Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

A rapid and sensitive method for methyl tert-butyl ether analysis in water samples by use of solid phase microextraction and gas chromatography-mass spectrometry

This work describes a rapid and sensitive solid-phase microextraction (SPME) method for the isolation and analysis of methyl tert-butyl ether in water samples. Methyl tert-butyl ether was extracted from aqueous solutions using SPME fibre coated with Divinylbenzene/Carboxen/polydimethylsiloxane (30 microm film thickness) and analysed by GC-MS with a Hewlett Packard 6890/5973 system equipped with a capillary column coated with Vocol (30 m x 0.25 mm, 1.5 microm film thickness). Extraction parameters and chromatographic separation conditions were optimised. The developed method showed good analytical performance in terms of precision (RSD between 2% and 8%) and accuracy (mean recovery from 96% to 104%) with a detection limit of 14 ppt. Finally the method was applied to surface, tap and commercial mineral water samples, as well as snow samples collected along a busy road of Bologna town area. The median concentration of methyl tert-butyl ether in all these samples (0.05-0.4 ppb) was well below the maximum aqueous contamination levels in water adopted in the United States (13 ppb).     

Investigation of acute toxicity of cadmium chloride (CdCl2 . H2O) metal salt and behavioral changes it causes on water frog (Rana ridibunda Pallas, 1771)

The 96-h LC(50) value of cadmium chloride (CdCl(2).H(2)O), a metal salt widely used in industry, was determined in the water frog (Rana ridibunda Pallas, 1771). The experiments were conducted in two series and a total of 140 frogs were used to determine acute toxicity. In addition, behavioral changes in the water frog were determined for each cadmium chloride concentration. Data obtained from the cadmium chloride investigation were evaluated by using the probit analysis statistical method and the 96 h LC(50) value for water frog was estimated to be 51.2 mg/l.     

Experimental and statistical validation of SPME-GC-MS analysis of phenol and chlorophenols in raw and treated water

A procedure based on solid-phase microextraction (SPME) and gas chromatography coupled with mass spectrometry (GC-MS) was developed and validated in order to analyse 10 phenols in water samples. The optimised conditions were obtained using polyacrylate fibre (PA), 20ml of sample volume, 10% NaCl, pH 4.0 and direct extraction at 35 degrees C and 1000rpm, for 40min. The linear range and quantification limits for these compounds by SPME-GC-MS were defined. An evaluation of the main uncertainty sources of this method is included, which allows expanded uncertainties in the 9.4-35% range for the majority of the compounds. The main source of uncertainty is associated with matrix effects. The validated method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from water supply system of a large area (Lisbon and neighbour municipalities).     

Analysis of organochlorine pesticides in water by novel activated carbon fiber-solid phase microextraction coupled with gas chromatography-mass spectrometry

This study describes a fast activated carbon fiber-solid phase microextraction (ACF-SPME) method for determining organochlorine pesticides (OCPs) in water. The pesticides in this study consist of Hexachlorobenzene (HCB) and alpha-, beta-, gamma-hexachlorocyclohexanes (HCHs). The optimal experimental procedures for the adsorption and desorption of four OCPs were evaluated. The linearity was obtained with a RSD of 20% for the OCPs studied over a range from 1.0 to 100 microg/L. The limits of detection at ng/L level were achieved with GC-MS under selected ion monitoring (SIM) acquisition mode. The proposed method was applied to the determination of OCPs concentration in tap water. The results have demonstrated the suitability of the ACF-SPME-GC-MS approach for the analysis of multi-residue OCPs in water. Compared to the commercial fiber, ACF has shown its advantages in solvent-resistance, thermal stability, and the cost. The results obtained in this study suggest that ACF is a promising choice in solid phase microextraction.     

