 ng/g) free of interfering compounds when analyzed. Correlation coefficients for the 9 extracted pesticide standard curves (linear regression analysis, n = 5) ranged from 0.9967 (+/- 0.0018) to 0.9999 (+/- 0.0001). Average percentage recoveries (82 +/- 4.8% to 97 +/- 3.6%, n = 25 for each insecticide), interassay (5.0 +/- 2.7% to 16.9 +/- 6.5%, n = 25 for each insecticide) and intraassay (1.8 to 4.7%, n = 5 for each insecticide) variabilities were indicative of an acceptable methodology for the analysis and screening of these residues in catfish muscle tissue.     

Pesticide residues in milk and fish samples collected from upper Egypt

In Egypt, buffalo milk is much preferred by consumers over cow's milk, while small catfish and bolti fish are common in the diet of farmers. Samples of buffalo milk, catfish, and bolti fish collected from Beni-Suef Governorate (Upper Egypt) were analyzed for organochlorines and polychlorinated biphenyls. The results obtained by gas chromatography and confirmed by thin-layer chromatographic techniques revealed high amounts of organochlorines in milk; residues were lower but occurred more frequently in fish samples. Pesticide contaminants found most often were HCH isomers including lindane, DDT complex, aldrin and dieldrin, heptachlor and heptachlor epoxide, hexachlorobenzene, and oxychlordane. Polychlorinated biphenyls were not detected in any of the analyzed samples.     

Effect of a sewage plant in the distribution of organochlorine residues in the Diyala River,Iraq

As a continuation of the National Pesticide Monitoring Program in Iraq, this work was carried out to study the distribution of organochlorine insecticide residues in sediments and water from the lower part of Diyala river, Iraq, where a large sewage treatment plant is located. Sediment and water samples were analyzed by gas chromatography and found to contain different levels of lindane, aldrin, dieldrin, heptachlor, heptachlor epoxide, chlordane and isomers and metabolites of DDT. High levels of these compounds were detected in water samples taken in April. No corelation with time was noticed in sediment samples. The highest and most frequet values were those of chlordane and DDT in sediment and water samples. It was difficult to assess the effect of the sewage treatment plant on water pollution with organochlorine residues.     

Residues of organochlorine insecticides in two lakes of Jaipur,India

The concentration of organochlorine insecticides/metabolites, namely, lindane, heptachlor, aldrin, p,p′-DDL, p,p′-DDD, and p,p′-DDT were determined in water samples taken from two lakes, Jalmahal and Mahalon, from June 1985 to July 1986. These lakes are contaminated with moderate to high level of residues of different insecticides. In Mahalon lake the residues were highest (6.6 μg L^?1) during October 1985 whereas in Jalmahal lake they were highest (9.6 μg L^?1) in September 1985. In both lakes, residues of DDT exceeded the recommended limit for water quality criteria. Lindane was found in most of the samples but in lower quantities. Aldrin was the second most common residue in these lakes.     

Gas chromatographic resolution of organochlorine insecticides on OV-1/OV-17, OV-210/OV-17, and OV-225/OV-17 mixed phase systems.

The resolution of organochlorine insecticides and their related compounds on OV-1/OV-17, OV-210/OV-17, and OV-225/OV-17 mixed phase column systems was investigated. Four BHC isomers and p,p'-DDT, its isomer, and their metabolites (except p,p'-DDE and o,p'-DDE) were resolved on the OV-210/OV-17 system. Heptachlor and heptachlor epoxide were separated on 5% OV-1/2% OV-17 or OV-225/2% OV-17. Resolution of aldrin, dieldrin, and endrin was obtained on 5% OV-210/2% OV-17, p,p'-DDE and o,p'-DDE could not be separated by any of the systems studied.     

Dissipation of teflubenzuron and triflumuron residues in field-sprayed and cold-stored pears.

Dissipation of residues of benzoylurea insecticides teflubenzuron (TFB) and triflumuron (TFM) under field conditions was evaluated on a pear orchard in Greece. Residues were determined by UV-HPLC analysis, with a detection limit of 0.030 mg/kg for both pesticides. TFB residues in pears were found to persist for 2 weeks and decline thereafter with 48% of the initial deposit remaining 42 days after the last application. TFM residues were found to decline following first-order kinetics and with a half-life of 39(+/-7) days. Residues of both pesticides found in pears collected at harvest maturity were lower than the maximum residue limits (MRLs) set by individual countries. Dissipation of TFB and TFM in cold-stored pears was also evaluated. TFB residues were very persistent for the whole storage period, whereas TFM residues did not dissipate for 6 weeks and then showed a constant decline; 7% of the initial concentration remained at the end of the storage period of 29 weeks.     

