Development of IC-ELISA for detection of organophosphorus pesticides in water

Diethyl (carboxymethyl) phosphonate (DECP) was used as the hapten to develop an indirect competitive enzyme-linked immunosorbent assay (IC-ELISA) for detecting organophosphorus pesticides (OPs). Conjugator of DECP with bovin serum albumin (BSA) was used as the immunogen for producing the polyclonal antibodies (PcAbs). Three antisera were obtained after the immune procedure. Characterization studies of the PcAbs indicated that the titer of antiserum-1 was highest in 3 antisera, and antiserum-1 had high affinity and specificity to the parathion, dichlorvos and pirimiphos. The IC-ELISA showed an IC₅₀ of 0.428 μ g/mL with a detection limit of 0.0125 μ g/mL to parathion. The assay also indicated that the IC₅₀ values of pirimiphos and dichlorvos were 0.331 μ g/mL and 1.25 μ g/mL respectively, and the detection limits of pirimiphos and dichlorvos were 0.0116 μ g/mL and 0.048 μ g/mL respectively. Recoveries of parathion, pirimiphos and dichlorvos spiked into water samples ranged from 90% to 160%. The results indicated that the ELISA could be a convenient and supplemental analytical tool for monitoring OPs residues in environmental water samples.     

Simple analytical method for determination of pesticide residues in human serum by liquid chromatography tandem mass spectrometry

The aim of this study was to develop an analytical method for the determination of residues of organophosphorus and carbamate pesticides which are widely used in Tunisia. This method involves a liquid-liquid extraction procedure followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for the identification and quantification of compounds. Ionization of molecules was performed by the electrospray mode. Multiple reactions monitoring (MRM) was the acquisition mode used for the monitoring of two MS/MS transitions for each compound. The average recoveries obtained, at three different fortification levels, ranged between 65% and 106% for most of the pesticides studied, except for methamidophos (lower than 25%).The linearity of the method was in the range of 5 to 50 μ g/L with a correlation coefficient from 0.995 to 0.999, depending on the analyte. The estimated limit of detection and limit of quantification were 2 μ g/L and 5 μ g/L, respectively. The precision of the analytical procedure was satisfactory and the coefficients of variation, evaluated at three concentration levels were lower than 15% for most pesticides studied. The application of the method was investigated in a population of agricultural workers chronically exposed to various pesticides some of which, such as carbofuran, carbendazim, methomyl and pirimicarb, were detected in some serum samples.     

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.     

Brominated flame retardants and perfluorinated chemicals, two groups of persistent contaminants in Belgian human blood and milk

We assessed the exposure of the Flemish population to brominated flame retardants (BFRs) and perfluorinated compounds (PFCs) by analysis of pooled cord blood, adolescent and adult serum, and human milk. Levels of polybrominated diphenyl ethers (PBDEs) in blood (range 1.6-6.5 ng/g lipid weight, lw) and milk (range 2.0-6.4 ng/g lw) agreed with European data. Hexabromocyclododecane ranged between <2.1-5.7 ng/g lw in milk. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) dominated in blood and ranged between 1 and 171 ng/mL and <0.9-9.5 ng/mL, respectively. Total PFC levels in milk ranged between <0.5-29 ng/mL. A significant increase in PBDE concentrations was detected from newborns (median 2.1) to the adolescents and adults (medians 3.8 and 4.6 ng/g lw, respectively). An identical trend was observed for PFOS, but not for PFOA. We estimated that newborn exposure to BFRs and PFCs occurs predominantly post-natally, whereas placental transfer has a minor impact on the body burden.     

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties

This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.     

