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.     

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.     

Arsenic speciation in plants growing in arsenic-contaminated sites

Concentrations of total arsenic and of arsenic species were determined by ICPMS and HPLC-ICPMS in terrestrial plant samples. The arsenic concentration in plant samples from the contaminated sites ranged from 1.14 to 98.5 mg kg(-1) (dry mass). However, a very high value, exceeding largely this range was found in a moss sample growing in the contaminated area (1750 mg kg(-1)). Plants growing in a non-contaminated area with similar geological characteristics contained 0.06-0.58 mg As kg(-1). Plant samples from different species were selected and extracted with water, water/methanol (9+1, v/v), and water/methanol (1+1, v/v). Water/methanol (9+1, v/v) was selected as extractant for the speciation analysis for all the plant samples. The extraction efficiencies ranged from 3.0% to 41.4%, with good agreement between samples from the same plant species. Arsenite and/or arsenate were found in all the plant samples. Additionally, methylarsonate (MA), dimethylarsinate (DMA), trimethylarsine oxide (TMAO) and tetramethylarsonium ion (TETRA) were also identified in several plants, and in some cases MA and DMA were the main species found. TMAO, which is usually found as a trace constituent in organisms, was also a significant arsenical in one of the studied samples, where it constituted 24% of the extracted arsenic. In the present study, the patterns of arsenic species varied with the plant species and much higher proportion of organoarsenicals was found in plants from the more contaminated sites.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Persistence,degradation and leaching of coumaphos in soil

Abstract

Dissipation, degradation and leaching of fresh ¹⁴C coumaphos, alkylated ¹⁴C coumaphos and aged residues of ¹⁴C coumaphos from vats were studied in alkaline sandy loam soil in soil columns in the field under subtropical conditions in Delhi for a year. Dissipation, degradation and bound residue formation was more in case of alkali treated coumaphos than fresh coumaphos. After 365 days total residues of fresh coumaphos accounted for 33.25% while that of alkali treated coumaphos was 19.12%. Bound residue formation was almost double in case of alkali treated coumaphos (18.95%) than fresh coumaphos (9.53%) after 150 days followed by release of bound residue in both the cases. The proportion of metabolites 4 ‐ methylumbelliferone, chlorferon and potasan collectively was 86.05% in fresh coumaphos extractable residues while the same was 91.74% in alkali treated coumaphos after 365 days. Aged residues from vats containing copper sulphate and buffer were found to be more persistent in soil as total residues remained were 95.58% in comparison with 83.09% total residues of aged residues from vats containing only buffer after 150 days of treatment. Copper sulphate seems to inhibit the degradatiion of coumaphos in soil by microorganisms. Chlorferon was the major metabolite in generally all the samples. Coumaphos did not leach below 10 cm in all the cases.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part II. Application to sediment and sludge samples in Austria

Soxhlet extraction and high-performance liquid chromatography (HPLC) coupled to tandem mass spectrometry detection (MS/MS) was used for the determination of selected quaternary ammonium compounds (QACs) in solid samples. The method was applied for the determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds in sediment and sludge samples in Austria. The overall method quantification limits range from 0.6 to 3 microg/kg for sediments and from 2 to 5 microg/kg for sewage sludges. Mean recoveries between 67% and 95% are achieved. In general sediments were especially contaminated by C12 chain benzalkonium chloride (BAC-C12) as well as by the long C-chain dialkyldimethylammonium chloride (DDAC-C18) with a maximum concentration of 3.6 mg/kg and 2.1mg/kg, respectively. Maxima of 27 mg/kg for DDAC-C10, 25 mg/kg for BAC-C12 and 23 mg/kg for BAC-C14 were determined for sludge samples. The sums of the 12 selected target compounds range from 22 mg/kg to 103 mg/kg in the sludge samples.     

Multiresidue determination of carbamate,organochlorine, organophosphorus,and dicarboximide pesticides in lettuce by GC/MS

An extraction method based on matrix solid-phase dispersion was developed to determine pirimicarb, methyl parathion, malathion, procymidone, α -endosulfan and β -endosulfan in lettuce using gas chromatography-mass spectrometry. The best results were obtained using 4.0 g of lettuce, 2.0 g of silica as dispersant sorbent, 0.1 g of activated carbon as clean up sorbent and acetonitrile as eluting solvent. The method was validated using lettuce samples fortified with pesticides at six different concentration levels (0.1 to 2.0 mg/kg). Average recoveries (7 replicates) ranged from 50 to 120 %, with relative standard deviations between 0.6 and 8.0 %. Detection and quantification limits for lettuce ranged from 0.01 to 0.02 mg/kg and 0.04 to 0.10 mg/kg, respectively.     

