Detection and occurrence of pentachlorophenol residues in chicken liver and fat

Abstract

A method for the detection of pentachlorophenol (PCP) residues in chicken liver and fat is presented. A detection limit of 0.002 mg/kg was achieved. Recoveries from liver and fat were in the range 82–88% and 95–97%, respectively.

Low level residues of PCP were found in all 1072 liver and 723 fat samples. These levels were <0.010 mg/kg in 92.7% of the fat and 75.6% of the livers. Only 0.75% of the liver samples had PCP levels>0.1 mg/kg. None of the more toxic impurities of PCP were detected in the chicken tissues.     

Environmental monitoring study of selected veterinary antibiotics in animal manure and soils in Austria

LC-MS/MS was used for determination of selected tetracyclines, sulfonamides, trimethoprim, and fluoroquinolones in manure samples of pig, chicken and turkey, as well as arable soils fertilized with manure. Recoveries from spiked samples ranged from 61 to 105%. Method quantification limits were set to 100 microg/kg for all substances. Analysis of 30 pig manure, 20 chicken and turkey dung, and 30 lyophilized soil samples taken in Austria revealed that in pig manure up to 46 mg/kg chlortetracycline, 29 mg/kg oxytetracycline and 23 mg/kg tetracycline could be detected. As representatives of the group of sulfonamides, sulfadimidine in pig manure and sulfadiazine in chicken and turkey dung were detected in significant amounts (maximum concentration, 20 and 91 mg/kg, respectively). Enrofloxacin was particularly observed in chicken and turkey samples. Positive detection of chlortetracycline, enrofloxacin, and ciprofloxacin, in soil samples should be outlined as most important results of this study.     

Pesticide residues in Nile tilapia (Oreochromis niloticus) and Nile perch (Lates niloticus) from Southern Lake Victoria, Tanzania

Nile tilapia (Oreochromis niloticus) and Nile perch (Lates niloticus) samples were collected from fish landing stations in nine riparian districts on the Tanzanian side of Lake Victoria and screened for residues of 64 organochlorine, organophosphorus, carbamate, and pyrethroid pesticides. The residue levels in the fish fillet were up to 0.003, 0.03 and 0.2 mg/kg fresh weight (0.7, 3.8 and 42 mg/kg lipid weight) of fenitrothion, DDT and endosulfan, respectively. Mean levels within sites were up to 0.002, 0.02 and 0.1 mg/kg fresh weight (0.5, 0.5 and 16 mg/kg lipid weight), respectively. The detection of higher levels of p,p'-DDT than the degradation products (p,p'-DDD and p,p'-DDE), and higher levels of endosulfan isomers (alpha and beta) than the sulphate, in fish samples, implied recent exposure of fish to DDT and endosulfan, respectively. Generally, most of the fish samples had residue levels above the average method detection limits (MDLs), but were within the calculated ADI.     

Pesticide and PCB levels in fish from Alberta (Canada)

Pesticide and PCB analyses were completed on fat and muscle samples of 750 fish collected from 11 major lakes and rivers in Alberta. Although phenoxy and organophosphate residues were always below detectable limits, traces of chlorinated pesticides and their derivatives, particularly DDE, DDD and chlordane, were detected in most fat samples. Methoxychlor was frequently found in goldeye from the North Saskatchewan River but not recorded in fish from any other lake or river. Its presence in goldeye, a highly migratory species, was probably a result of biting-fly control programs in the Saskatchewan part of the river. PCB levels exceeded 25 mg/kg in the fat of several species from the North Saskatchewan River but were generally lower in the other systems. Analysis of 160 sediment samples from the North Saskatchewan River revealed no point source of PCB contamination, with residues always <0.01 mg/kg dry weight.     

