Determination of Commonly Used Herbicides in Surface Water Using Solid-Phase Extraction and Dual-Column HPLC-DAD

The present study describes the application of different solid-phase extraction techniques for the extraction, separation, and quantitative determination of 10 commonly used herbicides with different chemical structures (chlorsulfuron, diuron, bentazone, linuron, chlorpropham, fenoxoprop-ethyl, MCPA, diclofop-methyl, fluazifop-butyl, trifluraline) in water. Octadecyl (C₁₈) Empore extraction disks, octadecyl (C₁₈), and stryene divinylbenzene (SDB) Bond Elut Env cartridges were compared for solid-phase extraction efficiency. Herbicides were separated and quantified by reversed-phase high performance liquid chromatography with diode-array detection (HPLC-DAD) with simultaneous separation on two columns of differing polarity (C₁₈ and CN) to confirm identification. Analytical separation was performed simultaneously on C₁₈ and CN columns. Reanalysis of the sample extracts on a (cyano) CN column were used to confirm the identity of these compounds. Method optimization and validation parameters were presented in this work. Recoveries varied from 76.0% to 99.0% for C₁₈ disks, from 75.1% to 100.0% for C₁₈ cartridges, and from 54.0% to 98.0% for SDB cartridges over concentrations at 0.025–0.4 μg L^?1. The limits of detection were 0.012–0.035 μg L^?1.     

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.     

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.     

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.     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, 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.     

High-performance liquid chromatography with conductimetric detection of perfluorocarboxylic acids and perfluorosulfonates

A rapid and simple method for separating and determining various environmentally harmful perfluorocarboxylic acids and perfluorosulfonates was successfully developed using high- performance liquid chromatography with conductimetric detection, for product and waste management of these compounds at manufacturing and processing sites. Compounds having C(3)-C(8) perfluoroalkyl groups were separated using a Tosoh TSKgel Super-ODS column and a mobile phase consisting of a mixture of methanol and aqueous NaH(2)PO(4) at several mixing ratios. The best detection limits for the compounds ranged from 0.12 to 0.66 mg l(-1) (ppm), and linear calibration graphs were obtained up to 87-109 mg l(-1). The combination of this method with concentration of the sample by solid-phase extraction with cartridges based on styrene-divinylbenzene-copolymer enabled the determination of approximately 50 microg l(-1) (ppb) for compounds with C(4)-C(8) perfluoroalkyl groups. This method was successfully used to monitor the artificial decomposition of the perfluorocarboxylic acid n-C(4)F(9)COOH induced by a photocatalyst.     

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.     

Measuring concentrations of volatile organic compounds in vinyl flooring

The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics. To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m2 section of new VF was punched randomly to produce -200 0.78-cm2 disks. The disks were milled to a powder at -140 degrees C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatography/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 microg/g VF for n-hexadecane to 130 microg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

A simplified method for sampling and analysis of high volume surface water for organic contaminants using XAD-2

A simple compressed-gas driven system for field processing and extracting water for subsequent analyses of hydrophobic organic compounds is presented. The pumping device is a pneumatically driven pump and filtration system that can easily clarify at 4 L/min. The extraction device uses compressed gas to drive filtered water through two parallel XAD-2 resin columns, at about 200 mL/min. No batteries or inverters are required for water collection or processing. Solvent extractions were performed directly in the XAD-2 glass columns. Final extracts are cleaned-up on Florisil cartridges without fractionation and contaminants analyzed by GC-MS. Method detection limits (MDLs) and recoveries for dissolved organic contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides are reported along with results of surface water analysis for the San Francisco Bay, CA.     

Method development for determination of fluroxypyr in water

Improved methods for extraction and clean up of fluroxypyr residue in water have been established. Two methods of fluroxypyr extraction were used, namely, Direct Measurement of fluroxypyr and Concentration of fluroxypyr onto A Solid Phase Extraction (SPE) Adsorbent, followed by elution with solvent before determination of fluroxypyr. The recovery for Direct Measurement of fluroxypyr in water containing 8-100 microg L(-1), ranged from 86 to 110% with relative standard deviation of 0.7 to 2.15%. For the second method, three types of SPE were used, viz. C18, C18 end-capped and polyvinyl dibenzene (ISOLUTE ENV+). The procedure involved concentrating the analyte from fluroxypyr-spiked water at pH 3, followed by elution of the analyte with 4 mL of acentonitrile. The recovery of fluroxypyr from the spiked sample at 1 to 50 microg L(-1) after eluting through either C18 or C18 end-capped ranged from 40-64% (with relative standard deviation of 0.7 to 2.15) and 41-65% (with standard deviation of 1.52 to 11.9). The use of ISOLUTE ENV+, gave better results than the C18, C18 end-capped or the Direct Measurement Methods. The recovery and standard deviation of fluroxypyr from spiked water using ISOLUTE ENV+ ranged from 91-102% and 2.5 to 5.3, respectively.     

