Simplified multiresidue method for liquid chromatographic determination of N-methyl carbamate insecticides in fruits and vegetables

A simplified method is described for determining 7 N-methyl carbamates (aldicarb, carbaryl, carbofuran, methiocarb, methomyl, oxamyl, and propoxur) and 3 related metabolites (aldicarb sulfoxide, aldicarb sulfone, and 3-hydroxy carbofuran) in fruits and vegetables. Residues are extracted from crops with methanol; coextractives are then separated by gel permeation chromatography (GPC) or GPC with on-line Nuchar-Celite cleanup for crops with high chlorophyll and/or carotene content (e.g., cabbage and broccoli). Carbamates are separated on a reverse-phase liquid chromatography column, using a methanol-water gradient mobile phase. Separation is followed by postcolumn hydrolysis to yield methylamine, and the formation of a fluorophore with o-phthalaldehyde and 2-mercaptoethanol prior to fluorescence detection. Recovery data were obtained by fortifying 5 different crops (apples, broccoli, cabbages, cauliflower, and potatoes) at 0.05 and 0.5 ppm. Recoveries averaged 93% at both fortification levels except for the very polar aldicarb sulfoxide for which recoveries averaged around 52% at both levels. The coefficient of variation of the method at both levels is less than 5% and the limit of detection, defined at 5 times baseline noise, varies between 5 and 10 ppb, depending on the compound.     

Comparison of analytical procedures for determination of soil sorption coefficients of some triazine herbicides

Abstract

The sorption behavior of three triazine herbicides: atrazine, metribuzin, and terbutryn was studied in two different soils. Three experimental procedures to determine the K_f values were assayed: the conventional batch equilibration method in which the sorbed concentration is calculated by difference from the change in solution concentration; an alternative mass balance equilibrium batch technique in which the solution and the sorbed phase concentration are measured directly; and the flow equilibration method in which a solution of known concentration was passed through a column of soil until the effluent reached the same concentration as the input solution. Four concentrations of each herbicide were selected and results were fitted to the linearized form of the Freundlich isotherm. Recovery of the herbicides was studied in soil and water samples using the same four concentrations employed in the sorption assays. Average recoveries ranged from 86 to 104% with standard deviations lower than 10%. The K_oc (mg^1–1/n kg^‐1 L^l/n) values obtained ranged from 43 to 87 for atrazine, 27 to 114 for metribuzin, and 355 to 505 for terbutryn. The exponents 1/n of the Freundlich adsorption isotherms were lower than unity, with only one exception, and varied from 0.72 to 0.86 for atrazine, 0.73 to 1.12 for metribuzin, and 0.76 to 0.99 for terbutryn. The solution method gave values of K_oc that were 1.25, 1.55, and 2.65 (average of both soils) times those of the mass balance method for terbutryn, atrazine and metribuzin, respectively. When adsorption was low, the mass balance calculation method is recommended if the batch equilibration method is used, since the solution method can produce a considerable overestimation of adsorption. The flow equilibration method produced similar values of adsorption than the mass balance batch equilibration method and it made the experimental procedure easier since pesticide solution concentration need not to be measured once the equilibration time has been determined to ensure that the equilibrium was reached.     

QuEChERS multiresidue method validation and mass spectrometric assessment for the novel anthranilic diamide insecticides chlorantraniliprole and cyantraniliprole

The gas-phase dissociation reactions of chlorantraniliprole (Rynaxypyr) and cyantraniliprole (Cyazypyr) have been studied in triple-quadrupole, ion trap, and orbitrap mass spectrometers equipped with electrospray and desorption electrospray ion sources, revealing the formation of odd-electron fragment ions, the structures of which were elucidated. The odd-electron fragments were unusually abundant, and their formation is proposed to occur via a tricyclic intermediate. The applicability of the QuEChERS multiresidue method for the quantitation of chlorantraniliprole and cyantraniliprole was also assessed in this study. Four matrices representative of oily, watery, acidic, and dry crop groups were tested, with a targeted limit of quantitation (LOQ) of 0.01 mg/kg. Average recoveries ranged between 87 and 107%, with relative standard deviations (RSD) of ≤ 8%. Linear calibration functions with correlation coefficients r > 0.99 were obtained. The study provides an expansion of the QuEChERS method to include anthranilic diamides and a mass spectrometric assessment for these two novel agrochemical active ingredients.     

