Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D - first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.     

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.     

Determination of nitrate and other water quality parameters in groundwater from UV/Vis spectra employing partial least squares regression

The use of UV/Vis spectroscopy in combination with partial least squares (PLS) regression for the simultaneous prediction of nitrate and non-purgeable organic carbon (NPOC) in groundwaters was evaluated. A model of high quality was obtained using first order derivative spectra in the range 200-300 nm. Inclusion of non-UV-absorbing constituents in the modeling procedure, i.e., chloride, sulfate, fluoride, total carbon (TC), inorganic carbon (IC), alkalinity, pH and conductivity was also evaluated. This model seemed to be useful for prediction of chloride, TC, IC, alkalinity and conductivity, while its ability to predict sulfate, fluoride and pH was poor. In conclusion, application of PLS regression, which requires neither filtration of samples nor addition of chemicals, is a promising alternative for fast interpretation of geochemical patterns of groundwater quality.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

Comparison of nonlinear least squares and log transformation procedures for calculating volatilization coefficients

A nonlinear least squares procedure and a log transformation procedure for calculating first-order rate coefficients from experimental concentration-versus-time data were compared using laboratory measurements of the volatilization from water of 1,1,1-trichloroethane and 1,2-dichloroethane and the absorption of oxygen by water. Ratios of the nonlinear least squares to log transformation volatilization and absorption coefficients for 77 tests ranged from 0.955 to 1.08 and averaged 1.01. Comparison of the maximum, minimum, and mean root-mean-square errors of prediction for six sets of coefficients showed that the errors for the nonlinear least squares procedure were almost always smaller than the errors for the log transformation procedure.     

Total and partial digestion of sediments for the evaluation of trace element environmental pollution

Four different sample treatment methods for the determination of trace elements have been compared: a total digestion with HNO3-H2O2-HF using microwave, and three different standardized methods of fractionation: BCR three-steps sequential extraction, USEPA standard 3050B and ISO standard 11466. The four treatment methods were applied to the determination of Cu and Ni in four samples collected in different areas of Cienfuegos Bay (Cuba). The location of samples and the analytes were selected on the basis of results obtained by previous studies. Analyses following total digestion and BCR three-steps procedure were performed by inductively coupled plasma mass spectroscopy whereas analyses following EPA and ISO procedures were performed by flame atomic absorption spectroscopy. The results obtained have been compared with an estimated anthropic fraction evaluated in each sampling point as the difference between the total concentration and an estimated background concentration level. The BCR three-steps provided the best approximation of the estimated anthropic fraction and was therefore applied also in the determination of Pb and Cd for further consideration.     

Fragment constant method for prediction of fish bioconcentration factors of non-polar chemicals

A fragment constant method for prediction of fish bioconcentration factor (BCF) was established based on experimental BCF values for 80 non-polar chemicals from nine classes. The model was evaluated using coefficients of determination and mean residuals, which are 0.995 and 0.1836, respectively. Jackknife tests were applied to examine the robustness of the prediction model on a class-by-class basis.     

Quantifying background nutrient concentrations in coastal waters: a case study from an urban embayment of the Baltic Sea

Successful management of damaged coastal ecosystems requires reliable scientific evidence of their past state. Here we demonstrate that the sediment record of biotic indicators can be used to quantitatively reconstruct nutrient concentrations preceding the short time span covered by monitoring records. We generated a diatom-based weighted-averaging partial least squares transfer function model for total dissolved nitrogen with a prediction accuracy of 0.09 microg L(-1) (log10 units). The model was applied to sediment core data from Laajalahti Bay, an urban embayment in Helsinki, Finland, where its performance was validated against a approximately 30 yr record of water-quality data and known land-use changes in the watershed. The model tracked well the trends in the nutrient record, although it underestimated very high nutrient concentrations in this highly impacted embayment. The generally good agreement between the actual and predicted values implies that the approach has considerable potential in assessing background nutrient concentrations in coastal waters.     

Comparison of the results obtained by four receptor modelling methods in aerosol source apportionment studies

In this work the performance and theoretical background behind two of the most commonly used receptor modelling methods in aerosol science, principal components analysis (PCA) and positive matrix factorization (PMF), as well as multivariate curve resolution by alternating least squares (MCR-ALS) and weighted alternating least squares (MCR-WALS), are examined. The performance of the four methods was initially evaluated under standard operational conditions, and modifications regarding data pre-treatment were then included. The methods were applied using raw and scaled data, with and without uncertainty estimations. Strong similarities were found among the sources identified by PMF and MCR-WALS (weighted models), whereas discrepancies were obtained with MCR-ALS (unweighted model). Weighting of input data by means of uncertainty estimates was found to be essential to obtain robust and accurate factor identification. The use of scaled (as opposed to raw) data highlighted the contribution of trace elements to the compositional profiles, which was key to the correct interpretation of the nature of the sources. Our results validate the performance of MCR-WALS for aerosol pollution studies.     

