Fate, distribution, and bioconcentration of pesticides impact on the organic farms of Cameron Highlands, Malaysia.

Occurrence and distribution of organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), and pyrethroid pesticides (PYRs) residues in the leafy vegetables were analyzed together with the soil samples using gas chromatography-electron capture detector. Edible tissues of vegetables showed detectable residues of these compounds indicating the influence of the conventional farms and nearby organic farms. In the vegetables, the OCPs concentrations were recorded as nd-133.3 ng/g, OPPs as nd-200 ng/g, and PYRs as nd-33.3 ng/g. In the soil, the OCPs concentrations were recorded as nd-30.6 ng/g, OPPs as nd-26.6 ng/g, and for PYRs as nd-6.7 ng/g. Bioconcentration factor (BCF) was higher for the OPPs (0.3) than the OCPs and PYRs (1.1). The OCPs concentration in the vegetables decreased in the following order: spinach > celery > broccoli > cauliflower > cabbage > lettuce > mustard. For OPPs, the concentration decreased in the following order: cauliflower > spinach > celery > cabbage > broccoli > lettuce > mustard and for PYRs as spinach > celery > lettuce > cabbage > broccoli. Principal component analysis indicates that the sources of these pesticides are not the same, and the pesticide application on the vegetables depends on the type of crop. There is a significant positive correlation between OPPs and the soil (r = 0.65) as compared to OCPs and PYRs (r = 0.1) as the vegetables accumulated OPPs more efficiently than OCPs and PYRs.

Determination of pesticide residues in leafy vegetables at parts per billion levels by a chemometric study using GC-ECD in Cameron Highlands, Malaysia.

A simple and sensitive analytical method has been developed employing gas chromatography coupled with electron capture detector (GC-ECD), and validated for screening and quantification of 15 pesticide residues at trace levels in cabbage, broccoli, cauliflower, lettuce, celery, spinach, and mustard. The method consists of two steps, first, to determine the significance of each factor by Pareto chart followed by optimization of these significant factors using central composite design (CCD). Minitab statistical software was used for these multivariate experiments for the generation of 24-1 design and CCD matrices. The method evaluation was done by external standard calibration with linearity range between 0.5 and 3mg/kg, with correlation coefficient 0.99, limit of detection (LOD) ranges between 0.02 and 4.5ng/g, and limit of quantification (LOQ) ranges between 0.2 and 45ng/g. The average recovery was between 60% and 128%, with RSD 0.2-19.8%. The method was applied on real vegetable samples from Cameron Highlands.

Limit of detection and limit of quantification development procedures for organochlorine pesticides analysis in water and sediment matrices.

BACKGROUND: Reliable values for method validity of organochlorine pesticides determination were investigated, in water by solid phase extraction and in sediment by Soxhlet extraction, followed by gas chromatography equipped with an electron capture detector. Organochlorine pesticides are categorized as Persistent Organic Pollutants. Hence, critical decisions to control exposure to these chemicals in the environment are based on their levels in different media; it is important to find valid qualitative and quantitative results for these components. In analytical chemistry, internal quality procedures are applied to produce valid logical results. RESULT: In this study, 18 organochlorine pesticides were targeted for analysis and determination in water and river sediment. Experiments based on signal-to-noise ratio, calibration curve slope and laboratory fortified blank methods were conducted to determine the limits of qualification and quantification. The data were compared with each other. The limitation values, following Laboratory Fortified Blank, showed significant differences in the signal-to-noise ratio and calibration curve slope methods, which are assumed in the results for the sample concentration factor to be 1,000 times in water and 10 times in sediment matrices. The method detection limit values were found to be between 0.001 and 0.005 µg/L (mean of 0.002 ± 0.001) and 0.001 and 0.005 µg/g (mean of 0.001 ± 0.001). The quantification limits were found to be between 0.002 and 0.016 µg/L (mean of 0.006 ± 0.004) and 0.003 and 0.017 µg/g (mean of 0.005 ± 0.003 µg/L) for water and sediment, respectively, based on the laboratory fortified blank method. Because of different slopes in the calibration methods, it was also found that the limitation values for some components from the internal standard were higher than from external standard calibration, because in the latter a factor for injection efficiency is applied for calibration. CONCLUSION: Technically, there are differentiations between detection limits for quality and quantity from component to component, resulting from noise, response factors of instruments and matrix interference. However, the calculation method is the cause of differentiation for each component of the different methods. The results show that for no matter what component, the relationship between these levels in different methods is approximately: Signal to Noise : Calibration Slope = 1:10. Therefore, due to different methods to determine LOD and LOQ, the values will be different. In the current study, laboratory fortified blank is the best method, with lower limitation values for Soxhlet and solid phase extraction of OCPs from sediment and water, respectively.

Distribution and fate of HCH isomers and DDT metabolites in a tropical environment-case study Cameron Highlands-Malaysia.