Determination of benzene, toluene, ethylbenzene, xylenes in water at sub-ng l-1 levels by solid-phase microextraction coupled to cryo-trap gas chromatography-mass spectrometry

A trace analytical method of benzene, toluene, ethylbenzene and xylenes (BTEX) in water has been developed by using headspace solid-phase microextraction (HS-SPME) coupled to cryo-trap gas chromatography-mass spectrometry (GC-MS). The chromatographic peak shape for BTEX was improved by using cryo-trap equipment. The HS-SPME experimental procedures to extract BTEX from water were optimized with a 75 microm carboxen/polydimethylsiloxane (CAR/PDMS)-coated fiber at a sodium chloride concentration of 267 g l(-1), extraction for 15 min at 25 degrees C and desorption at 290 degrees C for 2 min. Good linearity was verified in a range of 0.0001-50 microg l(-1) for each analyte (r(2)=0.996-0.999). The limits of detection (LODs) of BTEX in water reached at sub-ng l(-1) levels. LODs of benzene, toluene, ethylbenzene, m/p-xylene and o-xylene were 0.04, 0.02, 0.05, 0.01 and 0.02 ng l(-1), respectively. The proposed analytical method was successfully used for the quantification of trace BTEX in ground water. The results indicate that HS-SPME coupled to cryo-trap GC-MS is an effective tool for analysis of BTEX in water samples at the sub-ng l(-1) level.     

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.     

Development of an immunochromatographic assay for the rapid detection of bromoxynil in water

A rapid immunochromatographic one-step strip test was developed to specifically determine bromoxynil in surface and drinking water by competitive inhibition with the nano colloidal gold-conjugated monoclonal antibody (mAb). Bromoxynil standard samples of 0.01–10 mg L⁻¹ in water were tested by this method and the visual limit was 0.06 mg L⁻¹. The assay only required 5 min and one-step by dispensing a drop of sample solution onto a strip. Parallel analysis of water samples with bromoxynil showed comparable results from one-step strip test and ELISA. Therefore, the one-step strip test is very useful as a screening method for qualitative detection of bromoxynil in water.     

A fingerprint analysis method for characterization of dissolved organic matter in secondary effluents of municipal wastewater treatment plant

Dissolved organic matter (DOM) in wastewater and reclaimed water is related to water quality, safety, and treatability. In this study, DOM was characterized through a fingerprint analysis method for DOM characterization using resin fractionation followed by size exclusion chromatography (SEC). Resin fractionation was used in the first step to divide the DOM in water samples into six resin fractions, namely, hydrophobic acids (HOA), hydrophobic bases (HOB), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases (HIB), and hydrophilic neutrals (HIN). SEC analysis was then performed to separate each resin fraction into several (n) subfractions with different molecular weights (MW). Thus, the total DOM in the water sample was fractionated into 6n subfractions. After quantification of each subfraction by dissolved organic carbon (DOC), a fingerprint graph was constructed to express the distribution of DOM in the subfractions. The fingerprint analysis method was applied to a secondary effluent sample during ozonation. Ozonation (dose of 10 mg L^?1) removed the DOC only by 8 % and reduced UV₂₅₄ of the sample by 36 %. Fingerprint graphs also revealed that the resin fractions changed quite limitedly but transformation of subfractions occurred notably.     

Simultaneous voltammetric determination of four triazine herbicides in water samples with the aid of chemometrics

A novel differential pulse voltammetry (DPV) method was developed for the simultaneous analysis of herbicides in water. A mixture of four herbicides, atrazine, simazine, propazine and terbuthylazine was analyzed simultaneously and the complex, overlapping DPV voltammograms were resolved by several chemometrics methods such as partial least squares (PLS), principal component regression (PCR) and principal component–artificial networks (PC–ANN). The complex profiles of the voltammograms collected from a synthetic set of samples were best resolved with the use of the PC–ANN method, and the best predictions of the concentrations of the analytes were obtained with the PC-ANN model (%RPE_T = 6.1 and average %Recovery = 99.0). The new method was also used for analysis of real samples, and the obtained results were compared well with those from the GC-MS technique. Such conclusions suggest that the novel method is a viable alternative to the other commonly used methods such as GC, HPLC and GC-MS.     