A method to determine residue levels of persistent organochlorine pesticides in human milk from Indonesian women

A method has been developed for the analysis of organochlorine pesticides in human milk using solvent extraction, Florisil solid phase extraction clean-up and analysis by gas chromatography with an electron capture detector. The recovery of analytes from spiked milk samples was in the range 53 +/- 1% to 109 +/- 7% (n = 9). A small number of samples were obtained from women in a rural and an urban area of Indonesia and analysed using the developed method. The results are reported on a milk fat basis. All samples contained detectable residues of p,p'-DDT (urban mean 0.11 +/- 0.18 mgkg(-1) (n = 5), rural mean 0.07 +/- 0.03 mg kg(-1) (n = 5)) and p,p'-DDE (urban mean 0.05 +/- 0.04 m kg(-1) (n = 5), rural mean 0.76 +/- 1.46 mg kg(-1) (n = 5)). Residues of HCB, betaHCH, alpha-endosulfan and dieldrin were also detected in some samples. There was no significant difference (at the 95% confidence level) in levels of pesticides between urban and rural areas. The levels of organochlorine pesticides in milk from Indonesian women were lower than those reported from Indonesian women exposed to DDT through malaria eradication schemes and were similar to levels reported from UK and Japan.     

Background levels and dietary intake of PCDD/Fs in domestic and imported meat in South Korea

A survey was conducted in South Korea to determine residual levels and dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from meat. Altogether 119 domestic and 164 imported samples of beef, pork, and chicken were examined. The mean levels of PCDD/Fs in upper bound were 0.21, 0.22, and 0.04pg WHO-TEQ/g fat for beef, pork, and chicken, respectively. The low level of PCDD/Fs in chicken probably resulted from the low fat content in the samples used. The samples were separated into domestic and imported products in order to investigate the sources of contamination. PCDFs were the more dominant congeners in domestic beef and were similar to those found from emission of incineration. However, the congener profiles of domestic beef and incineration were difficult to compare because the environmental fate and animal metabolism were involved. The upper bound dietary intake of PCDD/Fs from beef, pork and chicken was calculated to be 0.04pg/WHO-TEQ/kgbw/day. The combined consumption of beef, pork, and chicken was found to be 84.8g per day for a person weighing 60kg and represented 5.7% of their total daily food intake.     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

Determination of acaricide residues in saudi arabian honey and beeswax using solid phase extraction and gas chromatography

Determination of acaricide residues of flumethrin, tau-fluvalinate, coumaphos, and amitraz in honey and beeswax was carried out using a rapid extraction method utilizing C-18 SPE cartridges and an analytical method utilizing GC with ECD, NPD, and MSD detectors for the four acaricides. Recovery percentages from the extraction method ranged from 90-102%, while the minimum detection levels ranged from 0.01-0.05 mg/kg for the acaricides. Nine of the 21 analyzed samples were found to be contaminated with the acaricides tau-fluvalinate and coumaphos. Neither flumethrin nor amitraz was detected in any of the honey or wax samples. Coumaphos was found only in honey samples in which two samples exceeded the tolerance levels set by EPA and EC regulations. It has not been detected in beeswax. Five honey samples and eight beeswax samples were found to be contaminated with tau-fluvalinate. One of the wax samples was contaminated with a relatively high residue of tau-fluvalinate and contained above 10 mg/kg.     

Concentrations of pentachlorophenol (PCP) in fish and shrimp in Jiangsu Province, China

Pentachlorophenol (PCP) concentrations were determined in 55 samples of fish, shrimp, crabs, frogs and turtles collected in Jiangsu Province and 55 freshwater shrimp samples collected from the Huiming Fish Market, Nanjing, China between 2003 and 2004. PCP concentrations ranged from less than the method detection limit (MDL: 0.5 microg/kg ww) to 61 microg/kg ww, with a mean of 5.2 microg/kg ww in 55 samples collected across Jiangsu Province and a mean of 0.5 microg/kg ww for freshwater shrimp collected from the Huiming Fish Market. Concentrations of PCP in common carp (Carassius auratus) were significantly greater than concentrations of PCP in other species from all of the areas studied. Grass carp (Ctenopharyngodon idella) contained the second greatest concentrations and crustacean species contained the least concentrations. Concentrations of PCP were greater in samples collected from Southern Jiangsu than those collected from other areas of Jiangsu Province. Concentrations of PCP in the freshwater shrimp (Macrobrachium nipponense) from the Huiming Fish Market were greater in March and September than those collected in June and December. Based on the allowable daily intake (ADI) set by the US National Academy of Science, current concentrations of PCP measured in aquatic products from Jiangsu Province presented minimus health risks to humans.     