Determination of the molecular weight of fulvic acids by UV/VIS spectroscopy

Partial least squares (PLS) modeling was applied to investigate number-average molecular weights (Mn) and weight-average molecular weights (Mw) of fulvic acids (FAs) in relation to the corresponding UV/VIS spectra. The Mn and Mw values were determined by size exclusion chromatography (SEC). The impact of pH control, wavelength range and density as well as smoothing and derivation of spectra were tested. It was found that PLS models based on absorbance spectra can be a fast and powerful complement to existing techniques employed for determination of molecular weights of FAs. Control of pH of the FA solutions is important for the performance of the models. The models were also compared with the best univariate alternatives.     

热解析-固相微萃取-气相色谱法测定空气样品中挥发性有机化合物

建立了热解析-固相微萃取-气相色谱法测定空气样品中挥发性有机化合物的分析方法，并对色谱分离条件、玻璃针筒保存样品的稳定性、固相微萃取萃取纤维、萃取时间、色谱进样时间等条件进行了优化，9种挥发性有机化合物的峰面积与其质量浓度在所测范围内有较好的线性关系，相对标准偏差＜8.8%，检出限为0.05～0.75 μg/100 mL，满足实际空气样品测定需要。     

The importance of outlier detection and training set selection for reliable environmental QSAR predictions

Empirical QSAR models are only valid in the domain they were trained and validated. Application of the model to substances outside the domain of the model can lead to grossly erroneous predictions. Partial least squares (PLS) regression provides tools for prediction diagnostics that can be used to decide whether or not a substance is within the model domain, i.e. if the model prediction can be trusted. QSAR models for four different environmental end-points are used to demonstrate the importance of appropriate training set selection and how the reliability of QSAR predictions can be increased by outlier diagnostics. All models showed consistent results; test set prediction errors were very similar in magnitude to training set estimation errors when prediction outlier diagnostics were used to detect and remove outliers in the prediction data. Test set prediction errors for substances classified as outliers were much larger. The difference in the number of outliers between models with a randomly and systematically selected training illustrates well the need of representative training data.     

Measurement of the pesticide methomyl by modified quartz crystal nanobalance with molecularly imprinted polymer

A simple and cost-effective analysis method based on quartz crystal nanobalance (QCN) coated with a molecularly imprinted polymer (MIP) for measurement of methomyl was investigated. In the first part of this study, a sensitive, selective and reliable quartz crystal nanobalance (QCN) sensor was designed for the selective determination of methomyl in aqueous solutions. In the second part, in order to demonstrate the applicability and performance of the fabricated sensor in the real world situation, it was successfully applied for the determination of methomyl residual in photo catalytic degradation by ZnO powders in aqueous solutions. The fabricated sensor presents a high selectivity and sensitivity (4.56 Hz per mg L^?1) for methomyl and it can be used for determination of methomyl concentration ranged between 1 to 45 mg L^?1. Furthermore, good reproducibility, R.S.D. = 2.14% (n = 5) was observed. To investigate the performance of the sensor, the change in the insecticide concentration during the photocatalytic degradation of methomyl by ZnO was investigated by QCN and UV/Vis spectroscopy. Results obtained from QCN sensor and UV/Vis spectroscopy measurement are in good mutual agreement. So the fabricated sensor may provide an efficient, low cost, easy-to-use method for the in-field evaluation of specific targeted analytes in aqueous solutions which in turn may lead to improved food and water safety.     

A comprehensive pollution survey of polychlorinated dibenzo-p-dioxins and dibenzofurans by means of principal component analysis and partial least squares regression

The combined use of principal component analysis and partial least squares regression to the interpretation of polychlorinated dibenzofuran (PCDF) and dibenzo-p-dioxin (PCDD) patterns in crabs are investigated. By exploratory principal component analysis, the PCDFs and the PCDDs are ranked according to their specificity to the emission source. Among the most specific PCDFs to the emission are the 12368/13479-PeCDF and 12478-PeCDF. The 123789-HxCDD isomer is the only specific PCDD to the emission source. Partial least squares regression is used both to explore the determination of sex specific isomers, and in confirmatory analysis by quantitatively relating the pollution waste to the distance from the emission source. 123678-HxCDF is statistically significant for the separation between male and female crabs collected at the same distance from the emission source, while no separation between male and female crabs is evident from 1234789-HpCDF, Octa-CDF, 2,3,7,8-TCDD and Octa-CDD. This observation is somewhat more shaded than what has previously been reported in the literature on differences in male and female crabs. A linear relationship exists between the logtransformed distance and the concentration of PCDFs and PCDDs in male crabs collected between 18 and 33 km from the source. This model underestimates the predicted distance of crabs collected between 33 and 56 km, possible due to a higher sedimentation rate at distances closer to the fjord and the factory.

Although applied to PCDF/PCDD data in this case, the outlined multivariate methods should be applicable to all kind of similar environmental surveys.     