Comparing solid phase extraction and direct injection for the analysis of ultra-trace levels of relevant explosives in lake water and tributaries using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid phase extraction and direct injection analysis were evaluated for the determination of traces of explosives such as TNT and its mono and diamino metabolites, HMX, RDX, nitroglycerin and PETN in lake water and tributaries applying liquid chromatography-electrospray tandem mass spectrometry. Improved chromatographic separation was achieved on a phenyl based stationary phase with baseline resolution of the mono- and diamino metabolites of TNT. Identification and quantification of the target compounds was performed by multiple reaction monitoring applying electrospray ionization in either the positive mode for the diaminometabolites of TNT or the negative mode for all other compounds. An extensive method validation was performed and limits of quantification were obtained for the explosives in preconcentrated lake water samples from 0.03 to 1 ng l(-1) and 0.1 to 5 ng l(-1) in river water. Direct injection analysis revealed comparable results to preconcentrated water samples for the most persistent explosives. Analysis of lake water samples collected at different depths showed the presence of HMX, RDX and PETN at concentrations from 0.1 to 0.4 ng l(-1). The analysis of main tributaries revealed concentrations from 0.1 to 0.9 ng l(-1) of the same compounds. They seem to be responsible for the contamination of the explosives in the lakes.     

基于聚类分析和水质标识指数的水质评价方法

为探讨一种适用于大尺度、多断面和长时间的水质评价方法,用层次聚类分析将2006~2008年海河5个监测断面的165个水质样本分为20组,并用方差分析验证了结果的可靠性。用综合水质标识指数表示水质样本的综合特征,与单因子评价法相比,该方法充分考虑了最差水质因子的影响,避免了单因子评价法以偏概全的缺陷,且分辨率高。将评价结果分解到各断面,结果表明:密云水库、官厅水库和于桥水库的水质处于II~III类水之间,可满足作为饮用水水源水的要求,三岔口断面大部分时间为IV~V类水,张家口八号桥断面全年有6个月以上水质属于劣V类。     

Parts-per-trillion LC-MS(Q) analysis of herbicides and transformation products in surface water

The goal of this study was to develop a robust method of analyzing surface water samples for S-triazine herbicides, chloroacetanilide herbicides, and their transformation products (TPs) using solid-phase extraction (SPE) followed by liquid chromatograph-mass spectrometry (LC-MS) with electrospray ionization (ESI) by in-source collision-induced dissociation (ISCID) capability of an orthogonal electrospray ionization probe on a single quadrupole LC-MS system. The method developed here met the goals of the study and yielded estimated method detection limits (EMDLs) averaging 0.3 ± 0.1 ng L(-1) for S-triazines and their TPs and 0.7 ± 0.4 ng L(-1) for chloroacetanilides and TPs. Spiked filtered river water yielded SPE recoveries ranging from 94.2 % ± 4.8 % for S-triazines and TPs after eliminating three compounds with less that 65 % recovery from analysis and 95.9 % ± 19 % for chloroacetanilides and their TPs. The method was field-tested with filtered water samples collected from four sites over a four-month period. Detectible values of S-triazines and TPs ranged from 0.3 to 1540 ng L(-1) with a mean of 79.3 and a median of 19.4 ng L(-1). Detectible values for chloroacetanilides and TPs ranged from 0.31 to 3780 ng L(-1) with a mean of 252 and a median of 25.6 ng L(-1). An additional goal was to determine if the method was useful for microbial degradation studies using native bacterial communities. The bacteria transformed atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) solely into 2-hydroxy atrazine (2-hydroxy-4-ethylamino-6-isopropylamino-S-triazine) with concentrations of 78.4, 63.3 and 32.5 ng L(-1) after 12 days of incubation compared with 6.3 and 7.1 ng L(-1) for control dark and control sunlight respectively.     

A real-time,dynamic early-warning model based on uncertainty analysis and risk assessment for sudden water pollution accidents

A real-time, dynamic, early-warning model (EP-risk model) is proposed to cope with sudden water quality pollution accidents affecting downstream areas with raw-water intakes (denoted as EPs). The EP-risk model outputs the risk level of water pollution at the EP by calculating the likelihood of pollution and evaluating the impact of pollution. A generalized form of the EP-risk model for river pollution accidents based on Monte Carlo simulation, the analytic hierarchy process (AHP) method, and the risk matrix method is proposed. The likelihood of water pollution at the EP is calculated by the Monte Carlo method, which is used for uncertainty analysis of pollutants’ transport in rivers. The impact of water pollution at the EP is evaluated by expert knowledge and the results of Monte Carlo simulation based on the analytic hierarchy process. The final risk level of water pollution at the EP is determined by the risk matrix method. A case study of the proposed method is illustrated with a phenol spill accident in China.     

The Application of the Karl Fischer Oven for the Determination of Water in Consumer Products

Abstract

The direct Karl Fischer (KF) titration method has known interferences for measuring water content. In addition, in analyzing some paints, KF can fail to produce an accurate analysis. The California Air Resources Board (GARB) staff has developed a KF procedure that can be used to determine the water content of consumer products. The procedure uses an oven accessory to the titration system, and is based on a distillation method developed by the California Polytechnical University at San Luis Obispo (Cal Poly). Samples are diluted in l-methoxy-2-propanol (MPA), and an aliquot is injected into an enclosed oven system, where the MPA/water azeotrope is swept directly into the KF titration vessel. The technique is accurate and precise and, thus far, proves to be a fast and reliable method for analysis.     

HPLC-PFD determination of priority pollutant PAHs in water,sediment, and semipermeable membrane devices

High performance liquid chromatography coupled with programmable fluorescence detection was employed for the determination of 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs) in water, sediment, and semipermeable membrane devices (SPMDs). Chromatographic separation using this analytical method facilitates selectivity, sensitivity (ppt levels), and can serve as a non-destructive technique for subsequent analysis by other chromatographic and spectroscopic techniques. Extraction and sample cleanup procedures were also developed for water, sediment, and SPMDs using various chromatographic and wet chemical methods. The focus of this publication is to examine the enrichment techniques and the analytical methodologies used in the isolation, characterization, and quantitation of 15 PPPAHs in different sample matrices.     

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.     

Validation of an efficient method for the determination of pesticide residues in fruits and vegetables using ethyl acetate for extraction

In this study, a version of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was modified to use ethyl acetate (EtOAc) rather than acetonitrile (MeCN) for extraction in the determination of multiple pesticide residues in fruits and vegetables. EtOAc is better suited than MeCN for gas chromatographic (GC) analysis with electron capture detection (ECD) and nitrogen-phosphorus detection (NPD). The method entailed extraction of 30 g chopped sample plus 5 g NaHCO(3) and 30 g anhydrous Na(2)SO(4) with 60 mL EtOAc using a probe blender. After a centrifugation step, removal of residual water and cleanup were performed using dispersive solid-phase extraction (dispersive-SPE) with MgSO(4) and primary secondary amine (PSA) sorbent. (14)C-labeled chlorpyrifos with liquid scintillation counting was used to assist in optimizing and characterizing the method, and GC-ECD and GC-NPD were used for analysis of 24 selected pesticides. The method was validated using tomato, apple and frozen green bean matrices spiked at 0.05, 0.5, and 5 mg/kg. For 22 of the analytes, recoveries averaged 93% for all three commodities over the validation range with a relative standard deviation of 10% (n = 1182). Lower recoveries of dichlorvos were obtained with the method and iprodione determination was compromised in the green beans by an interfering peak. Typical limits of detection were 0.005-0.01 mg/kg with the method.     

Influence of sulfide (S2-) on preservation and speciation of inorganic arsenic in drinking water

Generally, H2SO4, HNO3, HCl or the combination of ethylenediaminetetraacetate with acetic acid (EDTA-HAc) have been used to preserve arsenite and arsenate species prior to analysis. When these acidic preservatives are added in sulfidic water, instantaneous precipitation of poorly crystalline orpiment, As2S3(am), occurs, thereby lowering the total arsenic, As(Tot), analysis. A new method for the determination of As(Tot) was developed in which acid-preserved sulfidic water samples were oxidized with NaOCl, converting As2S3(am) and thioarsenic species to arsenate. A new method was also developed for the separation of uncharged arsenite and charged thioarsenic species in fresh, unpreserved sulfidic water by adsorbing the charged thioarsenic species while allowing uncharged arsenite to pass through a strong-base resin unhindered. The adsorbed thioarsenic species could be eluted efficiently with 0.16 M NaOCl solution.     

Analysis of Herbicide Krovar I™ by Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

A simple, very efficient method is presented for routine analysis of herbicide Krovar I? (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid–liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 µg L^?1 and for diuron 0.03 µg L^?1. Method detection limit for soil samples is 0.01 µg g^?1 dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.