Determination of acibenzolar-S-methyl and its acidic metabolite in soils by HPLC-diode array detection

A simple and accurate method for the analysis of acibenzolar-S-methyl (benzo[1,2,3]thiadiazole-7-carbothioic acid-S-methyl ester; CGA 245 704; ASM) and its major conversion product, benzo[1,2,3]thiadiazole-7-carboxylic acid (CGA 210 007; BTC), in soils is presented. ASM extraction from soil samples was performed using acetonitrile and BTC was extracted with a mixture of potassium phosphate buffer (0.5 M, pH 3) and acetonitrile (70:30 %, v/v). Both extracts were directly analyzed in a high-performance liquid chromatography-diode array detection (HPLC-DAD) system. Pesticide separation was achieved on a C18 (4.6 mm × 150 mm, 5 μm) analytical column with a isocratic elution of acetonitrile:water 40:60 % (v/v) with 0.6 mL L?1 acetic acid at a flow rate of 1 mL min?1. Linear regression coefficients (r (2)) of the external calibration curves were always above 0.9997. The limits of detection (LOD) and quantification (LOQ) of the method were 0.005 and 0.02 mg kg?1 for ASM, and 0.01 and 0.05 mg kg?1 for BTC, respectively. Recoveries were investigated at six fortification levels and were in the range of 90-120 % for ASM and 74-96 % for BTC with relative standard deviations (RSDs) below 11 % in all cases. The method was also validated by analyzing freshly spiked soil samples with 2.7% organic matter content at 0.5 mg kg?1 level, with slightly lower recovery values only for ASM. Moreover, recoveries for intermediate aged residues of the analytes were similar to fresh residues. This method was also applied to determine ASM half-life (t(?) = 8.7 h) and the rate of the acidic metabolite formation.     

Toxicity and tissue distribution of pentachlorophenol and permethrin in pipistrelle bats experimentally exposed to treated timber

The dependence of bats in Britain on houses as roosts may result in them being exposed to pesticides used in remedial timber treatments. Pentachlorophenol (PCP) and permethrin are used as a fungicide and an insecticide for timber treatment, respectively. The present study investigated toxicity and distribution in body tissues of these two pesticides in pipistrelle bats. Four groups of nine to ten bats were kept in separate outdoor flight enclosures and were provided with roost boxes treated with either PCP only, permethrin, PCP/permethrin mixture or solvent only (control). At the start of the experiment, mean (+/-SE) PCP and permethrin concentrations on the surface of wooden blocks that had been treated in the same way as roost boxes were 69.32+/-6.76 mg g(-1) (n=6) and 3.3+/-1.6 mg g(-1) (n=3), respectively. All bats exposed to PCP and PCP/permethrin treated boxes died within 24 and 120 h, respectively; nine out of the ten controls survived the 32 day experimental period (P<0.001; both groups compared with control). Bats exposed to permethrin treated boxes survived as well as controls. Mean (+/-SE) carcass PCP concentration (excluding deposits on fur) of bats exposed to PCP and PCP/permethrin treated boxes was 13.11+/-2.52 microg g(-1)BW (n=20). PCP burdens on fur were positively correlated with total weight of PCP in the carcass (P<0.001). PCP was present in fat depots, liver, kidney and the remainder of the body which, despite containing low PCP concentrations, was the main PCP reservoir (66.4+/-5.0% of carcass PCP load; n=20). Total PCP in the carcass was significantly correlated with lipid weight (P<0.005). Permethrin was not detectable in body washes and tissues of bats exposed to PCP/permethrin mixture or permethrin.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in marine mammals in the Canadian North