BTEX determination in water matrices using HF-LPME with gas chromatography-flame ionization detector

In the present work, a sample pre-treatment technique for the determination of trace concentrations of benzene, toluene, ethyl benzene and xylene (BTEX) in aqueous samples has been developed and applied to analysis of the selected analytes in environmental water samples. The extraction procedure is based on coupling polypropylene hollow-fiber liquid phase microextraction (HF-LPME) with gas chromatography by flame ionization detection (GC-FID). The effective parameters such as organic solvent, extraction time, agitation speed and salting effect were investigated. Good reproducibilities of the extraction performance were obtained, with the RSD values ranging from 2.02 to 4.61% (n=5). The method provided 41.47-128.01 fold preconcentration of the target analytes. The limits of detections for the BTEX were in the range of 0.005-03microg ml(-1). In addition, sample clean-up was achieved during LPME due to the selectivity of the hollow fiber, which prevented undesirable large molecules from being extracted. Real samples (River and waste waters) containing BTEX were examined using this method with good linearity and precision (RSDs most lower than 6.00%, n=5). All experiments were carried out at room temperature, 22+/-0.5 degrees C.     

Analysis of air pollution plant exposure data: The soft independent modelling of class analogy (SIMCA) and partial least squares modelling with latent variable (PLS) approaches

Air pollution plant exposure experiments sometimes involve registration of several plant variables (dependent variables) as a function of several treatment variables (independent variables). Both independent and dependent variables might be correlated, and the number of variables might exceed the number of observations. Analyzing one variable at a time gives a risk of spurious results. The multivariate statistical methods, soft independent modelling of class analogy (SIMCA) and partial least squares modelling with latent variables (PLS) allow all variables to be analyzed simultaneously. These methods are presented and applied to data from open-top chamber experiments with O3, SO2, and NO2 fumigation of three varieties of Lolium multiflorum Lam. The results demonstrate the dependence of the plant response to plant variety, plant age, climate, and pollutant dosages.     

Sorption equilibria of metal ions on bone char

The ability of bone char to adsorb three metal ions, namely, copper(II), zinc(II) and cadmium(II) ions from wastewater has been studied. Three single-component equilibrium systems and three binary equilibrium systems have been measured experimentally. The three single-component equilibrium data were analyzed using the Langmuir and the Sips equilibrium isotherm equations. The Sips isotherm gave a better fit of the experimental data than the Langmuir isotherm based on the sum of squares errors (SSE) analysis. The Cu-Zn, Cu-Cd and Cd-Zn binary equilibrium experimental data were examined by incorporating the Langmuir and the Sips isotherm equations into the ideal adsorbed solution theory (IAST). The solution methods and the predicted results for the three binary systems at different metal ion compositions have been evaluated. In addition, the application of the IAST to the model prediction for the fixed bed system is presented.     

Simultaneous determination of chlorothalonil and its metabolite 4-hydroxychlorothalonil in greenhouse air: dissipation process of chlorothalonil

An analytical method was developed and tested for the simultaneous determination of chlorothalonil and its main metabolite 4-hydroxychlorothalonil, in airborne samples. High performance liquid chromatography equipped with Ultra-violet detector was used to separate and quantify the analytes. Glass microfibre filters for the collection of the analytes' particles were tested. Solid sorbents, such as Tenax, Florisil, XAD-2 and silica gel, were studied to find out the most suitable material for the collection of the analytes in the gas phase. The results have shown that only chlorothalonil was trapped in the vapor phase with highest results obtained when silica gel was the sorbent of choice. Linearity was demonstrated in a wide concentration range 0.01-10.00 mg L(-1). Recoveries from spiked glass microfibre filters and silica gel cartridges for chlorothalonil and 4-hydroxychlorothalonil were almost quantitative. The quantification limits were calculated to be 8.4 and 19.6 ng m(-3) in air for chlorothalonil and 4-hydroxychlorothalonil, respectively. The two analytes spiked on the GF/A filters and silica gel cartridges were proven to be stable for more than 15 days, at 4degrees C and ambient temperature. The applicability of the present method was demonstrated by the analysis of the chlorothalonil and its metabolite in greenhouse air.     

Simultaneous gas chromatographic determination of chlorpyrifos and its impurity sulfotep in liquid pesticide formulations

An analytical method for simultaneous determination of the active substance (chlorpyrifos) and its relevant impurity (sulfotep) in commercial pesticide formulations has been developed and validated. The proposed method entails extraction of the analytes from samples by sonication with acetone and analysis by gas chromatography-flame ionization detection (GC-FID). The proposed method was characterized by satisfactory accuracy and precision. The repeatability expressed as relative standard deviation (RSD) was lower than the acceptable values calculated from the modified Horwitz equation whereas individual recoveries were in the range of 98–102% and 80–120% for chlorpyrifos and sulfotep, respectively. The limit of quantification (LOQ) for the impurity (sulfotep) was 0.003 mg mL^?1 corresponding to the maximum permitted level according to Food and Agricultural Organization of the United Nations (FAO) specifications for the active substance (chlorpyrifos) being 3 g kg^?1 of the chlorpyrifos content found. The main advantage of the proposed method was a considerable reduction in the analysis time since both analytes were determined based on a single injection into the GC-FID. Analysis of real samples of commercial pesticide formulations confirmed fitness-for-purpose of the proposed method.