Environmental contamination with polychlorinated biphenyls in the area of their former manufacture in Slovakia

Evidently increased environmental pollution as a consequence of the 25-year manufacture of polychlorinated biphenyls (PCBs) in eastern Slovakia was observed. PCB levels determined in ambient air, soil, surface water, bottom sediment, wildlife (fish and game) samples collected in a potentially contaminated area of about 250 km2 (a part of the Michalovce district) were compared with those determined in a control area (Stropkov district). Up to 1700 ng/m3 were found in ambient air in a village close to a manufacturer's dumping site and a highly contaminated manufacturer's effluent canal whereas PCB concentrations in ambient air samples taken in villages in the control area were about 80 ng/m3 only. While soil samples taken from the agricultural fields of the polluted area contained PCBs at levels comparable with soil samples from the control area (about 0.008 mg/kg) much higher values (from 0.4 to 53,000 mg/kg) were determined in soil taken in the vicinity of manufacturer's landfill and storage sites and especially plants preparing asphalted gravel using formerly PCBs in their heat-exchanging systems. The contamination of the Laborec river and large Zemplinska Sirava reservoir is caused by the manufacturer's effluent canal since PCB levels in the canal sediment are still to be found about 3000 mg/kg. While PCB levels in sediment samples from Michalovce watercourses ranged between 1.7 and 6 mg/kg, sediment samples from the control Stropkov district ranged between 0.007 and 0.052 mg/kg only. Fish living in contaminated Michalovce waters contained about hundred times higher PCB levels than those caught in Stropkov ones. Similarly, game animals shot in Michalovce forests contained several times higher levels than those shot in Stropkov ones.     

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.     

Method Development for Determination of Fluroxypyr in Soil

Abstract

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 µg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1–0.2 µg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4–50 µg/L ranged from 88 to 98% with relative standard deviations of 3.0–5.8% with a minimum detection limit of 4 µg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS® HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2–6.2%, respectively. The limit of detection in method 4 was further improved to 1 µg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1–50 µg/kg ranged from 82–107% with relative standard deviations of 0.5–4.7%.     

Solid-phase extraction for multi-residue analysis of pesticides in honey

A fast and simple multi-residue method for the analysis of 15 organophosphorus (OP), 17 organochlorine (OC), 8 pyrethroids (PYR), 12 N-methyl-carbamate (NMC) pesticide residues and bromopropylate in honey is presented. Ready–to–use EXtrelut®NT 20 column, eluted with dichloromethane, was used to extract the pesticide residues from the aqueous-acetone honey sample, obtaining a clean extract directly analyzable. Determination was carried out by gas chromatography (GC) coupled with flame photometric detector (FPD) for OP compounds and by GC coupled with mass spectrometry detector (MSD) for OC and PYR pesticides and bromopropylate. The NMC pesticides were analysed by liquid chromatography-double derivatization coupled with spectrofluorimetric detector (LC/DD/Fl). This method allows the determination of the 53 pesticide residues at low concentrations (0.0005–0.074 mg/kg) and can be used to assess the compliance with the Maximum Residues Levels (MRLs) set by the European Union. The performance of the method was evaluated and specificity, linearity, recovery, repeatability, reproducibility, limit of quantification (LOQ) and limit of detection (LOD) were determined. A good linearity (r²? 0.99) was found in the range 0.0005–0.074 mg/kg for the majority of the compounds studied. Most of the pesticides had recoveries in the range 70–103 % and values of relative standard deviation (RSD) < 20 for repeatability and reproducibility, showing good accuracy and precision of the method. Aldicarb partially degraded in aldicarb sulphoxide during the analytical procedure, giving anomalous values. The LOQ for all pesticides investigated was from 0.0005 to 0.025 mg/kg while the LOD ranged from 0.0002 to 0.008 mg/kg.     

Cyanide residue levels in extracted honey, comb honey and wax cappings.

Cyanide (CN) residue levels were determined in samples of extracted honey, comb honey and was cappings at 1 hr, 24 hr, and 48 hr intervals after destroying the bees in honey bee colonies with normal (ca. 8.5 g) and twice normal (ca. 17 g) doses of CyanogasR A-dust. Applications of CyanogasR A-dust, administered by means of a dust pump at normal and twice normal doses, gave an average residue of 0.01 and 0.04 microgram CN/g of extracted honey, 0.01 and 0.02 microgram CN/g of comb honey and 0.04 and 0.06 microgram CN/g of wax cappings, respectively. When the CyanogasR A-dust (ca. 17 g) was placed on a tray and placed on the bottom board of the hive, the average residue levels for extracted honey, comb honey and wax cappings were less than 0.004, 0.01 and 0.02 microgram CN/g, respectively. Random honey samples from beekeepers, who used CyanogasR to destroy bees, had a median level of 0.031 microgram CN/g, whereas honey from a packing plant and other commercial samples contained less than 0.004--0.026, median less than 0.004 microgram CN/g. Based on residue data from this study, the temporary registration for CyanogasR, to kill honey bees after crop removal, was revised to a full registration in May 1977.     

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.     

Analysis of organophosphorus pesticides in whole milk by solid phase microextraction gas chromatography method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-microm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30 degrees C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 microgL-1 to 1.75 microgL-1 for coumaphos and 0.69 microgL-1 to 6.90 microgL-1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 microgL-1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 microgL-1 for dichlorvos and 0.066 microgL-1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Comparison of Three Extraction Methods for 17 β-Estradiol in Sand,Bentonite, and Organic-Rich Silt Loam

Extraction is an important procedure for samples that contain soil because other compounds in soil may affect analysis of estrogens. This study was conducted to evaluate three different extraction methods for 17β-estradiol in soil. Sand, bentonite, and organic-rich silt loam were spiked with 1 mg kg^{? 1} of 17β-estradiol as a model compound of estrogens. 17β-estradiol and its metabolites, estrone and estriol, were extracted using (i) a modified Bligh and Dyer extraction, (ii) a pressurized fluid extraction, and (iii) a diethyl ether extraction, and measured by liquid chromatography tandem mass spectrometry. There were significant differences in the extraction efficiency for 17β-estradiol among the extraction methods and the soils: the efficiencies ranged from 10% to 97%. Overall, the diethyl ether extraction method had the largest efficiency of 17β-estradiol with 45% and 57% for bentonite and silt loam, respectively. Transformation of 17β-estradiol to estrone and estriol in the different extraction methods was less than 3.6% during the extraction procedures. This study underlined the importance of sample preparation for estrogen analysis in soil samples.     

Assessment of honey contamination with polycyclic aromatic hydrocarbons

The aim of this study was to assess honey contamination by polycyclic aromatic hydrocarbons. Six species of honey were examined, as well as rape blossom and soil from villages P?czerzyno and Przybys?aw in West Pomerania, Poland. The instrumental analysis was performed using a HP 6890 gas chromatograph coupled to a HP 5973 mass spectrometer with selected ion monitoring (SIM). Quantification was done by gas chromatography-mass spectrometry (GC-MS) using perdeuterated internal standards. Both soil samples showed high levels of all 23 PAHs, whereas honey contained mostly non-carcinogenic PAHs of low molecular weight. The most contaminated honey from P?czerzyno contained 0.24 μg kg-1 benzo[a]pyrene. Moreover, despite low contamination of honey, a positive correlation was found between PAH content in honey, blossom and soil.     