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in pooled samples of ringed seal (Phoca hispida) blubber, beluga (Delphinapterus leucas) blubber and polar bear (Ursus maritimus) liver and fat from several areas throughout the Canadian north and compared to mean PCB and HCB levels in the same samples. All seal samples, and all but one polar bear sample, had detectable 2,3,7,8-TCDD at concentrations ranging from 2 to 37 ng/kg, but TCDD was not found in beluga blubber (< 2 ng/kg). All seal samples and one of three beluga samples contained 2,3,7,8-TCDF at levels of 2 to 7 ng/kg, but TCDF was not found in any bear sample. TCDF must therefore be cleared rapidly by polar bears. No other PCDF congeners were found at detection limits of 4 to 8 ng/kg. OCDD concentrations in seal blubber and polar bear samples ranged from not detected (< 8 ng/kg) to 43 ng/kg. No apparent biomagnification of TCDD, OCDD or TCDF occurred from seal to bear fat, similar to previous findings for DDT, and unlike SigmaPCBs and HCB which biomagnified 6- to 17-fold. Highest concentrations of 2,3,7,8-TCDD and OCDD in seals and bears were found in the central Canadian Arctic Archipelago, and lowest were found in Hudson Bay, the reverse of PCB concentration distribution. The reason for higher levels of TCDD and OCDD in the Arctic than in the sub-Arctic is suggested to be trans-polar movement of aerosols with combustion-related origins in Eurasia. Levels of 2,3,7,8-TCDF were more evenly distributed throughout the North, and were positively correlated with PCB, but not with HCB or 2,3,7,8-TCDD levels in seals.     

Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Organochlorine compounds in Baltic salmon and trout. I. Chlorinated hydrocarbons and chlorophenols 1982

Polychlorinated hydrocarbons and chlorophenol compounds were analyzed in three populations of Baltic salmon (Salmo salar) and one population of Bothnian Bay trout (Salmo trutta). Muscles, livers and unfertilized eggs were studied and the analysis results treated by standard statistical methods. PCB, DDT residues, HCB and lindan were detected in most, 2,3,6-t-richlorocymene in some samples at levels which are near to the global baseline. Ten chlorophenol compounds were detected, 34DCC at 0–1000 ug/kg the others 0–100 ug/kg (fresh weight) levels. Chlorohydrocarbons showed some significant positive correlations with weight, and fat contents of the fish. Significances of the differences between populations and tissues were low or neglible except that the chlorophenols in liver were at clearly higher level than in muscle or eggs.     

Determination of Acaricide Residues in Saudi Arabian Honey and Beeswax Using Solid Phase Extraction and Gas Chromatography

Determination of acaricide residues of flumethrin, tau-fluvalinate, coumaphos, and amitraz in honey and beeswax was carried out using a rapid extraction method utilizing C-18 SPE cartridges and an analytical method utilizing GC with ECD, NPD, and MSD detectors for the four acaricides. Recovery percentages from the extraction method ranged from 90–102%, while the minimum detection levels ranged from 0.01–0.05 mg/kg for the acaricides. Nine of the 21 analyzed samples were found to be contaminated with the acaricides tau-fluvalinate and coumaphos. Neither flumethrin nor amitraz was detected in any of the honey or wax samples. Coumaphos was found only in honey samples in which two samples exceeded the tolerance levels set by EPA and EC regulations. It has not been detected in beeswax. Five honey samples and eight beeswax samples were found to be contaminated with tau-fluvalinate. One of the wax samples was contaminated with a relatively high residue of tau-fluvalinate and contained above 10 mg/kg.     

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R²) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.     