Long-chain perfluorinated chemicals in digested sewage sludges in Switzerland

This study focused on the occurrence of long-chain perfluorinated chemicals (PFCs) in anaerobically stabilized sewage sludges from 20 municipal WWTPs using current and historic samples to evaluate the levels of PFCs and to identify the relative importance of commercial and industrial sources. A quantitative analytical method was developed based on solvent extraction of the analytes and a LC-MS/MS system. For total perfluoralkyl carboxylates (PFCAs), the concentrations ranged from 14 to 50 μg/kg dry matter. Concentrations of perfluorooctane sulfonic acid (PFOS) ranged from 15 to 600 μg/kg dry matter. In three WWTPs, the PFOS levels were six to nine times higher than the average values measured in the other plants. These elevated PFOS concentrations did not correlate with higher levels of PFCAs, indicating specific additional local sources for PFOS at these WWTPs. Average concentrations in selected samples from the years 1993, 2002, and 2008 did not change significantly.     

Occurrence and dietary exposure assessment of PFOS and PFOA in cultured Trachinotus ovatus in China

In this study, investigation was conducted into concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in Chinese farmed Trachinotus ovatus between 2014 and 2015 using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) method. The tissue distribution (muscle, skin, liver, kidney and gill) in Trachinotus ovatus was also assessed. The detection frequencies of PFOS and PFOA in fish were 92% and 3%, respectively, and the mean concentrations were 0.392 and 0.015 μg/kg wet weight. The analysis of PFOS distribution in different tissues in Trachinotus ovatus showed the following trend: skin> gill> kidney> liver> flesh. Results revealeded farmed Trachinotus ovatus in China to generally be contaminated with PFOS. Moreover, the average daily intake for Chinese urban residents calculated on the basis of pollution content was 0.268 ng/kg body weight/d (PFOS) and 0.014 ng/kg body weight /d (PFOA), respectively. Both hazard ratio values were less than 1, indicating that exposure levels of PFOS and PFOA through Trachinotus ovatus consumption may not lead to adverse health effects in the Chinese population.     

Validation of an efficient method for the determination of pesticide residues in fruits and vegetables using ethyl acetate for extraction

In this study, a version of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was modified to use ethyl acetate (EtOAc) rather than acetonitrile (MeCN) for extraction in the determination of multiple pesticide residues in fruits and vegetables. EtOAc is better suited than MeCN for gas chromatographic (GC) analysis with electron capture detection (ECD) and nitrogen-phosphorus detection (NPD). The method entailed extraction of 30 g chopped sample plus 5 g NaHCO(3) and 30 g anhydrous Na(2)SO(4) with 60 mL EtOAc using a probe blender. After a centrifugation step, removal of residual water and cleanup were performed using dispersive solid-phase extraction (dispersive-SPE) with MgSO(4) and primary secondary amine (PSA) sorbent. (14)C-labeled chlorpyrifos with liquid scintillation counting was used to assist in optimizing and characterizing the method, and GC-ECD and GC-NPD were used for analysis of 24 selected pesticides. The method was validated using tomato, apple and frozen green bean matrices spiked at 0.05, 0.5, and 5 mg/kg. For 22 of the analytes, recoveries averaged 93% for all three commodities over the validation range with a relative standard deviation of 10% (n = 1182). Lower recoveries of dichlorvos were obtained with the method and iprodione determination was compromised in the green beans by an interfering peak. Typical limits of detection were 0.005-0.01 mg/kg with the method.     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

Determination of acidic herbicides in cereals by QuEChERS extraction and LC/MS/MS

A simple and rapid method has been studied for the determination of acidic herbicides (2,4-D, Dichlorprop, Dichlorprop-p, Fluazifop, Fluroxypyr, MCPA, Mecoprop and Mecoprop-p) on cereals (rye). The method involves an alkaline hydrolysis with sodium hydroxide in order to release covalently bound compounds, prior to QuEChERS extraction, followed by neutralization and analysis via liquid chromatography-double mass spectrometry LC/MS/MS. The performance of the method either with or without alkaline hydrolysis was studied in terms of recovery rates and limit of quantification (LOQ). In either case, recoveries were determined at four spiking levels (0.02 mg/kg, 0.05 mg/kg, 0.1 mg/kg and 0.5 mg/kg) with 5 replicates for each level. Mean recoveries ranged from 90 to 120 %, whereas relative standard deviations (RSD %) proved to be less than 20 %. Quantitative analysis was carried out by the internal standard (Nicarbazin) and the LC/MS/MS analysis was performed in electrospray ionisation (ESI) negative mode using a Zorbax XCB Eclipse column. The developed method was applied to the analysis of several cereals commercially available like as rye flour, oat meal, oat flakes and dehusked oat. Residue levels were found below the limit of quantification (LOQ) of the method. The method has been tested in EU Proficiency Tests for cereals with good results.     

Free Fatty Acids and Sterols in Swine Manure

Free fatty acids and sterols were assessed in fresh manure and anaerobic lagoon sludge from swine production facilities in North Carolina. Eight free fatty acids and five sterols were identified and quantified in both manure and sludge samples. Compound identification was performed by gas chromatography/mass spectroscopy (GC-MS), and compound quantities were determined by gas chromatography after solid phase extraction with a 50:50 mixture of diethyl ether and hexane. The free fatty acids occurring in greatest abundance in both fresh manure and lagoon sludge were palmitic, oleic, and stearic. Free fatty acid content in fresh manure ranged from approximately 3 μ g g^?1 dry weight (dw) to over 45 μ g g^?1 dw. In lagoon sludge, free fatty acid content ranged from about 0.8 μ g g^?1 dw to nearly 4 μ g g^?1 dw. Coprostanol and epicoprostanol were the sterols in largest concentrations in fresh manure and lagoon sludge samples. Total sterol content ranged from approximately 0.5 μ g g^?1 dw to around 11 μ g g^?1 dw in fresh manure and from 3.5 μ g g^?1 dw to almost 9 μ g g^?1 dw in lagoon sludge. Fresh manure and lagoon sludge both had high levels of inorganic cations (e.g., Ca, Mg, Fe) capable of binding free fatty acids and forming insoluble complexes, thereby potentially reducing fatty acid biodegradation. In anaerobic lagoons, sterols are an organic fraction of sludge that are resistant to bacterial degradation. In the case of fresh manure, fatty acids could represent a potential source of energy via the manufacture of biodiesel fuel, if efficient means for their extraction and transesterification can be devised.     

Toxicity of the pyrethroid pesticide fenvalerate to freshwater catfish clarias gariepinus: Lethality,biochemical effects and role of dietary ascorbic acid

Static bioassays were made in the laboratory to determine lethal concentration of the pyrethroid pesticide fenvalerate [(RS)-alpha-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate] for the freshwater catfish Clarias gariepinus and effects of sublethal concentrations of the pesticide on some biochemical parameters of the fish. For exposure periods of 24 to 96 h, LC₅₀ values of fenvalerate ranged from 5.83–4.76 μ g/L and 4.24–2.94 μ g/L, respectively for water and acetone soluble fenvalerate. Two sublethal concentrations of fenvalerate were used in the bioassays for biochemical parameters: 2.1 μ g/L for 24 h and 1.4 μ g/L for 96 h exposure, both concentrations representing 50% of LC₅₀ value of acetone soluble fenvalerate for the respective exposure period. Hepatosomatic index, liver glycogen, alkaline phosphatase of liver and ascorbic acid of blood, liver, and kidney decreased while haemoglobin (Hb) %, plasma glucose levels and acid phosphatase level of liver increased after 24 h exposure to 2.1 μ g/L fenvalerate. Longer exposure (96 h) to even a lower concentration (1.4 μ g/L) of fenvalerate resulted in reduction of all the parameters (except Hb %) tested as compared with control. Fish previously fed for 60 days with a diet supplemented by a high level of ascorbic acid (100 mg/100 g diet) could reverse most of the effects caused by 24 h exposure to 2.1 μ g/L fenvalerate. A lower level of ascorbic acid (50 mg/ 100 g diet) supplement could not influence these effects of fenvalerate. Even the higher dose of ascorbic acid supplementation (100 mg/100 g diet) could not relieve the stress parameters, except for Hb% and HSI, when the pesticide was applied at 1.4 μ g/L for a longer time period (96 h).     