BACKGROUND: The serious impact effects of persistent organic pollutants such as organochlorine pesticides, especially dichlorodiphenyltrichloroethane family (DDTs) and hexachlorocyclohexane isomers (HCHs) have been causing widespread concern, despite effective control on their manufacturing, agricultural and vector practices. In that, in addition to the previous global limitations on DDTs usage, α-HCH, ß-HCH and lindane have also became an on-going topic of global relevance based on the latest Stockholm Convention list on 10th of May 2009. Concentrations of dichlorodiphenyltrichloroethane family (DDTs) and hexachlorocyclohexane isomers (HCHs) were determined by GC-ECD in Cameron Highlands, the main vegetables and flowers farming area in Malaysia as an agricultural tropical environment. A total of 112 surface water and sediment samples at eight points were collected along the main rivers in the area namely Telom and Bertam in the dry and wet seasons of 2011. RESULTS: Total concentration of HCH isomers ranged from not detected to 25.03 ng/L in the water (mean of 5.55 ±6.0 ng/L), while, it ranged from 0.002 to 59.17 ng/g (mean of 8.06±9.39 ng/g) in the sediment. Total concentration of DDT and its metabolites in the water samples varied from not detected to 8.0 ng/L (mean of 0.90±1.66 ng/g), whereas, it was in the range of 0.025 to 23.24 ng/g (mean of 2.55±4.0 ng/g) in the surface sediment samples. The ratio of HCHs and DDTs composition indicated an obvious historical usage and new inputs of these pesticides. Among alpha, beta, gamma and delta isomers of HCH, gamma was the most dominant component in the sediment and water as well. Some seasonal variations in the level of selected pesticides were noted. CONCLUSIONS: The results illustrate distribution, behaviour and fate of HCHs, and DDTs have closely connected with topological and meteorological properties of the area beyond their chemical characterizations. The features of environmental circumstances exceed one or more of these characters in importance than the other. Although the results show that the situation is better than 1998, the impact of persistent agrochemicals such as lindane and 4,4'DDE are revealed in a key tropical area of Malaysia.

Chemometric application in identifying sources of organic contaminants in Langat river basin.

Increasing urbanization and changes in land use in Langat river basin lead to adverse impacts on the environment compartment. One of the major challenges is in identifying sources of organic contaminants. This study presented the application of selected chemometric techniques: cluster analysis (CA), discriminant analysis (DA), and principal component analysis (PCA) to classify the pollution sources in Langat river basin based on the analysis of water and sediment samples collected from 24 stations, monitored for 14 organic contaminants from polycyclic aromatic hydrocarbons (PAHs), sterols, and pesticides groups. The CA and DA enabled to group 24 monitoring sites into three groups of pollution source (industry and urban socioeconomic, agricultural activity, and urban/domestic sewage) with five major discriminating variables: naphthalene, pyrene, benzo[a]pyrene, coprostanol, and cholesterol. PCA analysis, applied to water data sets, resulted in four latent factors explaining 79.0% of the total variance while sediment samples gave five latent factors with 77.6% explained variance. The varifactors (VFs) obtained from PCA indicated that sterols (coprostanol, cholesterol, stigmasterol, ß-sitosterol, and stigmastanol) are strongly correlated to domestic and urban sewage, PAHs (naphthalene, acenaphthene, pyrene, benzo[a]anthracene, and benzo[a]pyrene) from industrial and urban activities and chlorpyrifos correlated to samples nearby agricultural sites. The results demonstrated that chemometric techniques can be used for rapid assessment of water and sediment contaminations.

Comparative study of sample preparation techniques coupled to GC for the analysis of halogenated acetic acids (HAAs) acids in tap water.

Halogenated acetic acids (HAAs) are one of the most common disinfection by-products formed during chlorination of drinking water. Currently, there are three U.S. Environmental Protection Agency-approved methods for analysis of HAAs in drinking water: U.S. EPA method 552.2, Standard Method 6251, and U.S. EPA method 552.3. The current U.S.EPA-approved HAA analysis methods require tedious and time-consuming liquid-liquid extraction (LLE) and the use of hazardous chemicals. Besides U.S. EPA methods, capillary electrophoresis (CE), liquid chromatography (LC), including ion chromatography (IC), and electrospray ionization mass spectrometry (ESI-MS) have been applied in order to determine the HAAs in portable water with high detection limits. Detection limits required to analyze portable water samples can be regularly achieved only by gas chromatography-electron capture detector (ECD) and ESI-MS. In this study, improved gas chromatography-mass spectrometry (GC-MS) method was able to achieve HAAs analysis at low detection limits. Thus, a safe and rapid method is needed for the micro-determination of HAAs. A method involving solid-phase extraction (SPE) followed by GC-MS was developed to determine the HAAs in tap water. Selectivity, percent recovery, and detection limit studies were carried out on a LC-SAX (quaternary ammonium anion exchanger) SPE. Under optimized conditions, average recoveries for all nine HAAs spiked in drinking water samples ranged from 78.7% to 100%. The relative standard deviation data was found to range from 1.0% to 12.5% based upon five repeat recovery experiments, and estimated detection limit ranging between 0.16-0.009 microg/L was obtained. On this basis, SPE was studied as a possible alternative to LLE for the analysis of HAAs in water. Finally, the performance of the SPE-GC-MS with spiked drinking water samples was tested, and the results were compared with those obtained using LLE-GC-ECD. The method was applied for determination of HAAs in drinking water and water samples.