Minor crops for export: A case study of boscalid,pyraclostrobin, lufenuron and lambda-cyhalothrin residue levels on green beans and spring onions in Egypt

Dissipation rates of boscalid [2-chloro-N-(4′ -chlorobiphenyl-2-yl)nicotinamide], pyraclostrobin [methyl 2-[1-(4-chlorophenyl) pyrazol-3-yloxymethyl]-N-methoxycarbanilate], lufenuron [(RS)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)urea] and λ-cyhalothrin [(R)-cyano(3-phenoxyphenyl)methyl (1S,3S)-rel-3-[(1Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate] in green beans and spring onions under Egyptian field conditions were studied. Field trials were carried out in 2008 in a Blue Nile farm, located at 70 kilometer (km) from Cairo (Egypt). The pesticides were sprayed at the recommended rate and samples were collected at pre-determined intervals. After treatment (T₀) the pesticide residues in green beans were 7 times lower than in spring onions. This is due to a different structure of vegetable plant in the two crops. In spring onions, half-life (t_1/2) of pyraclostrobin and lufenuron was 3.1 days and 9.8 days respectively. At day 14th (T₁₄) after treatment boscalid residues were below the Maximum Residue Limit (MRL) (0.34 versus 0.5 mg/kg), pyraclostrobin and λ -cyhalothrin residues were not detectable (ND), while lufenuron residues were above the MRL (0.06 versus 0.02 mg/kg). In green beans, at T₀, levels of boscalid, lufenuron and λ -cyhalothrin were below the MRL (0.28 versus 2 mg/kg; ND versus 0.02 mg/kg; 0.06 versus 0.2 mg/kg, respectively) while, after 7 days treatment (T₇) pyraclostrobin residues were above the MRL (0.03 versus 0.02 mg/kg). However, after 14 days the residue level could go below the MRL (0.02 mg/kg), as observed in spring onions.     

Priority organic pollutant assessment of sludges for agricultural purposes

A comprehensive characterization of five of the seven priority organic pollutants listed in the draft of the "Working document on sludge" [EU, 2000. Working Document on Sludge 3rd Draft. Unpublished, 19 p] has been carried out during 2001-2003 in sludge samples from Catalonia (NE Spain). One hundred and thirty-nine samples belonging to 20 Waste Water Treatment Plants (WWTPs), seven sludge treatment (thermal drying) and three composting sludge plants were taken in order to determine the concentration of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs), di-2-(ethyl-hexyl)-phthalate (DEHP), nonylphenol and nonylphenol ethoxylates with one or two ethoxy groups (NPE), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). PCDD/F concentrations were in general lower than the 100 ng I-TEQ/kg limit suggested in the above-mentioned document. In the same way, 98.5% for PCBs, 97% for PAH and 92.8% for DEHP of the samples presented concentrations lower than 0.8 mg/kg dm, 6 mg/kg dm and 100 mg/kg dm, respectively. In contrast, the vast majority of samples contained NPE concentrations much higher than 50mg/kg dm limit. The values ranged from 14.3 to 3150 mg/kg dm (median value=286.6 mg/kg) being composted sludge samples the less contaminated ones (17.9-363.4 mg/kg dm; median value=89.3 mg/kg). Special attention should be paid to the Catalan sludge NPE contamination owing to the high levels detected.     

Residue evaluation of famoxadone and trifloxystrobin in cultivated mushrooms

Dissipation of the fungicides famoxadone and trifloxystrobin in basidiocarps of Agaricus bisporus was studied in mushroom growing rooms. The mushroom samples taken at all three consecutive production flushes following single or split applications of the fungicides were extracted with solvents and the residues were determined by using a gas chromatograph equipped with an electron capture detector (GC-ECD). Recoveries from the fortified control samples ranged from 87 to 105%. Following drench applications at 0.1-1 g/m2 of culture bed area, the highest famoxadone residue determined in basidiocarps was 0.1447 mg/kg. Analysis of trifloxystrobin revealed a quantitative relationship between the application rate (0.8-1.8 g/m2) and the residue levels of both the parent compound and its acid metabolite. The maximal combined residues of trifloxystrobin and its metabolite were 0.1313 mg/kg. Short- and long-term dietary risk assessment for both fungicides was carried out using consumption data from World Health Organization and the UK Pesticide Safety Directorate's Ten Consumer Model. The potential acute and chronic residue intakes via mushroom consumption were below toxicologically significant indicators.