Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Hydrotalcites and organo‐hydrotalcites as sorbents for removing pesticides from water

Abstract

This paper reports on the adsorption of different organic pesticides by hydrotalcite, hydrotalcite heated to 500°C and organo‐hydrotalcite in aqueous medium by employing adsorption isotherms, and using X‐ray diffraction and infrared spectroscopy techniques. The results suggest that the adsorption capacity of the different materials depends on their nature as well as on the structure, polarity and hydrophobic or anionic nature of the pesticides. The results also show that hydrotalcite, both natural and after calcination at 500°C, is not a good sorbent of hydrophobic pesticides. The data demonstrated that both types of hydrotalcite, however, are very good sorbents of glyphosphate. Furthermore, the organo‐hydrotalcites may be as good sorbents as organo‐montmorillonites for hydrophobic pesticides.     

Residues of five pesticides in field‐treated alfalfa seeds and alfalfa sprouts

Abstract

Residues of five different pesticides applied to alfalfa seed crops were determined in the harvested seeds and in sprouts grown from these seeds. Although seeds are usually used for future production of alfalfa plants, some of these seeds may be sprouted for human food consumption. The pesticides studied — aldicarb (Temik®), chlorothalonil (Bravo®), chlorpyrifos (Lorsban®), methamidophos (Monitor®) and propargite (Comite®) — were applied at a normal usage rate and at two to three times that rate. Residues on the seeds and sprouts, if any, were insignificant at rates of application.     

Residues of carbofuran and its two carbamate metabolites in field‐treated rutabaga 1

Abstract

Carbofuran was applied over seeded rutabaga cv. York and residues (corrected for recovery) of carbofuran, 3‐hydroxy‐ and 3‐ketocarbofuran in the harvested roots averaged 0.15, 0.23 and 0.07 ppm in peel and 0.09, 0.14 and 0.05 ppm in pulp, respectively. Samples were extracted by hot acid digestion, partitioned in methylene chloride and cleaned up on Florisil. The 3‐hydroxy‐carbofuran was ethoxylated and the compounds were converted into their dinitrophenyl ethers and analysed by electron capture gas chromatography using 3% OV‐3 column.     

Volatilization of lindane from water in soil‐free and flooded soil systems

Abstract

Volatilization of ¹⁴C‐lindane from water in planchets and under flooded soil ecosystem was investigated. Lindane disappeared faster than parathion from planchets. More rapid loss of both insecticides occurred from water than from chloroform. Loss of lindane and parathion was related to measured losses of water by evaporation. During 5‐day incubation under flooded soil conditions, disappearance of lindane was faster from open vials than from sealed vials, whereas in nonflooded soil, no volatile loss of the insecticide was evident despite water evaporation. Over 5 day incubation under flooded conditions, greater volatile loss of lindane occurred in sandy soil than in alluvial soil apparently due to greater adsorption to the soil colloids decreasing the insecticide concentration in the standing water of the laterite soil. Under identical conditions of water evaporation, lindane loss was directly proportional to its initial concentration in the water. These results suggest that considerable loss of soil applied pesticides can occur by volatilization from the standing water in flooded rice fields, particularly under tropical conditions.     

Persistence of residues in water and sediment op a fresh‐water lake after surface application of technical chlordane

Abstract

A fresh‐water lake, free from detectable pesticide residues before this study, was treated with a commercial formulation of technical chlordane. Water and sediment samples were analysed for chlordane residues 7, 24, 52, 279. and 421 days after treatment. Residues moved rapidly from the water to the lake bottom, supporting earlier results of a laboratory study with other organochlorines.

In water, α‐ and γ‐chlordane concentrations remained proportional to total chlordane concentrations, as determined by total‐peak area measurements of gas‐liquid chronatogrammes. But in bottom sediments, α‐ and γ‐chlordane were more persistent than other constituents of technical chlordane, supporting recent evidence that quantification of technical chlordane residues on the basis of γ‐chlordane quantification only (or that of a‐ and γ‐chlordane only), can lead to incorrect results and that this method, although simple and fast, should no longer be recommended.     

