Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 +/- 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

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.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Thermal analysis of polyethylene glycol: evolved gas analysis with ion attachment mass spectrometry

The thermal decomposition of polyethylene glycol was investigated by using a technique combining evolved gas analysis (time-resolved pyrolysis) with ion-attachment mass spectrometry. This technique allows the detection of intact pyrolysis products and, therefore, offers the opportunity for direct real-time monitoring of thermal by-products. Unstable products can thus be detected; for instance, many highly reactive organic peroxides, such as CH₃OOH and HOCH₂OOH, were found in this study. Classification analysis revealed 10 major compositional formulas among the product species: C_nH_2n+2O, C_nH_2n+2O₂, C_nH_2n+2O₃, C_nH_2n+2O₄, C_nH_2n+2O₅, C_nH_2n+2O₆, C_nH_2n+2O₇, C_nH_2nO, C_nH_2nO₂, and HO(CH₂CH₂O)_nH ethylene glycol oligomers. The Li⁺ ion adduct mass spectra showed a characteristic profile in terms of both the appearance of unique components and the distribution of pyrolysis products. Among the products of the thermal decomposition of PEG, formaldehyde (HCHO) and organic peroxides were particularly interesting. Formaldehyde, one of the 10 most abundant products, is a known human carcinogen. The detection of peroxides suggests that they may form during the incineration of PEG, which may have important environmental implications. The existence of peroxide products may have implications for chemical evolution in incinerator systems.     

Determination of chlorinated paraffins in sediments from the Firth of Clyde by gas chromatography with electron capture negative ionisation mass spectrometry and carbon skeleton analysis by gas chromatography with flame ionisation detection

Short chain chlorinated paraffins (SCCPs) are a group of persistent organic pollutants (POPs) of increasing concern, but are to date not widely investigated in the environment, largely due to the challenges involved in their quantification. Here, SCCPs were quantified in marine sediments from the Firth of Clyde, Scotland, by gas chromatography with electron capture negative ionisation mass spectrometry (GC-ECNIMS) and through carbon skeleton analysis by gas chromatography with flame ionisation detection (GC-FID), and the analytical challenges encountered are discussed. Concentrations in the sediments ranged from 0.4 to 69 μg kg⁻¹ when determined by GC-ECNIMS, and from 5.6 to 379 μg kg⁻¹ when determined by GC-FID. For 8 out of 11 samples, analysis by GC-FID gave higher results than analysis by GC-ECNIMS. Unexpected aspects of the analysis, such as the presence of high concentrations of longer chain chlorinated paraffins in the samples, are also presented.     

Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

Nontarget analysis of polar contaminants in freshwater sediments influenced by pharmaceutical industry using ultra-high-pressure liquid chromatography-quadrupole time-of-flight mass spectrometry

A comprehensive analytical procedure for a reliable identification of nontarget polar contaminants in aquatic sediments was developed, based on the application of ultra-high-pressure liquid chromatography (UHPLC) coupled to hybrid quadrupole time-of-flight mass spectrometry (QTOFMS). The procedure was applied for the analysis of freshwater sediment that was highly impacted by wastewater discharges from the pharmaceutical industry. A number of different contaminants were successfully identified owing to the high mass accuracy of the QTOFMS system, used in combination with high chromatographic resolution of UHPLC. The major compounds, identified in investigated sediment, included a series of polypropylene glycols (n = 3-16), alkylbenzene sulfonate and benzalkonium surfactants as well as a number of various pharmaceuticals (chlorthalidone, warfarin, terbinafine, torsemide, zolpidem and macrolide antibiotics). The particular advantage of the applied technique is its capability to detect less known pharmaceutical intermediates and/or transformation products, which have not been previously reported in freshwater sediments.     