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%.     

Simultaneous determination of eight metabolites of organophosphate and pyrethroid pesticides in urine

A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r² ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r² ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.     

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 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).     

Quantification of steroid sex hormones using solid-phase extraction followed by liquid chromatography-mass spectrometry.

In this study, the occurrence of trace amounts of natural and synthetic steroid estrogens in the aquatic environment was studied using liquid chromatography coupled with electrospray mass spectrometry, following solid-phase extraction (SPE). The SPE was performed with C18 and NH2 cartridges. The first objective was to develop a reliable method for analyzing steroid estrogens (resulting from human and animal excretions) in different matrices. The method developed was then applied to quantify the occurrence of natural and synthetic hormones (estrone [E1], 17beta-estradiol [betaE2], 17alpha-estradiol [alphaE2], estriol [E3], and 17alpha-ethinylestradiol [EE2]) in environmental samples in surface water and wastewater treatment plant (WWTP) influent and effluent. In the WWTP influents, betaE2, alphaE2, and E3 were identified as ranging up to 72.6 ng/L in WWTP influent and to 16 ng/L in WWTP effluent. Analysis o f surface wa ter sampled upstream from the WWTP revealed the presence of all five estrogens, at levels up to 19.8 ng/L. These concentrations of estrogens pose an issue for large and small communities, because they are higher than the recommended guidelines for estrogen-active compounds and because a lot of communities use surface water as drinking-water sources.     

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.     

Determination of antibiotic compounds in water by on-line SPE-LC/MSD

This study attempts to provide an improved approach for the analysis of antibiotics, which normally exist at low concentration in complex matrices such as receiving streams of wastewater treatment plant discharge. The analytical method developed in this study combines an existing pretreatment technique of solid-phase extraction (SPE) with liquid chromatography mass spectrometry (LC/MSD) through on-line connection. The on-line connection suppressed the target loss by keeping the cartridge from drying, which resulted in improvement of the recovery and saving of the analytical time. For the on-line solid-phase extraction of 10 ml water samples, recoveries were between 74.3% and 116.5% and average LOQ was 0.11 microg l(-1) for the sulfonamide antibiotics (SA) and 0.09 microg l(-1) for the tetracycline antibiotics (TA). Application of the developed method for the analysis of fourteen antibiotics revealed that several antibiotics were detected at concentrations above the LOQ in ARW. Treated and untreated sewage and agricultural wastewater were mostly responsible for the antibiotics contamination of the river. Antibiotics were detected at much higher concentrations in the agricultural wastewater sample than in the sewage sample, implying substantial use of antibiotics in the agricultural industry. Wastewater treatment was generally effective in separation of the antibiotics tested in this study. The extent of the treatment depended on the type of antibiotics. Hydrophobic antibiotics were more effectively separated from the solution than hydrophilic antibiotics.     

Determination of toxic cyclic heptapeptides by liquid chromatography with detection using ultra-violet, protein phosphatase assay and tandem mass spectrometry

Microcystins, toxic cyclic heptapeptides and nodularin-R, a toxic cyclic pentapeptide, were determined using liquid chromatography (LC) with detection using photo-diode array ultra-violet (PDA-UV) and protein phosphatase (PP) assay. Positive fractions were analysed for toxins using collision-induced dissociation (CID) and tandem MS/MS experiments which were carried out simultaneously using electrospray ion-trap instrumentation. Reversed-phase liquid chromatography (LC) using an acetonitrile/water gradient was used for the LC-MS(2) determination of six microcystins standards and nodularin. The molecular related ion species, [M+H](+)([M+2H](2+) in the case of MC-RR), were used as the precursor ions for MS(2) experiments. Optimum calibration and reproducibility data were obtained for MC-LR using LC-MS(2); 0.1-5.0 microg/ml, r2 = 0.992 (n = 3); % RSD < or =7.3 at 0.25 microg MC-LR/ml (n = 3). The detection limit (S/N = 3) was better than 0.1 ng. Water samples for microcystin analysis were first screened using protein phosphatase (PP) assays and positives were concentrated using C-18 solid-phase extraction. The developed method was applied to examine a lake in Ireland contaminated by Microcystis sp. and MC-LR and MC-LA were identified.