Monitoring and modelling of siloxanes in a sewage treatment plant in the UK

Monitoring of cyclic volatile methylsiloxanes (cVMS) carried out at Anglian Water’s Broadholme sewage treatment plant (STP) is described. The method deployed used headspace gas chromatography/mass spectrometry (HS-GC/MS) and the addition of isotopically labelled cVMS to correct for partitioning in samples containing high levels of particulate and dissolved organic carbon. The method was capable of measuring cVMS in raw sewage samples, with recoveries of 80%, 85% and 71% respectively, for D₄, D₅ and D₆. The limit of quantification was 0.2 μg L⁻¹ for all three substances. Recoveries close to 100% were observed for all cVMS spiked into treated effluent (LOQ = 0.01 μg L⁻¹). Despite the volatile nature of cVMS and its ubiquitous presence in the ambient atmosphere, the methods deployed showed excellent recoveries, reproducibility and quantification limits. A distinct diurnal variation in cVMS concentration, probably linked with the use of personal care products was observed for raw sewage but not in treated sewage effluent. The estimated per capita consumption of D₅ (∼2.7 mg cap⁻¹ d⁻¹) derived for the population served by this plant was significantly lower than that derived in the Environment Agency (UK) risk assessment (11.6 mg cap⁻¹ d⁻¹). The cVMS were highly removed during sewage treatment with efficiencies greater than 98%. The methods and findings of this pilot study can be used as the basis for future studies on the fate of cVMS substances in STPs.     

Application of a LC–MS/MS method for multi-mycotoxin analysis in infant formula and milk-based products for young children commercialized in Southern Brazil

ABSTRACT

An analytical method based on liquid chromatography–tandem mass spectrometry (LC–MS/MS) was validated and applied for the analysis of aflatoxin M₁ (AFM₁), ochratoxin A (OTA) and deoxynivalenol (DON) in infant formula and milk-based products for young children commercialized in Brazil. A total of 38 samples were evaluated, including 12 infant formula, 14 follow-on formula and 12 samples of milk-based products. AFM₁ was detected in 12 (32%) samples, and seven (18%) samples contained AFM₁ levels above the method limit of quantification in a concentration range between 0.013 and 0.067 ng mL^?1 (0.026 ± 0.019). Two samples of milk-based products exceeded the maximum level (ML) fixed by the European Union for AFM₁ in baby foods, however, all samples were in agreement with the levels established by the Brazilian regulation. OTA and DON were not detected in any of the analyzed samples.     

Simultaneous determination of acidic pesticides in vegetables and fruits by liquid chromatography—tandem mass spectrometry

A sensitive and efficient method has been developed for the simultaneous determination of 73 multi-class acidic pesticides, such as phenoxy acid and sulfonylurea herbicides, in vegetables and fruits. The sample preparation procedure was carefully optimized for the efficient removal of co-extracted matrix components. The method involves extraction of acidic pesticides with acetonitrile containing hydrochloric acid, removal of water from crude extract by salting out, and sequential cleanup by octadecylsilyl silica gel and silica gel columns. For samples containing high amounts of pigments, such as spinach, additional cleanup using a graphitized carbon column was performed prior to liquid chromatography–mass spectrometry (LC–MS/MS) analysis. Recovery tests were performed for five times for each sample of cabbage, spinach, potato, eggplant, orange, and apple fortified at 0.01 mg kg?1. Out of the 73 tested pesticides, 70 for cabbage, 67 for spinach, 69 for potato, 67 for eggplant, 64 for orange, and 70 for apple were within the range of 70–120%, with relative standard deviations below 25%. Nitenpyram and pyrasulfotole showed low recoveries for all the samples tested, probably due to low recoveries from silica gel column. The developed method effectively removed co-extracted matrix components and was highly selective, with no interfering peaks found in the chromatograms of blank samples. The overall results indicate that the developed method is suitable for the quantitative analysis of acidic pesticide residues in vegetables and fruits.     

Development,validation and application of a method to analyze phenols in water samples by solid phase micro extraction-gas chromatography-flame ionization detector

In this work the development, validation and application of method using Solid Phase Microexctration (SPME) for the analyses of five pollutants (phenol, 2-nitrophenol, 2,4-dimethylphenol, 2,4-dichlorophenol and 4-chloro, 3-methyl phenol) in supplying water, using gas chromatography (GC) with flame ionization detector (FID) is described. The optimal conditions obtained for SPME were: fiber type: Poliacrylate (PA); extraction time: 40 minutes; extraction temperature: 70°C; amount of salt added to sample (NaCl): 15%; desorption temperature: 8 minutes. The parameters studied in the method validation were: limit of detection (0.3 and 3.5 μ g.L^{? 1}); precision, measured by the variation coefficient (between 2.1 and 8.8%); calibration curve and linearity, by using the external standardization method (between 1 and 50 50 μ g.L^{? 1}). After the methodology development, samples of water collected in Atibaia River (São Paulo - Brazil) were analyzed, using the optimized methodology. Three water samples collected in the rain season showed a peak with retention time close to 4-chloro, 3 methyl phenol further analyzed by Gas Chromatography-Mass Spectrometry for the identity confirmation. In spite of the fact that none target compounds were found in the river water samples analyzed, the presence of two phenols different from those investigated (p-terc butyl phenol; butylated hydroxytoluene) were detected. These results together with the results of the limit of detection (that showed to be lower than the maximum concentration of phenols demanded by different environment control agencies), and the results of the validation, indicate the applicability of this method for the analysis of selected phenols in river water samples.     