A laboratory study of the persistence of carbofuran and its 3‐hydroxy‐ and 3 keto‐metabolites in sterile and natural mineral and organic soils

Abstract

In a laboratory study, the persistence of carbofuran and its 3‐hydroxy‐ and 3‐keto‐metabolites was examined separately over 16 wk in sterile and natural organic (muck) and mineral (loam) soils. Carbofuran was relatively persistent in sterile soils; at 8 wk 77% remained in the sterile muck and about 50% remained in the sterile loam. In the natural muck 25% of initial carbofuran remained at 8 wk whereas in the natural loam carbofuran had completely disappeared by that time. The 3‐ketocarbofuran was very short‐lived even in the sterile muck where only 50% remained at 1 wk. The 3‐hydroxycarbofuran degraded appreciably on zero day in the natural soils (with conversion to 3‐ketocarbofuran) and about 90% had disappeared in 1 wk. A more detailed study of the persistence of 3‐hydroxycarbofuran in the natural soils showed complete disappearance in 2 days in loam and in 3 days in muck. The 3‐ketocarbofuran produced from the 3‐hydroxy‐carbofuran reached a maximum concentration in 1 day and then disappeared within 4 days in loam and about 1 wk in muck.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State,Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Transient‐phase and steady‐state kinetics of lipase‐catalyzed ester hydrolysis 1

Abstract

An experimental study has been made of both the steady‐state and the transient‐phase (presteady‐state) kinetics of the hydrolyses of several saturated aliphatic esters of p‐nitrophenol catalyzed by wheat germ lipase. The analysis of the presteady‐state part revealed two transients indicating that lipase‐catalyzed reactions proceed via a two‐intermediate mechanism suggested for other esterases. The possibility of more than one species of the enzyme engaged in catalytic activity is discussed and a reaction mechanism scheme is proposed accordingly.     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.     

An overview of short‐term tests for the mutagenic and carcinogenic potential of pesticides

Abstract

In the last few years, marked progress has been made in the development of methods for evaluating the mutagenic and carcinogenic potential of pesticide chemicals. The correlation of genetic and related biological activity in short‐term tests with carcinogenic activity in whole animals allows the utilization of short‐term mutagenicity bioassays to prescreen chemicals for effects related to mutation induction and presumptive carcinogenicity. In addition, bioassays now available can measure directly the chemical transformation of normal cells in culture into cells capable of producing tumors when injected into animals.

This paper will review briefly the major types of relevant short‐term tests and will develop a rationale for a phased approach to the evaluation of the mutagenic and carcinogenic potential of environmental chemicals. This approach involves the sequential application of bioassays which are organized into a three‐level matrix emphasizing first detection, then confirmation, and finally hazard assessment. Chemicals demonstrating positive results in the short‐term detection systems and confirmatory bioassays are pursued in higher level whole animal tests. A core battery of tests is proposed to operationally define a negative result. The phased approach should facilitate a cost effective utilization of limited testing resources and provide protection for human health in proportion to the anticipated hazard.

Results obtained in evaluating a series of thirty‐eight pesticide chemicals according to the phased approach are discussed in detail.     

Residues of chlorpyrifos‐methyl in balsam fir foliage,forest litter,soil, stream water,sediment and fish tissue after double aerial applications of Reldan®

Abstract

Chlorpyrifos‐methyl was applied twice at 70 g A.I./ha by means of a fixed‐wing aircraft to a mixed coniferous forest near Allardville, New Brunswick. Residue in balsam fir foliage was highest (1 ppm wet wt) 1 hr after spraying and rapidly declined to about 30% within 1 day, but persisted at a very low level (0.03 ppm wet wt) for 125 days. Current year's foliage contained a higher level of residue than old foliage. Chlorpyrifos‐methyl persisted longer in forest litter than in soil. After 125 days, trace amounts (< 6 ppb wet wt) were still found in litter but were not detected in soil. In stream water the residue dissipated very rapidly; more than 90% disappeared 3 hours after the second application and were not detected after 4 days. Low‐level residue (< 0.1 ppm wet wt) was present in the sediment and persisted for 10 days. Although brook trout and slimy sculpin captured in the stream within 3 days of the second application contained residues (< 0.05 ppm fresh wt) none were detected in any fish captured, 9 and 47 days later.     

Influence of usage and chemical–physical properties on the atmospheric transport and deposition of pesticides to agricultural regions of Manitoba,Canada

This study quantified the masses of 14 pesticides deposited as wet (precipitation) versus dry (gaseous and particle) atmospheric deposition at a research farm in southwestern Manitoba, Canada. The concentration in air of these pesticides was also measured. Total bulk deposition amounts (wet + dry) ranged from 0.009 to 2.3 μg m^?2 for the 12 pesticides detected, and for the six pesticides with both wet and dry deposition detections, dry deposition contributed 12–51% of the total deposition over the crop growing season. Although not applied at the site, eight herbicides registered for use in Canada, as well as lindane (γ-HCH), were all frequently detected (92–100%) in the 12 air samples analyzed during the crop growing season, with by-product isomer α-HCH (75%), clopyralid (50%) and atrazine (8%) detected to a lesser extent. The chemical’s physicochemical properties and the relative mean mass of each agricultural pesticide applied in the province of Manitoba and in a 13 km radius were significant parameters in explaining the trends in the concentrations of pesticides detected in our samples. The important contribution of dry deposition to total pesticide deposition warrants greater attention in arid and semi-arid areas such as the Prairie Region of Canada, also because under a changing climate this region is estimated to experience more severe droughts while the more favorable conditions predicted for pest infestations could lead to increased pesticide applications in agricultural and urban areas.     

Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. A case study: Suquía River basin (Argentina)

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC–MS). The optimized methodology showed LOQs at ng L^?1 levels (ranging 0.2–3.5 ng L^?1) in addition to acceptable precision and robustness (recoveries ranged 63–104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants.This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max. = 433.9 ng L^?1), alpha-cypermetrine (max. = 121.7 ng L^?1) and endosulfan sulfate (max. = 106.7 ng L^?1) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.     

Rapid multiresidue determination for currently used pesticides in agricultural drainage waters and soils using gas chromatography–mass spectrometry

An efficient and sensitive method for simultaneous determination of 38 pesticides in agricultural drainage waters and soils has been developed and validated. Water samples were extracted using solid-phase extraction with C18 cartridges while solid samples (suspended particle matter and soil) were extracted by using the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction method. The target pesticides were analyzed by using gas chromatography-mass spectrometry with electron impact ionization. The proposed method allowed a simultaneous determination and confirmation of a large number of pesticides in agricultural drainage waters, suspended particle matters and soils/sediments with a good reproducibility and low detection limits. The developed method was applied to a survey of pesticides in a vegetable growing area of Guangzhou, China. The pesticides commonly found in the area were butachlor, carbofuran, dichlorvos, fipronil, isocarbophos and pyridaben.     

Sorption–desorption of indaziflam and its three metabolites in sandy soils

Indaziflam is a relatively new herbicide for which sorption–desorption information is lacking, and nothing is available on its metabolites. Information is needed on the multiple soil and pesticide characteristics known to influence these processes. For four soils, the order of sorption was indaziflam (N-[1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 5.9, 1/n_f = 0.7, K_foc = 447; sandy loam: K_f = 3.9, 1/n_f = 0.9, K_foc = 276) > triazine indanone metabolite (N-[(1R,2S)-2,3-dihydro-2,6-dimethyl-3-oxo-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 2.1, 1/n_f = 0.8, K_foc = 177; sandy loam: K_f = 1.7, 1/n_f = 0.9, K_foc = 118) > fluoroethyldiaminotriazine metabolite (6-[(1R-1-Fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 28; sandy loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 22) = indaziflam carboxylic acid metabolite (2S,3R)-3-[[4-amino-6-[(1R)-1-fluoroethyl]-1,3,5-triazin-2-yl]amino]-2,3-dihydro-2-methyl-1H-indene-5-carboxylic acid) (sandy clay loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 22; sandy loam: K_f = 0.5, 1/n_f = 0.8, K_foc = 32). The metabolites being more polar than the parent compound showed lower sorption. Desorption was hysteretic for indaziflam and triazine indanone metabolite, but not for the other two metabolites. Unsaturated transient flow K_d's were lower than batch K_d's for indaziflam, but similar for fluoroethyldiaminotriazine metabolite. Batch K_d's would overpredict potential offsite transport if desorption hysteresis is not taken into account.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Accelerated degradation of carbofuran in standing water from carbofuran‐retreated Azolla plots

Abstract

Carbofuran (2, 3‐dihydro‐2, 2‐dimethyl‐7‐benzofuranyl N‐methylcarbamate) was mixed with standing water from six flooded Azolla (a fern harboring a nitrogen fixing alga, Anabaena azollae) plots that had been regularly treated with carbofuran before. The insecticide completely disappeared in 5 to 10 days when mixed with water from three of the six plots. The enrichment culture, prepared by further additions of carbofuran to the standing water from an Azolla plot, degraded bendiocarb (2, 2‐dimethyl‐l, 3‐benzidioxol‐4‐yl‐N‐methylcarbamate), carbofuran and carbosulfan [2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl (di‐n‐butyl‐aoinosulfenyl) methyl‐carbamate ] in that order. Enrichment culture, upon sterilization by autoclavlng, lost its ability to degrade carbofuran. Evidently, accelerated degradation of carbofuran in standing water from retreated Azolla plots was mediated by microorganisms.