Levels of pesticide residues in Egyptian human milk samples and infant dietary intake

Contamination of human milk with residues of organochlorine pesticides and polychlorinated biphenyls was studied in a series of investigations concerned with the monitoring of these chemicals in Egyptian food. The DDT complex was the most frequently found pesticide, followed by total hexachlorocyclohexane isomers. Heptachlor and its epoxide, dieldrin, hexachlorobenzene, and oxychlordane were also found but less frequently. Estimated dietary intakes (EDIs) of these contaminants by the breast-fed infants were compared to acceptable daily intakes (ADIs). EDIs of DDT complex, lindane (gamma-HCH), heptachlor + heptachlor epoxide, and oxychlordane were below ADIs. Dieldrin EDI exceeded the acceptable daily intake.     

Long-term preservation of egg and tissue homogenates for determination of organochlorine compounds: freezing versus freeze-drying

Storage of wet egg homogenates at temperatures from -18 degrees to -28 degrees C was more suitable for long-term preservation than freeze-drying. Changes in residue levels of heptachlor epoxide, oxychlordane, dieldrin, hexachlorobenzene,p,p'-DDE, mirex, and PCBs were not significant over a 3-year period in fresh herring gull egg homogenates stored at -18 degrees to -28 degrees C. Compounds with gas chromatographic retention times shorter than hexachlorobenzene vaporized during freeze-drying at a rate proportional to their volatility. Evaporative losses of components with vapor pressures less than hexachlorobenzene did not occur in naturally contaminated herring gull eggs after storage at room temperature for up to 1 year. Higher losses of all compounds, up to 25% for p,p'-DDE, occurred in freeze-dried whole-body herring gull homogenates. Easily dehydrochlorinated compounds were rapidly degraded in freeze-dried chicken egg homogenate at room temperature: The half-life of p,p'-DDT and p,p'-DDD was about 20 days, and that of alpha- and gamma-hexachlorocyclohexane was much less than 16 days. About one-third of oxychlordane in herring gull eggs was lost in 1 year under these conditions, but none was lost after freeze-drying when the homogenate was stored at -18 degrees to -28 degrees C.     

Residues in broiler chick tissues from low level feedings of seven chlorinated hydrocarbon insecticides.

Two chlorinated insecticide feeding studies from 1967-1968, using broiler chicks, have been completed. In Study I, lindane, heptachlor epoxide, dieldrin, endrin, methoxychlor, and DDT were fed in combination at 3 levels: 0.05, 0.15, and 0.45 ppm. Data show that, in fat tissues, heptachlor epoxide attained a level approximately 20 times the respective levels in the feed; dieldrin 15 times; endrin 10 times; p,p'-DDT 9 times; lindane 3 times; and o.p'-DDT less than the feeding levels. Of the DDT metabolites, p.p'-DDE and p,p'-DDD, only p,p'-DDE was significant at 3 times the 0.45 ppm feeding level. Endrin ketone, a metabolite of endrin, reached plateau levels approximately equal to feeding levels. All residue levels in liver tissues were less than 0.02 ppm. In Study II, technical chlordane was fed singly at the 0.05, 0.15, and 0.45 ppm levels. Results are tabulated for both total chlordane and for 6 identifiable isomers. Total chlordane in fat tissues attained plateau levels 3-5 times the respective feeding levels. Total chlordane levels in liver and breast tissues were all less than 0.01 ppm.     

Determination of fungicide residues in field-grown strawberries following different fungicide strategies against gray mold (Botrytis cinerea)

In a 2 year experiment, residues in field-grown strawberries were investigated from the fungicides fenhexamid, pyrimethanil, tolylfluanid, and kresoxim-methyl resulting from different strategies, as regards the dose, number, and time of fungicide applications. Kresoxim-methyl was only used the first year and in full or no dose to control powdery mildew. In the first year, the highest concentrations analyzed were 0.66 mg kg(-1) for pyrimethanil and 0.63 mg kg(-1) for fenhexamid resulting from the use of recommended dose rates and a preharvest interval (PHI) of 10 days, thus not exceeding the Danish maximum residue limit (MRL) of 1 mg kg(-1). Tolylfluanid was used no later than 21 days before harvest, which left residue contents in the berries of 0.48 mg kg(-1), a value well below the MRL of 5 mg kg(-1). In the second year, fungicide residues found in the samples were generally lower, 0.39 and 0.03 mg kg(-1) for pyrimethanil and fenhexamid, respectively. No residues of kresoxim-methyl were found in any of the samples from the field trials, indicating that kresoxim-methyl residues had declined to a level well below the detection limit within the 28 day period between the last application and the harvest.     

