Method development for determination of fluroxypyr in soil

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 microg/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 microg/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 microg/L ranged from 88 to 98% with relative standard deviations of 3.0-5.8% with a minimum detection limit of 4 microg/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 pg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1-50 microg/kg ranged from 82-107% with relative standard deviations of 0.5-4.7%.     

Determination of the herbicide fluroxypyr in oil matrices

The purpose of this study was to develop a method for the determination of fluroxypyr (4-amino-3,5-dichloro-6-fluro2-pyridyloxyacetic acid) residue in palm oil namely crude palm oil (CPO) and crude palm kernel oil (CPKO). The method involves the extraction of the herbicide from the oil matrix followed by low temperature precipitation and finally quantification of the residues using the high performance liquid chromatography (HPLC). The extraction efficiency of the method was evaluated by conducting recovery studies. The recovery of fluroxypyr from the fortified CPO samples ranged from 78%-111% with the relative values for the coefficient of variation ranging from 1.4 to 8.6%. Furthermore, the recovery of fluroxypyr from the spiked CPKO samples ranged from 91-107% with the relative values for the coefficient of variation ranging from 0.6 to 4.5%. The minimum detection limit of fluroxypyr in CPO and CPKO was 0.05 microg/g. The method was used to determine fluroxypyr residues from the field-treated samples of CPO and CPKO. When fluroxypyr was used for weed control in oil palm plantations no residue was detected in CPO and CPKO irrespective of the sampling interval and the dosage applied at the recommended or double the manufacturer's recommended dosage.     

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 with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

Determination of the herbicide fluroxypyr in oil matrices

The purpose of this study was to develop a method for the determination of fluroxypyr (4-amino-3,5-dichloro-6-fluro2-pyridyloxyacetic acid) residue in palm oil namely crude palm oil (CPO) and crude palm kernel oil (CPKO). The method involves the extraction of the herbicide from the oil matrix followed by low temperature precipitation and finally quantification of the residues using the high performance liquid chromatography (HPLC). The extraction efficiency of the method was evaluated by conducting recovery studies. The recovery of fluroxypyr from the fortified CPO samples ranged from 78%–111% with the relative values for the coefficient of variation ranging from 1.4 to 8.6%. Furthermore, the recovery of fluroxypyr from the spiked CPKO samples ranged from 91–107% with the relative values for the coefficient of variation ranging from 0.6 to 4.5%. The minimum detection limit of fluroxypyr in CPO and CPKO was 0.05 μg/g. The method was used to determine fluroxypyr residues from the field-treated samples of CPO and CPKO. When fluroxypyr was used for weed control in oil palm plantations no residue was detected in CPO and CPKO irrespective of the sampling interval and the dosage applied at the recommended or double the manufacturer's recommended dosage.     

Solid-phase extraction and capillary electrophoresis determination of phenols from soil after alkaline CuO oxidation

Alkaline CuO oxidation has been used on molecular-level analyses of phenols from organic matter in the last decades. This method, originally developed by Hedges and Ertel [Hedges, J.I., Ertel, J.R., 1982. Characterization of lignin by gas capillary chromatography of cupric oxide oxidation products. Anal. Chem. 54, 174-178] has several drawbacks that have limited is wider utilization. In this paper, we propose a modification of the method using a solid-phase extraction (SPE) instead of a liquid-liquid extraction. The SPE procedure using C18 cartridges was optimized to obtain high recoveries. The sequential elution with acetonitrile and methanol was found to be the most appropriate procedure. Recoveries of the 12 phenols in individual standard solutions ranged from 84% to 113% with relative standard deviation (RSD) lower than 12%. Experiments with a mixed standard solution highlighted the competition between the different phenols for the adsorbing sites. Recoveries decreased with polarity, reaching 30% for p-hydroxybenzoic acid when present at a concentration of 2.5 x 10(-3)M. A sample soil subjected to a CuO oxidation was used to test the reproducibility of the SPE method and good results were achieved, RSD ranged between 0.4% and 28.3%. The performance of the CE method was also evaluated by correlation coefficients (higher than 0.9920), linearity (higher than 99.902%) and limit of detection (ranging from 2.64 x 10(-6) to 1.25 x 10(-5)M). SPE procedure presents several advantages such as fast sample preparation, good recoveries, good accuracy, low sample handling and safety improvement due to reduced solvent/sample exposure and glassware management.     