Photodegradation of triazine herbicides in aqueous solutions and natural waters

The photodegradation of three triazines, atrazine, simazine, and prometryn, in aqueous solutions and natural waters using UV radiation (lambda > 290 nm) has been studied. Experimental results showed that the dark reactions were negligible. The rate of photodecomposition in aqueous solutions depends on the nature of the triazines and follows first-order kinetics. In the case of the use of hydrogen peroxide and UV radiation, a synergistic effect was observed. The number of photodegradation products detected, using FIA/MS and FIA/MS/MS techniques, suggests the existence of various degradation routes resulting in complex and interconnected pathways.     

Liquid chromatographic method for multiresidue determination of benzimidazoles in beef liver and muscle: collaborative study

A liquid chromatographic method for determination of thiabendazole, 5-hydroxythiabendazole, oxfendazole, mebendazole (MBZ), and fenbendazole (FBZ) in cattle liver and muscle was collaboratively studied in 7 laboratories in 1986. For blind fortified samples containing 800 ppb FBZ, average recovery and relative standard deviations for repeatability and reproducibility (RSDr and RSDR) based on results from 6 of the participating laboratories were 83%, 12.7%, and 14.0%, respectively. Recoveries of FBZ from incurred liver samples were more variable. Recoveries of MBZ from livers fortified at the 100 ppb level were encouraging; however, the drug levels were too low in the incurred samples used for MBZ studies. Except for FBZ and MBZ in liver, the study data were not satisfactory. The method has been adopted official first action by AOAC for determination of 800-1600 ppb fenbendazole in liver. The analysis should be repeated using a smaller sample size when initial analyses show levels greater than 1600 ppb FBZ.     

Bioavailability of triazine herbicides in a sandy soil profile

The bioavailability of atrazine was evaluated in a Danish soil profile (Drengsted) using a combination of soil sorption, transport and mineralisation methods as well as inoculation using Pseudomonas ADP. Sorption of atrazine decreased markedly with depth as indicated by K_d values of 5.2 l kg^-1 for the upper soil and 0.1 l kg^-1 for the subsoils. The transport of atrazine was evaluated using soil TLC plates and the resulting R_f values were 0.1 for the upper soil and 0.9 for the subsoil. Only a relatively small amount of atrazine leached through undisturbed soil columns taken from the upper 60 cm. Inoculating with Pseudomonas strain ADP (1᎒⁶ CFU g^-1 dry weight soil) revealed that the degradation of 0.01 ppm atrazine was fully completed (80% mineralisation) within 10 days in the subsoil, while it reached less than 15% in the upper soil. Over a period of 500 days, a total mineralisation of 37% of added atrazine in the upper soil was found (2 mg kg^-1 incubated at 20° C). However, in the subsurface soil where 0.02 mg kg^-1 of atrazine was incubated at 10°C, the degradation was slower, only reaching about 12%. Terbuthylazine mineralisation was found to be temperature-dependent and low (less than 5%) in the upper soil and very much lower in the subsoil. Desethylterbuthylazine was the most frequently found metabolite. Finally, Pseudomonas strain ADP inoculated into soils from different depths increased the mineralisation of terbuthylazine dramatically. Modelling using a "two-compartment model" indicated that desorption of terbuthylazine is the limiting step for its mineralisation.     