吹扫捕集-GC/MS法测定南宁市竹排冲黑臭河道水体嗅味物质

利用吹扫捕集-GC/MS法对引起南宁市竹排冲河道水体黑臭的嗅味物质进行检测分析。结果表明,导致竹排冲水体黑臭的嗅味物质主要为苯系物、硫类化合物和氯苯类化合物,其中甲硫醚(相对含量1.70%)、二甲基二硫醚(相对含量3.19%)、甲基丙基二硫醚(相对含量6.11%)等挥发性有机物为竹排冲水体中的主要致嗅物质,是竹排冲水体嗅味产生的主要原因。     

固相微萃取/气相色谱质谱法测定水中松节油

固相微萃取是一种操作简便、分析快速、无溶剂参与的样品前处理技术。通过采用固相微萃取富集水中的松节油,气相色谱质谱法分析,整个过程只需要25 min。该方法检出限为0.02 mg/L,样品加标回收率为90.0%～130%,相对标准偏差为3.49%～14.6%,完全能够满足日常环境管理需要。     

Bacteria additives to the changes in gaseous mass transfer from stored swine manure

Abstract

A bacteria additives treatment experiment in assessing the changes in gaseous mass transfer from stored swine manure is presented. The experiment is tested for ammonia, methane, hydrogen sulfide, and carbon dioxide emission data sampled from pilot swine manure columns and analyzed by GC/MS. The result shows that bacteria additives slightly reduce the methane and carbon dioxide releases, while the same additives do not show any effect on the reduction of ammonia. The hydrogen sulfide contents of stored swine manure continued to be low. Gas concentrations emitted from treated and untreated stored swine manure were: 3.76 and 2.2 ppm for methane, 0.35 and 0.11 ppm for ammonia, and 1000 and 470 ppm for carbon dioxide, respectively. A simple model to estimate gas emission rates is also developed from the viewpoint of two‐film resistance theory. The average emission rates calculated from the model for methane, ammonia, and carbon dioxide are respectively: 0.01, 0.0005, and 13.98 g/min from untreated stored manure; while 0.07, 0.096, and 0.55 g/min from treated manure. The emission model also indicates that for most gaseous pollutants of environmental concern, liquid phase transfer coefficient controls the rate of volatile compounds emitted from stored swine manure and gas phase transfer coefficient has insignificant effect in the calculation of overall mass transfer coefficient.     

Levels of dechlorane plus and polybrominated diphenylethers in human milk in two Canadian cities

Flame retardant dechlorane plus (DP) and several polybrominated diphenylether (PBDE) congeners have been measured in 87 human milk samples collected in two Canadian cities: Kingston and Sherbrooke. The levels of PBDEs in human milk (mean (median), ng g^− 1 lipid weight = 10 (5.9), 4.1 (2.8), 3.0 (1.6), 5.12 (1.6), and 15 (ND) for BDE-47, BDE-99, BDE-100, BDE-153, and BDE-209, respectively) were comparable to those reported in Europe, U.S.A. and China. The levels of DP, with a mean value of 0.98 ng g^− 1 and a median value of 0.60 ng g^− 1 (lipid weight), were two to ten times lower than those of concurrently measured major PBDEs including BDE-209. While there is little difference in the levels of measured contaminants in milk samples collected from the two cities, the contaminants levels in human milk show, indicated by Principal Components Analysis, that DP, deca-BDE, and penta-BDE come from three distinct sources. The mean and median isomer ratio values of DP in milk were 0.67 and 0.69, respectively, very similar to that of DP commercial products.     

紫外光照处理低浓度萘普生废水

萘普生为水体中常见的一种非甾体药物类污染物。以300W汞灯为光源,研究紫外光照降解法对于含低浓度萘普生废水的处理效果,发现pH对萘普生光解效果有直接影响,降解优异性顺序为酸性>碱性>中性。通过实验,确定了萘普生光解的最佳pH值为4,光照时间为40 min,在该实验条件下,萘普生的降解率达到97.6%。通过液相色谱-质谱联用法对降解后水样进行检测,初步推导出光解中间产物为6-甲氧基-2-乙酰基萘、6-甲氧基-2-乙烯萘及β-萘酚。     

Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters.