Development of the DGT technique for Hg measurement in water: comparison of three different types of samplers in laboratory assays

The Diffusive Gradients in Thin films (DGT) technique is an operationally defined method to determine the dissolved fraction of trace elements in water. The aim of this study was to develop this technique for the measurement of the bioavailable mercury species in natural waters. For that purpose, three types of DGT units (commercial, manufactured with agarose diffusive gel (DG) and manufactured with polyacrylamide DG) were tested under controlled conditions using an Hg(II) solution both with and without dissolved organic matter (DOM). An acid digestion method using aqua regia was optimised to efficiently digest the resin gel discs prior to analysis. A good performance was obtained for the three DGT types when deployed in a DOM-free mercury solution in the laboratory, and it was demonstrated that polyacrylamide gel can be used as diffusive layer for mercury sampling. However, when the DGT units were deployed in a mercury solution containing DOM, performance differences were observed. Furthermore, the mass of background mercury (blanks) varied among the different DGT types. In the light of the results, the devices manufactured with polyacrylamide DG seemed to be the best choice for dissolved mercury determination.     

城镇化地区水文过程实验观测与模拟——以太湖西苕溪流域安吉实验小区为例

城镇化的发展使不透水面积不断增加,往往导致地区的水文过程发生较为明显的改变。以太湖上游西苕溪流域内的安吉城镇化实验小区为例,在对研究流域50多a长系列水文气象资料和区域城镇化特征作较详细分析的基础上,结合2005~2008年短时间尺度降雨径流观测实验,通过雨量、水位以及下垫面等数据分析,选用Storm Water Management Model这一暴雨洪水管理模型对该地区的典型洪水过程进行了模拟,对其降雨径流规律进行了分析。结果表明：该模型对该区域的模拟效果较好,误差较小,可以用于该城镇化地区的降雨径流过程模拟和洪水规律定量分析;分析该实验小区降雨径流过程可知,城镇化使该地区洪水上涨过程明显加快,6场典型洪水的峰型系数均值为305,洪峰流量增大而滞时缩短,较快的汇流速度使该地区的防洪压力较大。实验观测方法及模拟分析成果将有助于对太湖地区小流域城镇洪水过程特征与规律的认识,对我国东部城镇地区的防洪、规划与管理也具有重要的借鉴意义     

Unusual Salinity Conditions in the Yangtze Estuary in 2006: Impacts of an Extreme Drought or of the Three Gorges Dam?

During the extreme dry year of 2006, abnormal salinity conditions in the Changjiang Estuary of the Yangtze River occurred in partial coincidence with the second impoundment phase of the TGD (Three Gorges Dam). Analysis of discharge observations in the upper reaches of the estuary and of salinity observations in the estuary as a whole reveals that in 2006 salinity was over 100 mg/l during 275 days, over 250 mg/l during 75 days and over 400 mg/l during 48 days. It is well known that this is due to extreme low discharges from the upper catchment area into the estuary. Moreover, large amounts of water consumed along the lower reaches of the Yangtze River can also aggravate the low discharges that lead to stronger saltwater intrusion in the estuary. Of the 75 days that salinity was over 250 mg/l, the low discharge was decreased further by 10 to 20% due to water consumption. The additional impact of the impoundment phase of the TGD (lasting 37 days in autumn) was noticeable only during 7 days in 2006. During that period, the relative contributions of the TGD and the water consumption in the lower reaches of the Yangtze River amounted to 70 and 30%, respectively. It may be concluded that the impact of the second impoundment phase of the TGD on salinity intrusion in the estuary was modest, while the extreme drought of 2006 was the dominant cause.     

Microbial Contamination of Groundwater at Small Community Water Supplies in Finland

The raw water quality and associations between the factors considered as threats to water safety were studied in 20 groundwater supplies in central Finland in 2002-2004. Faecal contaminations indicated by the appearance of Escherichia coli or intestinal enterococci were present in five small community water supplies, all these managed by local water cooperatives. Elevated concentrations of nutrients in raw water were linked with the presence of faecal bacteria. The presence of on-site technical hazards to water safety, such as inadequate well construction and maintenance enabling surface water to enter into the well and the insufficient depth of protective soil layers above the groundwater table, showed the vulnerability of the quality of groundwater used for drinking purposes. To minimize the risk of waterborne illnesses, the vulnerable water supplies need to be identified and appropriate prevention measures such as disinfection should be applied.     

