Statistical evaluation of an analytical IC method for the determination of trace level perchlorate

Trace level perchlorate analysis in water initiated a new development in the Ion Chromatography (IC) technology. Maintenance of a low detection limit may be highly affected by the operating conditions of the IC system. In this paper the homoscedasticity of the IC system within the calibration concentration range, the effect of the system drift on the calibration curve and the effect of the self regeneration suppressor (SRS) current on the detection limit were investigated. The experimental results were evaluated by statistical methods such as the Cochran test and the lack of fit test. The detection limits were obtained by two ways. One through method detection limit (MDL) and the other through detection limit from the calibration curve (DTC). The Cochran test results revealed the homoscedasticity of the IC system. The effect of system drift on the calibration curve was noticed by the lack of fit test. MDL yielded a lower but less reliable detection limit than DTC. An acceptable detection limit can be achieved under the lower SRS current (100 mA).     

Development of a comprehensive analytical method for the determination of chlorinated paraffins in spruce needles applied in passive air sampling

Conifer needles are used for the monitoring of atmospheric persistent organic pollutants. The objective of the present study was to develop a method for the detection of airborne chlorinated paraffins (CPs) using spruce needles as a passive sampler. The method is based on liquid extraction of the cuticular wax layer followed by chromatographic fractionation and detection of CPs using two different GCMS techniques. Total CP concentrations (sum of short (SCCP), medium (MCCP) and long chain CPs (LCCP)) were determined by EI-MS/MS. SCCP and MCCP levels as well as congener group patterns (n-alkane chain length, chlorine content) could be evaluated using ECNI-LRMS. For the first time, data on environmental airborne CPs on spruce needles taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) are presented providing evidence that spruce needles are a suitable passive sampling system for the monitoring of atmospheric CPs.     

Development of an SPME-GC-MS/MS method for the determination of pesticides in rainwater: laboratory and field experiments

A solid-phase microextraction -- coupled to a gas chromatography -- ion trap tandem mass spectrometry (SPME-GC-MS/MS) method was developed for the quantitative determination in rainwater of 8 pesticides amongst the most used in France and 3 triazines metabolites. The main factors affecting the SPME process were studied. Using a 3 mL sample, the method developed showed good linearity for concentrations ranging from 0.05 to 50 microgL(-1) with correlation coefficients between 0.997 and 0.9999 and relative standard deviations (% RSD) below 14%. The study of matrix effects showed that rainwater was too diluted to have any significant influence on the extraction efficiency. To validate the method, a field campaign was carried out on the rain events, which occurred in Strasbourg during a one-year period. The rain concentrations showed patterns of high pesticide concentrations during spring months, which were correlated to the spraying periods of most of these substances.     

Testing of a sampling system and analytical method for determination of semivolatile organic compounds in ambient air

A sampling system and analytical procedure for determining PCDD/Fs, PCBs, HCB, and PAHs in ambient air was tested. The reproducibility of the concentrations and the gas/particle partitioning was ± 10% for most compounds. The removal of gaseous compounds on the XAD resin trap was greater than 99%. The adsorption of gaseous substances on the glass fiber filter was negligible for compounds primarily found in the gas phase, but could not be ruled out for compounds found mainly on particles.     

Comparison of analytical techniques for the determination of aldehydes in test chambers

The level of carbonyl compounds in indoor air is crucial due to possible health effects and the high prevalence of their potential sources. Therefore, selecting a convenient and rapid analytical technique for the reliable detection of carbonyl compound concentrations is important. The acetyl acetone (acac) method is a widely used standard procedure for detecting gaseous formaldehyde. For measuring formaldehyde along with other carbonyl compounds, the DNPH-method is commonly applied. The recommended procedure for measuring volatile organic compounds (VOCs) is sampling on Tenax TA, followed by thermal desorption and GC/MS analysis. In this study, different analytical techniques for the quantification of formaldehyde, pentanal, and hexanal are critically compared. It was found that the acac- and DNPH-method are in very good agreement for formaldehyde. In contrast, the DNPH-method significantly underestimates indoor air concentrations of the higher aldehydes in comparison to sampling on Tenax TA, although both methods are strongly correlated. The reported results are part of the EURIMA-WKI study on levels of indoor air pollutants resulting from construction, building materials and interior decoration.     

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.     

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.     

Development of an analytical method for analysis of flubendiamide,des-iodo flubendiamide and study of their residue persistence in tomato and soil

Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v^?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v^?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg^?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare^?1 were 0.83 and 1.68 mg kg^?1,respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha^?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha^?1 were below detectable level (BDL, < 0.01 mg kg^?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.     

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.     

Development of an analytical method for analysis of flubendiamide, des-iodo flubendiamide and study of their residue persistence in tomato and soil

Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare?1 were 0.83 and 1.68 mg kg?1, respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha?1 were below detectable level (BDL, < 0.01 mg kg?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

The evaluation of an analytical method for polychlorinated terpenes (PCC) in biological samples using an internal standard

The quantitative analysis of PCC (Toxaphene) residues in biological samples using gas chromatography with electron capture detection has been evaluated. Dechlorane 603, a chloroalicyclic compound is used as internal standard and modifications of the injection system for proper evaporation of this high-boiling compound is described. In the cleanup procedure PCB (and 1 – 3 % of the PCC) are removed by adsorption chromatography. Chlordane components and DDT compounds remaining in the PCC fraction constitute 5 – 10 % and 13 – 16 %, respectively, of the peak area in the chromatograms of the samples investigated. The quantitative results are influenced by the number of PCC-peaks chosen for the calculations and have to be specified together with the PCC-levels reported. The recoveries of PCC from spiked samples (20 ug PCC per gram crude fat above “natural” level) are 61 – 98 %, the lower figures obtained with samples containing low levels of PCC-residues. The practical limit of detection is about 10 ng PCC per g extracted fat.     