Sample preparation for GC analysis of selected pesticides in surface water.

A new isolation procedure for the determination of nitrogen/phosphorous containing pesticides and organochlorine pesticides in water was tested, and statistical evaluation of the recoveries was performed. The procedure, designed specifically for the analysis of semi-volatile compounds in water containing Suspended Particulate Matter (SPM), utilizes a specially designed filtration vessel coupled directly to an SPE cartridge. The studies were based on surface water samples (from the Vistula River) spiked with pesticides. SPM separation and analyte isolation/concentration were carried out in a special filtration vessel. Pesticides were sorbed both on the SPE cartridge and on the suspended matter. The cartridge and the filter with the suspended matter were extracted separately with a solvent, which enabled the determination of analyte distribution between the two. For organochlorine pesticides, between 3 and 60% of the initial amount was found on the filter, while the recoveries in the filtrate ranged from 30 to 98%. Total recoveries of organochlorine pesticides from surface water samples spiked with pesticides using the method described were high, ranging from 90 to 101%. The amounts of nitrogen/phosphorus containing pesticides recovered from the filter were lower than 2%, while those from the filtrate ranged from 69 to 92%. Total recoveries of nitrogen/phosphorus containing pesticides from surface water samples were high, ranging from 71 to 92%.     

Preliminary findings on the antimony levels of Quiroga river water in the vicinity of a long-abandoned stibnite mine

A UV-Vis spectrophotometric method was developed as a preliminary approach to the determination of antimony in water samples from a river that flows very close to an abandoned mining site. The analyte is complexed with ammonium pyrrolidinedithiocarbamate and absorbance of the complex is measured at 291.06 nm. The standard additions method is mandatory in view of the matrix effect observed, and the response is linear at least up to 9.3 microg/mL of antimony. The sensitivity of the method is 2.609 x 10(-2) mL/microg, whereas the limits of detection and quantification are, respectively, 0.2 and 0.6 microg/mL. The repeatability, expressed as mean relative standard deviation of the measurements within the calibration range, is 2.0%, whereas the repeatability of the entire procedure is 0.3%. The mean analytical recovery within the calibration range was 102.6%. The method was successfully applied to river water samples.     

Screening of compost for PAHs and pesticides using static subcritical water extraction.

Static subcritical water extraction (SubWE) along with solid phase extraction (SPE) was used for the analysis of PAHs and pesticides in municipal solid waste compost. Yields obtained for PAHs in certified reference sediment (CRM 104) were acceptable. The extraction method was simple, rapid, used small sample sizes, and no sample drying was required. Analysis of samples was performed by GC/MS and HPLC. Recovery of spiked pesticides was greatest at 110 degrees C for 20 min extraction time. The optimum extraction for PAH analysis was achieved at 150 degrees C for 20 min. Addition of C-18 resin as an "alternate sorbent" upon cooling increased recovery of PAHs but not of pesticides, however, it increased the stability of atrazine and propazine at higher temperatures. Analysis of three municipal compost samples from the Dayton, OH (USA) area showed no pesticides above the detection limit, however, PAH totals for 11 PAHs were 15.97, 14.42, and 20.79 microg g(-1). The totals of six of the seven carcinogenic PAHs, for which remediation goals in the United States is 4.6 microg g(-1), were determined to be 9.89, 6.77, and 13.06 microg g(-1) dry weight. The highest PAH totals were obtained from compost containing sewage sludge.     