Uptake and bioconcentration of dieldrin,dimethoate, and permethrin by Tetrahymena pyriformis

A ciliate protozoan, Tetrahymenapyriformis was exposed to three insecticides, dieldrin, dimethoate, and permethrin for 12 hr to study the uptake and bioconcentration potential. Ciliates concentrated 922, 3547, and 1056 gg g^?1 dry wt. over an initial concentration of 1 gg mL^?1 of dieldrin, dimethoate, and permethrin, respectively. The highest bioconcentration factor for three insecticides was 2095, 3547, and 1110, respectively. It is suggested that if levels in the environment reach 1 gg mL^?1 the chief effects would be reduction of cell population, and accumulation of the toxicants by ciliates. Accumulation of insecticides by ciliates would permit the toxicants to enter aquatic food chains. Thus the compounds could exert toxic effects at higher trophic levels.     

Trace analysis of chloramphenicol residues in eggs, milk, and meat: comparison of gas chromatography and radioimmunoassay

A radioimmunological assay (RIA) to detect chloramphenicol (CAP) residues in eggs, milk, and meat is described. For tissues and other edible products of chloramphenicol-treated animals (chickens, cows, and pigs), the limit of detection is about 200 ng/kg. Residue levels above 1 microgram/kg can easily be quantitated. When highly specific antisera produced in sheep were used, cross-reactivity was insignificant except for metabolites deviating from the parent compound in the acyl side chain only. Thiamphenicol fails to bind to the antisera; hence, it does not interfere with the assay. In the procedure described, the role of cleanup is merely to remove lipids. Thus, skim milk can be analyzed following appropriate dilution without cleanup. The results obtained by RIA were confirmed by gas chromatography with electron capture detection. The new RIA allows rapid, sensitive, and specific screening of large numbers of samples.     

Multiresidue gas chromatographic method for determining organochlorine pesticides in poultry fat: collaborative study

A gas chromatographic electron capture detector method is described for the quantitative determination of organochlorine pesticide residues in poultry fat. The samples are rendered and cleaned up using automated gel permeation chromatography. The collaborative samples consisted of 10 fortified samples and one incurred residue sample, all in duplicate. Fortification levels ranged from 0.15 to 1.0 ppm for alpha-BHC, lindane, cis- and trans-chlordane, octachlor epoxide, o,p' and p,p'-DDT, p,p'-DDE, p,p'-TDE, hexachlorobenzene, heptachlor epoxide, dieldrin, endrin, methoxychlor, mirex, and toxaphene. The average recovery was 91.9% with a range of 81-102%. The ranges of coefficients of variation were: CVo = 3.39-14.79%; CVL = 0-16.6%; and CVx = 5.82-19.0%. The results indicate accuracy and precision comparable to other official methodology. The method has been adopted official first action.     

Chemometric classification of the fat residues from the conditioning operations of table olive processing, based on their minor components

The work characterizes the unsaponifiable matter of fats released in pitting green (GP) and ripe (RP) olives, in pitting/stuffing green olives with vegetable (GPSV) and animal (GPSA) products and in the fat settled at the end of the factory sewer system (W). The unsaponifiable matter ranged from 1.94% (RP) to 5.91% (GPSA); total sterols from 1319 mg/kg fat (GPSV) to 2002 mg/kg fat (RP), with β-sitosterol as the most abundant. Fatty alcohols ranged from 242 mg/kg (GP) to 556 mg/kg (W), with C22 as the most abundant. Triterpene diols were found only in GPSV (erythrodiol + uvaol, 0.80%). Wax was not present in the fats from GP and RP but increased with the general fat degradation in the order GPSV (128 mg/kg), GPSA (171 mg/kg) and W (263 mg/kg). Chemometric analysis was able to detect differences among the diverse fats; sterols + fatty alcohols cluster analysis was useful for fat grouping.     