Pilot scale application of a method for the analysis of perfluorinated compounds in surface soils

A growing number of studies now indicate that perfluorinated compounds (PFCs) are globally distributed in the environment. Their widespread distribution and presence in remote locations has led to questions about the importance of atmospheric and oceanic transport. Describing their distribution in surface soils is also an essential but neglected element in developing a comprehensive understanding of their occurrence in the environment. Soils are the critical link between global atmospheric and hydrologic processes where both local and distant contaminants can accumulate and be released into aquatic and terrestrial communities. Because PFC concentrations in soils will influence ground and surface water, wildlife, and crops, methods to accurately measure PFCs in soil are clearly needed. To help answer this need, we developed a method for the analysis of nine perfluorinated carboxylic acids and four perfluorinated sulfonic acids in soil. Samples from six nations (n = 10 per nation) were analyzed by LC-MS/MS to demonstrate the method performance parameters and to make preliminary observations about the occurrence of the PFCs in soils in different parts of the world. The resulting method shows acceptable performance characteristics for the target compounds in most soils while documenting the widespread occurrence of PFCs in surface soils.     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min^?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76–128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m^?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

Simultaneous determination of organochlorine and pyrethriod pesticide residues in the Chinese patent medicines by gas chromatography-tandem mass spectrometry

A simple, sensitive, reliable method was developed for the simultaneous determination of organochlorine and pyrethriod pesticide residues in Chinese patent medicines Six ingredient rehmannia pills and Xiaoyao pills. These pesticides were extracted by ethyl acetate. The extraction time and volume of ethyl acetate were optimized. Cleanup of extracts was performed with dispersive-solid phase extraction using graphitized carbon black as the sorbent. The determination of pesticides in the final extracts was carried out by gas chromatography–tandem mass spectrometry in multiple reaction monitoring mode (GC-MS/MS, MRM). The linearity of the calibration curves is good in matrix-matched standard and yields the coefficients of determination (R²) ≥0.99 for all of the target analytes. Under optimized conditions, the average recoveries (five replicates) for most pesticides range from 75.5% to 114.6%, and RSDs are less than 10.0%. The LODs of 18 pesticides in Six ingredient rehmannia pill and Xiaoyao pills are in the range of 0.01–8.82 μg kg^?1. The developed method meets the requirements of pesticide residue analysis and could be effectively used for routine analysis of the organochlorine and pyrethriod pesticide residues in Six ingredient rehmannia pills and Xiaoyao pills.     

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

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 MgSO₄ plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO₄ 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%.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

Monitoring and modelling of siloxanes in a sewage treatment plant in the UK

Monitoring of cyclic volatile methylsiloxanes (cVMS) carried out at Anglian Water’s Broadholme sewage treatment plant (STP) is described. The method deployed used headspace gas chromatography/mass spectrometry (HS-GC/MS) and the addition of isotopically labelled cVMS to correct for partitioning in samples containing high levels of particulate and dissolved organic carbon. The method was capable of measuring cVMS in raw sewage samples, with recoveries of 80%, 85% and 71% respectively, for D₄, D₅ and D₆. The limit of quantification was 0.2 μg L⁻¹ for all three substances. Recoveries close to 100% were observed for all cVMS spiked into treated effluent (LOQ = 0.01 μg L⁻¹). Despite the volatile nature of cVMS and its ubiquitous presence in the ambient atmosphere, the methods deployed showed excellent recoveries, reproducibility and quantification limits. A distinct diurnal variation in cVMS concentration, probably linked with the use of personal care products was observed for raw sewage but not in treated sewage effluent. The estimated per capita consumption of D₅ (∼2.7 mg cap⁻¹ d⁻¹) derived for the population served by this plant was significantly lower than that derived in the Environment Agency (UK) risk assessment (11.6 mg cap⁻¹ d⁻¹). The cVMS were highly removed during sewage treatment with efficiencies greater than 98%. The methods and findings of this pilot study can be used as the basis for future studies on the fate of cVMS substances in STPs.     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Evaluation of a multiresidue method for pesticides in cereals using supercritical fluid extraction and gas chromatographic detection