Development and validation of LC-MS/MS method for the determination of Ochratoxin A and its metabolite Ochratoxin α in poultry tissues and eggs

The objective of this study was to develop a liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the determination of Ochratoxin A (OTA) and Ochratoxin α (OTα) in poultry tissues and eggs. The two toxins were extracted by a mixture of acetonitrile/water, purified with a reversed phase C18 solid phase extraction column (SPE) and determined by LC-MS/MS. The LC-MS/MS method performances were evaluated in terms of linearity in solvent and in matrix (ranged from 0.5 to 15.10 µg L^?1 for OTA and from 0.60 to 17.85 µg L^?1 for OTα), limit of detection (LOD), limit of quantitation (LOQ), specificity, accuracy and precision in repeatability conditions. Recovery experiments were performed by spiking poultry liver, kidney, muscle and eggs around 1 µg kg^?1 and 10 µg kg^?1. LODs were 0.27 and 0.26 µg kg^?1 while LOQs were fixed at 1.0 and 1.2 µg kg^?1 for OTA and OTα, respectively. Main recoveries for OTA ranged from 82 to 109% and for OTα ranged from 55 to 89%. The values of within-laboratory relative standard deviation (RSD_r) were equal to or below 20%. Considering the results obtained and that all analytical performance criteria were fulfilled, the new extraction and purification method developed for OTA and OTα determination in animal tissues and eggs was found appropriate for control laboratories and research activities designed to ensure food safety.     

3种短链脂肪酸对活性污泥储存PHA的影响

采用经乙酸钠驯化培养具有一定聚羟基烷酸酯(PHA)储存能力的活性污泥,考察乙酸、丙酸和丁酸3种短链脂肪酸,以及乙酸、丁酸分别与丙酸按1∶1、1∶2、2∶1比例组合成的6种混合酸作为碳源时对活性污泥中PHA的储存和转化的影响。实验结果表明,在3种短链脂肪酸中,以丁酸为碳源得到活性污泥PHA储存量最高,为40.53 mg/g;在混合酸中,乙酸与丙酸按1∶2组合时,系统PHA储存量最高,为773.4 mg/g。混合酸相对于单一的脂肪酸碳源更有利于活性污泥储存PHA。在混合酸总量一定的条件下,随着丙酸比例的增加,乙酸与丙酸混合比丁酸与丙酸混合更有利于微生物的PHA储存。     

Development,validation of QuEChERS-based method for simultaneous determination of multiclass pesticide residue in milk,and evaluation of the matrix effect

Extraction and quantification of pesticide residue from the milk matrix at or below the established maximum residue limit (MRL) is a challenging task for both analytical chemists and the regulatory institutions to take corrective actions for the human health and safety. The main aim of the study is to develop a simple rapid and less expensive QuEChERS extraction and cleanup method for simultaneous analysis of 41 multiclass pesticide residue in milk by gas chromatography-electron capture detector (GC-ECD), followed by confirmation of the residues with gas chromatography-mass spectrometer (GC-MS). Effect of sorbent type, temperature, spiking concentration, matrix effect (ME), measurement uncertainty (MU), inter- and intra-assay repeatability, reproducibility of recovery, and trueness of the results were investigated to validate the effectiveness of the method. Limit of determination (LOD) and limit of quantitation (LOQ) for all the analytes ranged within 0.001–0.02 and 0.002–0.05 µg mL^?1, respectively. The % recovery of all the pesticides ranged between 91.38 and 117.56% with relative standard deviation (RSD) below 2.79%. The MU for all the analytes was ≤29% of respective LOQs, and except for few pesticides, the ME was largely negative. The method fulfilled all the SANTE guidelines and thus can be extended for routine analysis of multiclass pesticide residue in milk.     

Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland

We performed a trace analytical study covering nine hormonally active UV-filters by LC-MS/MS and GC-MS in river water and biota. Water was analysed at 10 sites above and below wastewater treatment plants in the river Glatt using polar organic chemical integrative samplers (POCIS). Four UV-filters occurred in the following order of decreasing concentrations; benzophenone-4 (BP-4) > benzophenone-3 (BP-3) > 3-(4-methyl)benzylidene-camphor (4-MBC) > 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC). BP-4 ranged from 0.27 to 24.0 μg/POCIS, BP-3, 4-MBC and EHMC up to 0.1 μg/POCIS. Wastewater was the most important source. Levels decreased with higher river water flow. No significant in-stream removal occurred. BP-3, 4-MBC and EHMC were between 6 and 68 ng/L in river water. EHMC was accumulated in biota. In all 48 macroinvertebrate and fish samples from six rivers lipid-weighted EHMC occurred up to 337 ng/g, and up to 701 ng/g in 5 cormorants, suggesting food-chain accumulation. UV-filters are found to be ubiquitous in aquatic systems.     

Runoff of trifluralin,metolachlor, and metribuzin from a clay loam soil of Louisiana

Trifluralin[2,6-dinitro-N,N-dipropyl-4-(trifluormethyl)benzenamine], metolachlor[2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] and metribuzin[4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)one] were applied as pre-emergent herbicides to soybean plots in Louisiana (LA) at the rate of 1683 g/ha, 2759 g/ha and 609 g/ha, respectively. The concentrations of trifluralin in the runoff water ranged between 0.09 ng/mL and 0.02 ng/mL, which is lower than the 2 ng/mL US Environmental Protection Agency (EPA) advisory level for trifuralin in drinking water. Metolachlor concentrations in the runoff water ranged from 9.0 ng/mL to 221.5 ng/mL, which is both lower and higher than the 175 ng/mL EPA advisory level for metolachlor. Similarly, metribuzin concentrations in the runoff water ranged between 1.5 ng/mL and 56.2 ng/mL, which is also lower and higher than the 10 ng/mL EPA advisory level for metribuzin. Accordingly, from the field plots located on a Commerce clay loam soil in LA, although the concentration of trifluralin in runoff water were substantially lower than the EPA advisory level, metolachlor and metribuzin concentrations are likely to exceed the EPA advisory levels early on in the application season with a subsequent rapid decrease to safe levels. The total loss of trifluralin in runoff water was 0.005% of the applied amount over an 89 day period after application. The total loss of metolachlor and metribuzin in the runoff water was 4.67% and 5.36% of the applied amount, respectively, over a 22 day period after application. As such, there was almost no movement of trifluralin in the runoff water, whereas metolachlor and metribuzin were much more easily moved.     

Determination of dimethyl fumarate (DMFu) in silica gel pouches using gas chromatography coupled ion trap mass spectrometry

A simple method for the determination of dimethyl fumarate (DMFu) in silica gel pouches has been developed. The gas chromatographic behaviour of DMFu was investigated; the instrumental method, based on EI mass spectrometry coupled with an Ion Trap Detector operating whether in full scan mode or in MS/MS mode was also investigated. Several factors have been evaluated and optimized during the development process: solvent and temperature of extraction, type of stationary phase in capillary column. The analytical procedure consists of two steps as follows: (a) the sample preparation using 10 g of sample extracted with acetonitrile in an ultrasonic, heated bath and (b) the determination by gas chromatography-ion trap mass spectrometry. Mass spectrometry in conjunction with chromatographic separation is a very powerful combination for identification of an analyte in the extract in spite of selective detectors employed with GC, such as ECD, FPD and NPD, that offer only limited specificity. Blank samples show no interfering peaks in the areas of interest, so the specificity of the method was assured under the investigated GC/MS conditions. The method has been validated in terms of recovery, repeatability, linearity, detection limits and measurement uncertainty. The results obtained meet both the method validation criteria and requirements of the European/National legislation. The method was verified to be accurate with 97 % mean recoveries at 0.05 mg/kg and 1.00 mg/kg levels; the repeatability (expressed as RSD %) was found to be better than 15 %. Good linearity was found in the range between 0.05 μg/mL and 5.0 μg/mL and a value of R2 > 0.9998 was calculated. The procedure ensures high specificity and a good sensitivity with detection limit (ld) of 0.02 mg/kg and quantification limit (LOQ) of 0.05 mg/kg. This procedure has been successfully applied for the analysis of several hundred of real samples collected during a monitoring control plan started last year in our country. All samples exceeding the maximum allowed level of DMFu (0, 1 mg/kg) were confirmed by GC/MS/MS (ITD) for a higher degree of confidence in identification. The main advantages of this method include: rapidity, simplicity (few, simple steps), reliability, cheapness, no need for long and difficult clean-up and evaporation steps, high specificity by using GC/MS and GC/MS/MS, availability for routine monitoring.     