Persistence, degradation and leaching of coumaphos in soil

Dissipation, degradation and leaching of fresh 14C coumaphos, alkylated 14C coumaphos and aged residues of 14C coumaphos from vats were studied in alkaline sandy loam soil in soil columns in the field under subtropical conditions in Delhi for a year. Dissipation, degradation and bound residue formation was more in case of alkali treated coumaphos than fresh coumaphos. After 365 days total residues of fresh coumaphos accounted for 33.25% while that of alkali treated coumaphos was 19.12%. Bound residue formation was almost double in case of alkali treated coumaphos (18.95%) than fresh coumaphos (9.53%) after 150 days followed by release of bound residue in both the cases. The proportion of metabolites 4-methylumbelliferone, chlorferon and potasan collectively was 86.05% in fresh coumaphos extractable residues while the same was 91.74% in alkali treated coumaphos after 365 days. Aged residues from vats containing copper sulphate and buffer were found to be more persistent in soil as total residues remained were 95.58% in comparison with 83.09% total residues of aged residues from vats containing only buffer after 150 days of treatment. Copper sulphate seems to inhibit the degradatiion of coumaphos in soil by microorganisms. Chlorferon was the major metabolite in generally all the samples. Coumaphos did not leach below 10 cm in all the cases.     

Determination of PAHs in wastewater irrigated agricultural soil using accelerated solvent extraction

A procedure was developed for determination of 16 polycyclic aromatic hydrocarbons (PAHs) in heavily contaminated paddy soil from wastewater irrigated farmland near Tianjin. The sample was distilled with accelerated solvent extraction (ASE), purified by a silica gel column, and measured with GC/MS. The optimal conditions for the distillation were at 140 degrees C (1500 psi) with a 1:1 mixture of dichloromethane and acetone for 5 min. Application of cyclohexane for extract transfer improved the recovery when the ASE extraction was followed by a silica gel cleanup procedure. Recoveries from the method for 16 PAHs ranged from 57-140% with the coefficients of variation of the results ranging from 0.35% to 5.75%. The total 16 PAHs in a composite sample collected from a wastewater irrigated paddy field near Tianjin was 3.90 mg/kg.     

Removal of PCBs from a Contaminated Soil Using CF-Systems® Solvent Extraction Process

ABSTRACT

The U.S. Environmental Protection Agency’s (EPA) Superfund Technical Assistance Response Team (START) in cooperation with EPA’s Superfund Innovative Technology Evaluation (SITE) program evaluated a pilot scale solvent extraction process developed by CF-Systems. This process uses liquefied propane to extract organic contaminants from soils, sludges, and sediments. A pilot-scale evaluation was conducted in Golden, CO at Hazen Research, Inc., using CF-Systems’ trailer-mounted organics extraction unit. Approximately 1,000 pounds of soil, with an average poly-chlorinated biphenyl (PCB) concentration of 260 mg/kg, was obtained from a remote Superfund site. Six 100-pound batches of the contaminated soil were extracted using multiple extraction sequences. Three of the six batch runs were subjected to three extraction sequences each, so that process variability could be evaluated. Results showed that PCB removal efficiencies varied between 91.4 and 99.4%, with the propane-extracted soils retaining low concentrations of PCBs (19.0–1.8 mg/kg). Removal efficiencies of oil and grease (O&G) were found to be 96.0 to 99.6% with propane-extracted soils retaining O&G concentrations from 279 to <20 mg/kg. Overall extraction efficiency was found to be dependant upon the numberof extraction cycles used.     

Determination of hydrocarbons in old creosote contaminated soil using headspace solid phase microextraction and GC-MS.

Headspace solid phase microextraction (HS-SPME) has been used together with GC-MS to analyze organic substances directly in a soil, heavily contaminated with PAHs/creosote (approximately 300 mg/kg soil), from an old gaswork site in Stockholm, Sweden. The HS-SPME results, both qualitative and quantitative, were compared with traditional liquid extraction using ethyl acetate/hexane (20:80). It was shown that the concentrations determined with HS-SPME at 60 degrees C correlated well, for compounds containing up to two and three aromatic rings (naphthalenes, acenaphthene, acenaphthylene and fluorenes, while a lower concentration was obtained for phenanthrene, anthracene, fluoranthene and pyrene. The total concentrations for each compound determined with HS-SPME ranged from 2 to 25 microg/g soil. Quantification was done using standard addition of compounds directly to the soil samples. The bioavailable fraction of the compounds in the contaminated soil at 20 degrees C was analyzed using external calibration by spiking sterile uncontaminated sand (same texture and particle size as the contaminated soil but without a heavily sorbed organic fraction) with hydrocarbon standards in different concentrations. Storage of exposed fibers at 20 degrees C showed that analysis should be done within two days to make qualitative measurements and earlier (as soon as possible) for quantitative determinations.