Fast and versatile multiresidue method for the analysis of botanical insecticides on fruits and vegetables by HPLC/DAD/MS

A simple multiresidue method for screening analysis of 12 botanical insecticides used by organic farmers has been developed. The method involves a rapid and small-scale extraction procedure with acetonitrile. For all fruit and vegetable samples, there was no need for clean up. Rotenone, azadirachtin, ryanodines, and pyrethrins can be separated by high-performance liquid chromatography, quantified, and confirmed with a diode array detector (DAD) and atmospheric pressure chemical ionization mass spectrometry (APCI-MS) in the select ion-monitoring mode (SIM). The majority of pesticide recoveries for various fruits and vegetables were >70% in the concentration range from 0.01 to 5 mg/kg. The limit of quantitation for most of the pesticides was 0.01 mg/kg, with the majority of relative standard deviations (RSD) mostly below 10%.     

Simplified extraction and cleanup for multiresidue determination of pesticides in lanolin

In the proposed method, a light petroleum solution of lanolin (wool fat) is adsorbed on diatomaceous earth in an Extrelut column, and the pesticides are eluted with acetonitrile saturated with light petroleum. After evaporation to a small volume, the extract is subjected to solid-phase extraction (SPE) on a C-18 column. The acetonitrile eluate is evaporated to dryness and the residue is taken up in light petroleum. Organophosphorus pesticides are determined by temperature-programmed gas chromatography (GC) on a wide-bore column using a flame photometric detector in the phosphorus mode. Organochlorine pesticides are determined after miniaturized Florisil cleanup by classic GC on an OV-17/QF-1 packed column, using an electron capture detector. This procedure is more rapid and straightforward than the time-consuming AOAC extraction method, 29.014. Cleanup was better and the results obtained were comparable. Recoveries for 13 organochlorine and organophosphorus pesticides, frequently found in lanolin, ranged from 80 to 90%.     

Transgenic rice plants expressing human CYP1A1 remediate the triazine herbicides atrazine and simazine

The human cytochrome P450 CYP1A1 gene was introduced into rice plants (Oryza sativa cv. Nipponbare). One-month-old CYP1A1 plants grown in soil clearly showed a healthy growth and tolerance to 8.8 microM atrazine and 50 microM simazine, but nontransgenic plants were completely killed by the herbicides. Although transgenic and nontransgenic plants metabolized the two herbicides into the same sets of compounds, CYP1A1 plants metabolized atrazine and simazine more rapidly than did control plants. In small-scale experiments, residual amounts of atrazine and simazine in the culture medium of CYP1A1 plants were 43.4 and 12.3% of those in control medium; those of nontransgenic Nipponbare were 68.3 and 57.2%, respectively. When cultivated in soil with 2.95 microM atrazine and 3.15 microM simazine for 25 days, CYP1A1 plants eliminated 1.3 times more atrazine and 1.4 times more simazine from the soil than did control plants. Thus, CYP1A1 rice plants make it possible to remove atrazine and simazine more rapidly from the culture medium and soil than can nontransgenic Nipponbare.     

A reliable and sensitive immunoassay for the determination of crustacean protein in processed foods

Among food allergens, crustacea such as shrimps, crabs, and lobsters are a frequent cause of adverse food reactions in allergic patients. The major allergen has been identified as a muscular protein, tropomyosin. A novel sandwich enzyme-linked immunosorbent assay (ELISA) for the detection and quantification of crustacean protein in processed foods was developed using the sample dilution buffer that is added to porcine tropomyosin. The sandwich ELISA method was highly specific for the Decapoda group, apart from minor cross-reactivities to other crustacea and mollusks. The recovery ranged from 85 to 141%, while the intra- and interassay coefficients of variation were less than 2.8 and 8.4%, respectively.     