Residue depletion of cefquinome in swine tissues after intramuscular administration

A high-performance liquid chromatography (HPLC) method with ultraviolet (UV) detection was developed for the detection of cefquinome (CEQ) residues in swine tissues. The limit of detection (LOD) of the method was 5 ng g(-1) for muscle and 10 ng g(-1) for fat, liver, and kidney. Mean recoveries of CEQ in all fortified samples at a concentration range of 20-500 ng g(-1) were 80.5-86.0% with coefficient of variation (CV) below 10.3%. Residue depletion study of CEQ in swine was conducted after five intramuscular injections at a dose of 2 mg kg(-1) of body weight with 24 h intervals. CEQ residue concentrations were detected in muscle, fat, liver, and kidney using the HPLC-UV method at 265 nm. The highest CEQ concentration was measured in kidney tissue during the study period, indicating that kidney was the target tissue for CEQ. CEQ concentrations in all examined tissues were below the accepted maximum residue limit (MRL) recommended by the Committee for Veterinary Medical Products of European Medical Evaluation Agency (EMEA) at 3 days post-treatment.     

Occurrence and distribution of persistent organochlorine compounds in U.K. sewage sludges

A total of 444 sewage sludges, sampled from sewage treatment works in the U.K., were analyzed for polychlorinated biphenyls (PCB) and the organochlorine insecticides γ-Hexachlorocyclohexane (γ-HCH), aldrin, dieldrin and endrin. PCB, γ-HCH and dieldrin were found to occur more frequently and at higher concentrations in sewage sludges than aldrin and endrin. In order to investigate the temporal variation of these compounds in sewage sludge, three sewage treatment works were sampled at monthly intervals over an 18 mo period. PCB, γ-HCH and dieldrin were again the most frequently detected compounds. Concentrations of aldrin and endrin were only sporadically detected. The results of a serial correlation analysis of these data indicated that some short term correlation of PCB and dieldrin concentrations above and below the mean value was evident. The data acquired in the course of this survey have been compared with the results of similar work conducted previously in the U.K. and other countries. The possible implications of the presence of persistent organochlorine compounds in sewage sludges which are disposed to the environment are discussed.     

Collaborative study of an extension of the Mills et al. method for the determination of pesticide residues in foods.

Fifteen laboratories collaboratively determined parathion, o,p'-DDT, p,p'-DDT, and p,p'-DDE in kale, and lindane, dieldrin, heptachlor epoxide, and p,p'-DDE in eggs, using electron capture gas-liquid chromatography (potassium chloride thermionic detector for parathion). Pesticide levels ranged from 0.033 ppm heptachlor epoxide to 3.32 ppm p,p'-DDT. Mean recoveries (+/- standard deviations) were: parathion 91+/-15%, o,p'-DDT 99+/-8%, P,P'-DDT 97+/-8%, lindane 94+/-4%, dieldrin 106+/-8%, heptachloro epoxide 106+/-5%, p,p'-DDE 94+/-8% in eggs and 101+/-9% in kale. The methods have been adopted as official first action.     

Acute Toxicity of Seven Selected Pesticides (Alachlor, Atrazine, Dieldrin, Diuron, Pirimiphos-Methyl, Chlorpyrifos, Diazinon) to the Marine Fish (Turbot, Psetta maxima)

The present study evaluated the short-term toxicity of seven selected pesticides: four insecticides (chlorpyrifos, dieldrin, diazinon and pirimiphos-methyl) and three herbicides (diuron, alachlor and atrazine). With this aim, a standard toxicity test with the highly sensitive early life stages (ELS) of a marine fish was used. The turbot, Psetta maxima, is abundant in shallow estuarine and costal habitats and is currently the most commonly cultivated fish species in Galicia, NW Spain. According to the turbot ELS test results, chlorpyrifos was the most toxic pesticide tested for both embryos and larvae and was followed in order of decreasing toxicity by dieldrin, pirimiphos-methyl, diazinon, alachlor, atrazine and diuron. Larvae were more sensitive than embryos to the seven pesticides. The median lethal concentrations of the selected pesticides during a 48- and a 96-h exposure for turbot embryos and larvae were, respectively (in micrograms per litre): chlorpyrifos, 116.6 and 94.65; dieldrin, 146 and 97; pirimiphos-methyl, 560 and 452; diazinon, 1,837 and 1,230; alachlor, 2,177 and 2,233; diuron, 10,076 and 7,826; and atrazine, 11,873 and 9,957. According to their acute toxicity, the insecticides were more toxic than the herbicides. Furthermore, all insecticides and herbicides appear to be teratogenic to turbot ELS.