Leaching of trifluralin,metolachlor, and metribuzin in a clay loam soil of Louisiana

Trifluralin[2,6-dinitro-N,N-dipropyl-4-(trifluormethyl)benzenamine], metolachlor[2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], and metribuzin[4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)one] were applied in field plots located on a Commerce clay loam soil near Baton Rouge, Louisiana at the rate of 1683 g/ha, 2759 g/ha and 609 g/ha, respectively. The half-lives of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth were found to be 54.7 days, 35.8 days and 29.8 days, respectively. The proportion of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth was 94.7%, 86.6%, and 75.4%, respectively of that found in the top 0-60 cm soil depth 30 days after application. Trifluralin concentrations were within a range of 0.026 ng/mL to 0.058 ng/mL in 1 m deep well water, and between 0.007 ng/mL and 0.039 ng/mL in 2 m deep well water over a 62 day period after application. Metolachlor concentrations in the 1 m and 2 m wells ranged from 3.62 ng/mL to 82.32 ng/mL and 8.44 ng/mL to 15.53 ng/mL, respectively. Whereas metribuzin concentrations in the 1 m and 2 m wells ranged from 0.70 ng/mL to 27.75 ng/mL and 1.71 ng/mL to 3.83 ng/mL, respectively. Accordingly, trifluralin was found to be strongly adsorbed on the soil and showed negligible leaching. Although metolachlor and metribuzin were also both readily adsorbed on the soil, their leaching potential was high. As a result, in the clay loam soil studied, metribuzin concentration in groundwater with shallow aquifers is likely to exceed the 10 mg/L US Environmental Protection Agency (EPA) advisory level for drinking water early in the application season, whereas trifluralin and metolachlor concentrations are expected to remain substantially lower than their respective 2 ng/mL and 175 ng/mL EPA advisory levels.     

Assessing solvent derivatization and carbon dioxide supercritical fluid simultaneous extraction/derivatization of cyprodinil

Derivatization of cyprodinil with different reagents and solvents has been evaluated to improve the GC/MS characterization of this fungicide. After assessing some preliminary acylation and silylation reactions, derivatization with anhydrous heptafluorobutyric anhydride (HFBA) was selected as the best derivatization option for cyprodinil. The HFBA-cyprodinil derivative was clearly identified and characterized by GC/MS (ion-trap). The spectrum of the HFBA derivative of cyprodinil was characterized by the base peak, 252 m/z ion, and two other ions with relative abundances of 5% (224 m/z ion) and 4% (420 m/z molecular ion). Conversion rates in the range of 83–92% were obtained when 0.1–1 μg cyprodinil were derivatized in vial without solvent at 25ºC temperature for 120 min, with 5 μL HFBA and 5 μL pyridine. Simultaneous extraction-derivatization of cyprodinil in supercritical carbon dioxide was only achieved when no modifier was present, but conversion/recovery rates obtained in the replicate experiments carried out with 15 mL supercritical carbon dioxide at 50°C and 200 atm (n = 5), 300 atm (n = 7), and 400 atm (n = 5) were no reproducible (RSD > 50%) and ranged between 10% and 45% (related to the signal obtained for derivatization in vial).