Development of a fast instrumental method for the analysis of pharmaceuticals in environmental and wastewaters based on ultra high performance liquid chromatography (UHPLC)-tandem mass spectrometry (MS/MS)

This work describes the development, optimization and validation of an analytical method for the simultaneous detection and identification of 74 pharmaceutically active compounds (PhACs), from various therapeutic groups, in both environmental (ground and surface water) and wastewaters (WW). The method is based on the simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS). Two selected reaction monitoring (SRM) transitions have been monitored per compound in order to fulfil the EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantification is performed by internal standard approach, applying 24 specific isotopically labeled compounds. The main advantages of the developed method, besides the selectivity and reliability of the results, is its high throughput. All compounds are extracted in a single step and the instrumental analysis lasts 5 min (NI mode) + 8 min (PI mode), allowing fast throughput of samples. The limits of detection range from 0.01 to 50 ng L⁻¹, depending on the matrix, for most of the compounds. Finally, the method developed has been applied to the analysis of pharmaceuticals in the Ebro river basin (NE Spain).     

Interference by the activated sludge matrix on the analysis of soluble microbial products in wastewater

The objective of this study was to demonstrate the effects of complex matrix effects caused by chemical materials on the analysis of key soluble microbial products (SMP) including proteins, humics, carbohydrates, and polysaccharides in activated sludge samples. Emphasis was placed on comparison of the commonly used standard curve technique with standard addition (SA), a technique that differs in that the analytical responses are measured for sample solutions spiked with known quantities of analytes. The results showed that using SA provided a great improvement in compensating for SMP recovery and thus improving measurement accuracy by correcting for matrix effects. Analyte recovery was found to be highly dependent on sample dilution, and changed due to extraction techniques, storage conditions and sample composition. Storage of sample extracts by freezing changed SMP concentrations dramatically, as did storage at 4 °C for as little as 1 d.     

Contamination and bioaccumulation of benzotriazole ultraviolet stabilizers in fish from Manila Bay, the Philippines using an ultra-fast liquid chromatography-tandem mass spectrometry

Methyl methacrylate (MMA) is grafted on multiwalled carbon nanotubes (MWCNTs) by using N₂ plasma technique. The MMA grafted MWCNTs (MWCNT-g-pMMA) are characterized by using Raman spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis-differential thermal analysis (TGA-DTA), and potentiometric acid-base titration method. The application of MWCNT-g-pMMA in the removal of 4,4′-dichlorinated biphenyl (4,4′-DCB) from large volumes of aqueous solutions is investigated under ambient conditions. The results indicate that the adsorption of 4,4′-DCB on MWCNT-g-pMMA is much higher than that of 4,4′-DCB on MWCNTs, and the adsorbed 4,4′-DCB is difficult to be thermally decomposed from MWCNT-g-pMMA according to the TGA-DTA analysis. MWCNT-g-pMMA are suitable materials in the preconcentration and immobilization of polychlorinated biphenyls (PCBs) from large volumes of aqueous solutions in environmental pollution cleanup.     

Genotoxic assessment on river water using different biological systems

This paper reports genotoxicity and toxicity data in water samples collected in Sinos River, an important water course in the hydrographic region of Guaíba Lake, Rio Grande do Sul State, south of Brazil. This river is exposed to intense anthropic influence by numerous shoes, leather, petrochemical, and metallurgy industries. Water samples were collected at two moments (winter 2006 and spring 2006) at five sites of Sinos River and evaluated using in vitro V79 Chinese hamster lung fibroblasts (cytotoxicity, comet assay and micronucleus test) and Allium cepa test (toxicity and micronucleus test). Comet and micronucleus tests revealed that water samples collected exerted cytotoxic, toxic, genotoxic and mutagenic effects. The results showed the toxic action of organic and inorganic agents found in the water samples in all sites of Sinos River, for both data collections. The main causes behind pollution were the domestic and industrial toxic discharges. The V79 and A. cepa tests were proved efficient to detect toxicity and genotoxicity caused by complex mixtures. This study also showed the need for constant monitoring in sites with strong environmental degradation caused by industrial discharges and urban sewages.     