Multivariate optimization of solid-phase extraction applied to iron determination in finished waters

In this work, Amberlite XAD-4 resin functionalized with salicylic acid was synthetized, characterized and applied as a new packing material for an on-line system to iron determination in aqueous samples. The detection method is based on the sorption of Fe(III) ions in a minicolumn containing the synthesized resin, followed by a desorption step using an acid solution and measurement of iron by vis-spectrophotometry (CAS method). The optimization of the solid-phase extraction system was performed using factorial design and Doehlert matrix considering six variables: sample percolation rate (0.5-9 ml min(-1)), sample metal concentration (20-200 microg l(-1)), flow-through sample volume (0-5 ml) (all three directly linked to the extraction step), elution flow-rate (0.5-9 ml min(-1)), concentration and volume of eluent (HCl 0.1-0.5M) (all three directly linked to the elution step). The aim of this study was to obtain a set of operating ranges for the six variables tested in order to obtain--by means of a mathematical function allowing maximisation of each response (desirability function)--at least 90% of iron recovery rates. Using the experimental conditions defined in the optimization, the method allowed iron determination with achieved detection limit of 2.3 microgl(-1) and precision (assessed as the relative standard deviation) of 9.3-2.8% for iron solutions of 10.0-150 microgl(-1). Real samples (coming from a water treatment unit) were used successfully when evaluating potentialities of the developed SPE procedure coupled to a spectrophotometric determination.     

On-line solid-phase extraction and fluorescence detection of selected endocrine disrupting chemicals in water by high-performance liquid chromatography

A high-performance liquid chromatographic method was developed to analyse selected endocrine disrupting chemicals in water by using automated on-line solid-phase extraction with a fluorescence detector. The excitation and emission wavelengths of the fluorescence detector were 230 nm and 290 nm, respectively. The selected endocrine disrupting chemicals include hormone steroids such as estradiol (E2), estriol (E3), ethynylestradiol (EE2), and ethynylestradiol 3-methyl ether (MeEE2) as well as nonylphenols (NP), octylphenols (OP), POE(1-2) nonyl phenol (NPE) and bisphenol A (BP). Three types of on-line cartridges (C18, PLRP-s and PRP-1) were tested to pre-concentrate the endocrine disruptors in deionised water. It was found that the recoveries of these chemicals at 1 microg/L were close to 100% except for 4-octyl phenol and 4-n-nonyl phenol, which had recoveries of about 40% to 80%. The two polymer cartridges (PLRP-s and PRP-1) gave higher recoveries than the C18 cartridges. The addition of methanol at 5% to 10% in water significantly improved the recovery of 4-octyl phenol and 4-n-nonyl phenol. The addition of methanol also led to an improvement in the recovery with C18 cartridges. With the addition of methanol in water samples, these three types of cartridges gave similar recoveries for the chemicals. The detection limits of this method ranged from 20 ng/L to 50 ng/L. A river water sample spiked with these chemicals was analysed using the above method and we found no interference with the peaks of the selected endocrine disrupting chemicals. The recoveries for these chemicals were more than 92% except for 4-NP with a recovery of 61%. This relatively simple method is useful for laboratory studies on the environmental fate of these endocrine disrupting chemicals in water.     

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.     

Gas chromatography/mass spectrometry applied for the analysis of triazine herbicides in environmental waters

The excess use of triazine herbicides in agriculture causes severe contamination to the environment especially for ground water. Gas chromatography coupled with mass spectrometry (GC/MS) was used to analyze simazine, atrazine (ATR), cyanazine, as well as the degradation products of ATR such as deethylatrazine and deisopropylatrazine in environmental water samples. These compounds were baseline separated by the established GC method. The water samples were pre-concentrated by solid-phase-extraction (SPE) and analyzed by ion trap MS at sub- to low-ppt levels. Recovery of ATR by the SPE pre-concentration using a C18 cartridge was determined as 90.5 +/- 3.5%. Detection limit of the method using selected ion monitoring technique for ATR was 1.7 ppt when one liter water was analyzed. The relative analytical error for ATR fortified water samples at 200 ppt was -12.5% (n=12) with triple analysis and the relative standard deviation was 3.2%. Trace levels of ATR at 3.9 and 9.7 ppt were determined in water samples collected from a reservoir and a river in Hong Kong.     