Organoarsenical species contents in fresh and processed seafood products

A study was carried out to determine organic species of arsenic in the main varieties of seafood consumed in the Basque country (Spain). The concentrations of arsenobetaine (AB), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), arsenocholine (AC), and tetramethylarsonium ion (TMA(+)) in 64 samples corresponding to different food items are presented. The study provides information about a possible distribution pattern of organoarsenical species in seafood products. AB was detected in all of the samples [0.3-104.1 microg g(-1) dry weight (dw)]. DMA was detected in all of the samples except squid and salted cod (0.027-1.757 microg g(-1) dw). MMA was detected only in certain fatty fish (0.004-0.028 microg g(-1) dw) and bivalves (0.031-0.047 microg g(-1) dw). AC was only present in some samples of lean fish (0.014-0.089 microg g(-1) dw), and TMA(+) was detected only in anchovy (0.039-0.169 microg g(-1) dw) and crustaceans (0.044-0.966 microg g(-1) dw).     

Availability of triazine herbicides in aged soils amended with olive oil mill waste

Amendments are frequently added to agricultural soils to increase organic matter content. In this study, we examined the influence of alperujo, an olive oil mill waste, on the availability of two triazine herbicides, terbuthylazine and atrazine, in two different sandy soils, one from Sevilla, Spain, and the other from Minnesota. The effect of aging on herbicide sorption and bioavailability was also studied. Soils were amended with alperujo at a rate of 3-5% (w:w) in laboratory studies. Apparent sorption coefficients for the triazine herbicides were calculated as the ratio of the concentrations of each herbicide sequentially extracted with water, followed by aqueous methanol, at each sampling time. These data showed greater sorption of terbuthylazine and atrazine in amended soils as compared to nonamended soils, and an increase in the amount of herbicide sorbed with increasing aging time in nonamended soils. The triazine-mineralizing bacterium Pseudomonas sp. strain ADP was used to characterize triazine bioavailability. Less mineralization of the herbicides by Pseudomonas sp. strain ADP was observed in soils amended with alperujo, as compared to the unamended soils, and, despite the increase in sorption with aging in unamended soils, herbicide mineralization also increased in this case. This has been attributed to Pseudomonas sp. strain ADP first using alperujo as a more readily available source of N as compared to the parent triazines. In summary, addition of alperujo to the soils studied was shown to increase triazine herbicides sorption and hence to reduce its availability and potential to leach.     

Supercritical fluid extraction of atrazine and other triazine herbicides from fortified and incurred eggs

Triazines are a class of important pre-emergent weed herbicides. Some members of this class of herbicides exhibit carcinogenic and immunotoxicity properties, which make their use controversial in areas where animal feed crops are grown. It is therefore important to determine if triazine residues are transported to animal food products in order to ascertain the extent of human exposure. Most of the current herbicide residue extraction methods are time-consuming and solvent intensive. Supercritical fluid extraction (SFE) using CO(2) has been used as a alternative for other residue extraction methods as a replacement for hazardous organic solvents. In this study, 10 triazines were extracted from eggs fortified at 100 ppb using unmodified supercritical CO(2) at a pressure of 10000 psi and a temperature of 50 degrees C with off-line collection on a solid phase extraction cartridge containing Florisil. Atrazine recovery averaged 90.4% with an RSD of 3.3%. The other triazines were recovered at mean levels >73%. In a separate feeding study, atrazine and two of its dealkyl metabolites were detected in the egg. The results indicate that SFE is a viable technique for isolating triazine residues from eggs, requiring only 8 mL of solvent for each analysis.     

Total and inorganic arsenic in fresh and processed fish products

Total arsenic and inorganic arsenic contents were determined in 153 samples of seafood products consumed in the Basque Country (Spain): fish (white fish and blue fish), mollusks, crustaceans, and preserved fish. White fish presented higher levels of total arsenic and lower levels of inorganic arsenic than the blue fish, indicating possible differences in the metabolization of inorganic arsenic. For total arsenic, 66% of the samples exceeded the maximum permitted level by the strictest international legislation in seafood products [1 microg g(-)(1), wet weight (ww)]. The levels of inorganic arsenic were considerably lower than the maximum authorized in New Zealand (2 microg g(-)(1), ww), the only country with legislation for inorganic arsenic in fish and fish products. It is recommended that legislation based on levels of inorganic arsenic should be established.