Supercritical fluid extraction (SFE) was evaluated to be applied for residue analysis of 22 gas chromatography/electron capture detector-nitrogen phosphorus detector (GC/ECD-NPD) amenable pesticides in rice, wild rice and wheat. Samples were extracted with supercritical carbon dioxide at 200 atm pressure and 50°C temperature, using methanol as a static modifier. Mean recoveries obtained with the proposed SFE method at two spiking levels with four replicates per level are compared with those obtained with an ethyl acetate-based solvent extraction/gel permeation chromatography (GPC) clean up method. Both methods gave consistent high recoveries for almost all the pesticides from all the commodities with overall mean recoveries higher than 70% with relative standard deviations lower than 20%. Remarkable exceptions were captafol and dimethoate, for which low and/or non-reproducible recoveries were obtained with the SFE method. Residue levels determined with both methods in nine different incurred samples of wheat, containing some of the studied pesticides, were very similar, but, in all cases, slightly higher levels were determined with the SFE method.     

Analysis of accumulation, extractability, and metabolization of five different phenylarsenic compounds in plants by ion chromatography with mass spectrometric detection and by atomic emission spectroscopy

Phenylated arsenic compounds occur as highly toxic contaminants in former military areas where they were formed as degradation products of chemical warfare agents. Some phenylarsenic compounds such as roxarsone and aminophenylarsonic acids were applied as food additive and veterinary drugs in stock-breeding and therefore pose an environmental risk in agricultural used sites. Very few data exist in the literature concerning uptake and effects of phenylarsenic compounds in plants growing on contaminated soils. In this study, the accumulation, extractability, and metabolization of five different phenylarsenic compounds, phenylarsonic acid, p- and o-aminophenylarsonic acid, phenylarsine oxide, and 3-nitro-4-hydroxyphenylarsonic acid called roxarsone, by the terrestrial plant Tropaeolum majus were investigated. Ion chromatography coupled to inductively coupled plasma mass spectrometry was used to differentiate these arsenic compounds, and inductively coupled plasma atomic emission spectroscopy was used for total arsenic quantification. All compounds considered were taken up by the roots and transferred to stalks, leaves, and flowers. The strongest accumulation was observed for unsubstituted phenylarsonic acid followed by its trivalent analogue phenylarsine oxide that was mostly oxidized in soil whereas the amino- or nitro- and hydroxy-substituted phenylarsonic acids were accumulated to a smaller degree.The highest extraction yield of 90% for ground leaf material was achieved by 0.1 M phosphate buffer, pH 7.7, in a two-step extraction with a total extraction time of 24 h. The extraction of higher amounts of arsenic (50–70% of total arsenic present in leaves depending on arsenic species application) from non-ground intact leaves with deionized water in comparison with the buffer (20–40% of total arsenic) is ascribed to osmotic effects. The arsenic species analysis revealed a cleavage of the amino groups from the phenyl ring for plants treated with aminophenylarsonic acids. A further important metabolic effect consisted in the production of inorganic arsenate and arsenite from the phenylated arsonic acid groups.     

Suitability of a magnetic particle immunoassay for the analysis of PBDEs in Hawaiian euryhaline fish and crabs in comparison with gas chromatography/electron capture detection-ion trap mass spectrometry

A gas chromatograph/electron capture detector-ion trap mass spectrometer (GC/ECD-ITMS) was used for the determination of polybrominated diphenyl ethers (PBDEs) in euryhaline fish and crabs. GC/ECD-ITMS results showed that average recoveries from the spiked fish samples are in a range of 58-123% with relative standard deviations (RSDs) of 5-19%. PBDE concentrations obtained from GC/ECD-ITMS ranged from 28 ng/g to 1845 ng/g lipid weight (lw) in all aquatic species collected from Hawaiian brackish waters. The general BDE congener concentration profile observed in this study is BDE-47 > BDE-100 > BDE-154 > BDE-99 > BDE-153 > BDE-28 > BDE-183. The ELISA results expressed as BDE-47 equivalents correlated well with those of GC/ECD-ITMS, with a correlation coefficient (R² = 0.68) and regression coefficient (slope = 0.82). Comparison of ELISA with GC/ECD-ITMS results demonstrated that ELISA provides a timely and cost-effective method to screen PBDEs in fish and crab samples.