An analytical method for the measurement of nonviable bioaerosols.

Exposures from indoor environments are a major issue for evaluating total long-term personal exposures to the fine fraction (<2.5 microm in aerodynamic diameter) of particulate matter (PM). It is widely accepted in the indoor air quality (IAQ) research community that biocontamination is one of the important indoor air pollutants. Major indoor air biocontaminants include mold, bacteria, dust mites, and other antigens. Once the biocontaminants or their metabolites become airborne, IAQ could be significantly deteriorated. The airborne biocontaminants or their metabolites can induce irritational, allergic, infectious, and chemical responses in exposed individuals. Biocontaminants, such as some mold spores or pollen grains, because of their size and mass, settle rapidly within the indoor environment. Over time they may become nonviable and fragmented by the process of desiccation. Desiccated nonviable fragments of organisms are common and can be toxic or allergenic, depending upon the specific organism or organism component. Once these smaller and lighter fragments of biological PM become suspended in air, they have a greater tendency to stay suspended. Although some bioaerosols have been identified, few have been quantitatively studied for their prevalence within the total indoor PM with time, or for their affinity to penetrate indoors. This paper describes a preliminary research effort to develop a methodology for the measurement of nonviable biologically based PM, analyzing for mold and ragweed antigens and endotoxins. The research objectives include the development of a set of analytical methods and the comparison of impactor media and sample size, and the quantification of the relationship between outdoor and indoor levels of bioaerosols. Indoor and outdoor air samples were passed through an Andersen nonviable cascade impactor in which particles from 0.2 to 9.0 microm were collected and analyzed. The presence of mold, ragweed, and endotoxin was found in all eight size ranges. The presence of respirable particles of mold and pollen found in the fine particle size range from 0.2 to 5.25 microm is evidence of fragmentation of larger source particles that are known allergens.     

Improvements to standard methodologies for the analytical determination of metals in stationary-source emissions samples

Deficiencies with the current European reference method for the analysis using inductively couple plasma-mass spectrometry of metals in samples from stationary emissions sources are presented based on experimental data obtained from real samples. The effect of these deficiencies on the quality and accuracy of data is highlighted with biases of up to 40% being observed in real samples. Suggestions to improve the performance of the standard method are presented. In particular, the beneficial effect of using a drift correction procedure to account for the decrease in instrument sensitivity observed during an analytical measurement series is demonstrated. It is shown that this corrective procedure results in substantial improvements to the accuracy of data produced.     

A semi-target analytical method for quantification of OH-PCBs in environmental samples

Environmental Science and Pollution Research - Hydroxylated polychlorinated biphenyls (OH-PCBs) are oxidative metabolites of PCBs and residuals found in original Aroclors. OH-PCBs are known to play...     

Comparison of different analytical procedures in the determination of trace elements in lichens

A BCR standard reference material of lichen (CRM 482) was used to validate an analytical procedure consisting of a microwave oven digestion associated with ICP-OES, ICP-MS and GFAAS techniques for the analysis of trace elements (Al, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in biomonitor samples. Two different acid mixtures were used: (a) 7 ml of HNO3, 1 ml of H2O2; (b) 7 ml of HNO3, 1 ml of H2O2 and 200 microl of HF; all digestions were carried out using 100-250 mg samples brought to a final volume of 50 ml. The validation of the procedure was carried out by two laboratories in terms of accuracy and precision; the former was estimated as percentage recovery by comparing experimental data with certificate values; the latter evaluated according to ISO standard 5725. Real lichen samples were analysed too with the procedures above described. In certified CRM 482 and real lichen samples the procedure with HF showed higher recovery values for Al, Ti, V, Ba and Fe than the procedure without HF. For all the other elements the two procedures gave comparable results both in terms of accuracy and precision. The recovery obtained with HF procedure for all the elements was generally better than 90-103%.     

高碘酸钾氧化中性红测定间苯二酚

在酸性和75℃条件下,微量的间苯二酚对高碘酸钾氧化中性红褪色反应具有显著的抑制作用,据此建立了测定间苯二酚的新的动力学光度法。该方法灵敏、快速、操作简便,此法的线性范围为0．1～3．0μg／mL,检出限为0．082μg／mL,对1．0μg／mL的间苯二酚测定11次的相对标准偏差为2．26％。     

A new method for the determination of collection efficiency of an aerosol sampler by electron microscopy

A method was developed to determine the particle collection efficiency of an aerosol sampler by electron microscopy. The determination method measures the absolute concentration of particles and the particle size distribution at the sampler inlet by two aerosol samplers connected in series. Particle samples collected in each sampler were microscopically observed and analyzed by electron microscopy. By this “double-sampler method”, the particle collection efficiencies of the thermal and electrostatic precipitators were determined as a function of particle size. The average particle size ranged from 0.02 to 0.4 μm and mean collection efficiencies were found to be 72 and 79% for the thermal and electrostatic precipitators, respectively.     

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.