Chemometric approach to validating faecal sterols as source tracer for faecal contamination in water.

Faecal sterols detection is a promising method for identifying sources of faecal pollution. In this study, faecal contamination in water samples from point source (sewage treatment plants, chicken farms, quail farms and horse stables) was extracted using the solid phase extraction (SPE) technique. Faecal sterols (coprostanol, cholesterol, stigmasterol, beta-sitosterol and stigmastanol) were selected as parameters to differentiate the source of faecal pollution. The results indicated that coprostanol, cholesterol and beta-sitosterol were the most significant parameters that can be used as source tracers for faecal contamination. Chemometric techniques, such as cluster analysis, principal component analysis and discriminant analysis were applied to the data set on faecal contamination in water from various pollution sources in order to validate the faecal sterols' profiles. Cluster analysis generated three clusters: coprostanol was in cluster 1, cholesterol and beta-sitosterol formed cluster 2, while cluster 3 contained stigmasterol and stigmastanol. Discriminant analysis suggested that coprostanol, cholesterol and beta-sitosterol were the most significant parameters to discriminate between the faecal pollution source. The use of chemometric techniques provides useful and promising indicators in tracing the source of faecal contamination.

Determination of volatile organic compounds pollution sources in malaysian drinking water using multivariate analysis.

A field investigation was conducted at all water treatment plants throughout 11 states and Federal Territory in Peninsular Malaysia. The sampling points in this study include treatment plant operation, service reservoir outlet and auxiliary outlet point at the water pipelines. Analysis was performed by solid phase micro-extraction technique with a 100 microm polydimethylsiloxane fibre using gas chromatography with mass spectrometry detection to analyse 54 volatile organic compounds (VOCs) of different chemical families in drinking water. The concentration of VOCs ranged from undetectable to 230.2 microg/l. Among all of the VOCs species, chloroform has the highest concentration and was detected in all drinking water samples. Average concentrations of total trihalomethanes (THMs) were almost similar among all states which were in the range of 28.4--33.0 microg/l. Apart from THMs, other abundant compounds detected were cis and trans-1,2-dichloroethylene, trichloroethylene, 1,2-dibromoethane, benzene, toluene, ethylbenzene, chlorobenzene, 1,4-dichlorobenzene and 1,2-dichloro - benzene. Principal component analysis (PCA) with the aid of varimax rotation, and parallel factor analysis (PARAFAC) method were used to statistically verify the correlation between VOCs and the source of pollution. The multivariate analysis pointed out that the maintenance of auxiliary pipelines in the distribution systems is vital as it can become significant point source pollution to Malaysian drinking water.

Formation, modeling and validation of trihalomethanes (THM) in Malaysian drinking water: a case study in the districts of Tampin, Negeri Sembilan and Sabak Bernam, Selangor, Malaysia.

A modeling procedure that predicts trihalomethane (THM) formation from field sampling at the treatment plant and along its distribution system using Tampin district, Negeri Sembilan and Sabak Bernam district, Selangor as sources of data were studied and developed. Using Pearson method of correlation, the organic matter measured as TOC showed a positive correlation with formation of THM (r=0.380,P=0.0001 for Tampin and r=0.478,P=0.0001 for Sabak Bernam). Similar positive correlation was also obtained for pH in both districts with Tampin (r=0.362,P=0.0010) and Sabak Bernam (r=0.215,P=0.0010). Chlorine dosage was also found to have low correlation with formation of THM for the two districts with Tampin (r=0.233,P=0.0230) and Sabak Bernam (r=0.505,P=0.0001). Distance from treatment plant was found to have correlation with formation of THM for Tampin district with r=0.353 and P=0.0010. Other parameters such as turbidity, ammonia, temperature and residue chlorine were found to have no correlation with formation of THM. Linear and non-linear models were developed for these two districts. The results obtained were validated using three different sets of field data obtained from own source and district of Seremban (Pantai and Sg. Terip), Negeri Sembilan. Validation results indicated that there was significant difference in the predictive and determined values of THM when two sets of data from districts of Seremban were used with an exception of field data of Sg. Terip for non-linear model developed for district of Tampin. It was found that a non-linear model is slightly better than linear model in terms of percentage prediction errors. The models developed were site specific and the predictive capabilities in the distribution systems vary with different environmental conditions.