Incomplete aerobic degradation of the antidiabetic drug Metformin and identification of the bacterial dead-end transformation product Guanylurea

Active pharmaceutical ingredients as well as personal care products are detected in increasing prevalence in different environmental compartments such as surface water, groundwater and soil. Still little is known about the environmental fate of these substances. The type II antidiabetic drug Metformin has already been detected in different surface waters worldwide, but concentrations were significantly lower than the corresponding predicted environmental concentration (PEC). In human and mammal metabolism so far no metabolites of Metformin have been identified, so the expected environmental concentrations should be very high.To assess the aerobic biodegradability of Metformin and the possible formation of degradation products, three Organisation of Economic Cooperation and Development (OECD) test series were performed in the present study.In the Closed Bottle test (OECD 301 D), a screening test that simulates the conditions of an environmental surface water compartment, Metformin was classified as not readily biodegradable (no biodegradation). In the Manometric Respiratory test (OEDC 301 F) working with high bacterial density, Metformin was biodegraded in one of three test bottles to 48.7% and in the toxicity control bottle to 57.5%. In the Zahn-Wellens test (OECD 302 B) using activated sludge, Metformin was biodegraded in both test vessels to an extent of 51.3% and 49.9%, respectively.Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MS(n)) showed in the tests vessels were biodegradation was observed full elimination of Metformin and revealed Guanylurea (Amidinourea, Dicyandiamidine) as single and stable aerobic bacterial degradation product. In another Manometric Respiratory test Guanylurea showed no more transformation. Photodegradation of Guanylurea was also negative.A first screening in one of the greatest sewage treatment plant in southern Germany found Metformin with high concentrations (56.8 μg L⁻¹) in the influent (PEC = 79.8 μg L⁻¹), but effluent concentration was much lower (0.76 μg L⁻¹) whereas Guanylurea was detected in a low influent and high effluent concentration (1.86 μg L⁻¹). These data support the experimental findings in the OECD tests and analytical results of other studies, that Metformin under aerobic conditions can bacterially be degraded to the stable dead-end transformation product Guanylurea.     

Assessment of bisphenol A released from reusable plastic, aluminium and stainless steel water bottles

Bisphenol A (BPA) is a ubiquitous high volume industrial chemical that is an estrogen and an environmental endocrine disrupting chemical. Bisphenol A is used extensively in the production of consumer goods, polycarbonate plastics, epoxy resins and coatings used to line metallic food and beverage cans. There is great concern regarding the possible harmful effects from exposures that result from BPA leaching into foods and beverages from packaging or storage containers. The objective of this study was to independently assess whether BPA contamination of water was occurring from different types of reusable drinking bottles marketed as alternatives to BPA-containing polycarbonate plastics. Using a sensitive and quantitative BPA-specific competitive enzyme-linked immunosorbent assay we evaluated whether BPA migrated into water stored in polycarbonate or copolyester plastic bottles, and different lined or unlined metallic reusable water bottles. At room temperature the concentration of BPA migrating from polycarbonate bottles ranged from 0.2 to 0.3 mg L⁻¹. Under identical conditions BPA migration from aluminium bottles lined with epoxy-based resins was variable depending on manufacturer ranging from 0.08 to 1.9 mg L⁻¹. Boiling water significantly increased migration of BPA from the epoxy lined bottles. No detectable BPA contamination was observed in water stored in bottles made from Tritan™ copolyester plastic, uncoated stainless steel, or aluminium lined with EcoCare™. The results from this study demonstrate that when used according to manufacturers’ recommendations reusable water bottles constructed from “BPA-free” alternative materials are suitable for consumption of beverages free of BPA contamination.