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.     

Residue determination and dissipation of ioxynil octanoate in maize and soil

A simple and efficient residue analysis method for direct determination of ioxynil octanoate in maize and soil was developed and validated with High Performance Liquid Chromatography-Ultra Violet (HPLC-UV). The samples were extracted with mixtures of acetonitrile and deionized water followed by Solid Phase Extraction (SPE) to remove co-extractives prior to analysis by HPLC-UV. The recoveries of ioxynil octanoate extracted from maize and soil samples ranged from 86 %-104 % and 84 %-96 %, respectively, with relative standard deviation (RSD) less than 7.84% and sensitivity of 0.01 mg kg(-1). The method was applied to determine the residue of ioxynil octanoate in maize and soil samples from experimental field. Data had shown that the dissipation rate in soil was described as pseudo-first-order kinetics and the half-life (t(1/2)) was less than 1.78 days. No ioxynil octanoate residue (<0.01 mg kg(-1)) was detected in maize at harvest time withholding period of 60 days after treatments of the pesticide. Direct confirmation of the analytes in field trial samples was realized by Liquid Chromatography-Mass Spectrometry (LC-MS).     

Simultaneous determination of imidacloprid, thiacloprid, and thiamethoxam in soil and water by high-performance liquid chromatography with diode-array detection

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C18 cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 +/- 4.2% for thiamethoxam, 99 +/- 4.2% for imidacloprid and 94 +/- 1.4% for thiacloprid. The recoveries for water samples ranged from 87 +/- 3.4% for thiamethoxam to 97 +/- 3.9% for imidacloprid and 97 +/- 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5g), and 2, 2, 0.5, micro/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.     

Application of the new C18 speedisks to the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in water and effluent samples

A recently introduced disk for solid-phase extraction of pollutants from water (C18 Speedisk) has been tested for the analysis of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). The complete procedure of analysis has been validated with spiked deionized water. The accuracy, expressed as recovery for the sum of 2,3,7,8-substituted congeners. is 92% and the precision, expressed as the RSD of reproducibility, is 5.8%. The limit of detection (LOD), using 2 l of water, is 4.2 pg/l (0.6 pg ITEQ/l) for the sum of 2,3,7,8-substituted congeners. Actually, the C18 Speedisks have substituted the use of other C18 membrane disks in our laboratory because they allow the fast and efficient analysis of samples with high content of suspended material and reduce the time of elution of free-particulate samples. These disks have been successfully applied to the analysis of water from different sources and with very different physical and chemical characteristics: seawater, rain water, an industrial effluent, a landfill leachate and the inlet and chlorinated and non-chlorinated outlet water from a wastewater treatment plant.     

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Separation of dissolved iron from the aqueous system with excess ligand

A new technique for the separation and pre-concentration of dissolved Fe(III) from the ligand-rich aqueous system is proposed. A solid phase extraction (SPE) system with an immobilized macrocyclic material, commonly known as molecular recognition technology (MRT) gel and available commercially, was used. Synthetic Fe(III) solution in aqueous matrices spiked with a 100-fold concentration of EDTA was used. Dissolved iron that was ‘captured’ by the MRT gel was eluted using hydrochloric acid and subsequently determined by graphite furnace atomic absorption spectrometry. The effect of different variables, such as pH, reagent concentration, flow rate and interfering ions, on the recovery of analyte was investigated. Quantitative maximum separation (∼100%) of the dissolved Fe(III) from synthetic aqueous solutions at a natural pH range was observed at a flow rate of 0.2 mL min^-1. The extraction efficiency of the MRT gel is largely unaltered by the coexisting ions commonly found in natural water. When compared with different SPE materials, the separation performance of MRT gel is also much higher.