Detecting N-nitrosamines in water treatment plants and distribution systems in China using ultra-performance liquid chromatography-tandem mass spectrometry

N-nitrosodimethylamine (NDMA) and several other N-nitrosamines have been detected as disinfection by-products in drinking waters in many countries around the world. An ultra-performance liquid chromatographytandem mass spectrometry method with solid phase extraction sample preparation was developed to study the occurrence of N-nitrosamines in several water treatment plants and distribution systems in China. Isotope labeled N-nitrosodi-n-propylamine-d14 (NDPA-d14) was selected as the internal standard for quantification. The solid phase extraction procedures including pH, enrichment process and MS/MS parameters including capillary voltage, cone gas flow, cone voltage, collision energy were optimized to give average recoveries of 26% to 112% for nine N-nitrosamine species. The instrument detection limits were estimated to range from 0.5 to 5 ??g·L^?1 for the nine N-nitrosamine species. NDMA and several other N-nitrosamines were found at fairly high concentrations in several water treatment plants and distribution systems. NDMA was found in all locations, and the highest concentrations in cities B, G, T, and W were 3.0, 35.7, 21.3, and 19.7 ng·L^?1, respectively. A wide range of N-nitrosamines concentrations and species were observed in different locations. Higher concentrations of N-nitrosamines were detected in distribution systems that were further away from the treatment plants, suggesting that the contact time between the residual disinfectant and natural organic matter may play an important role in the formation of these compounds.     

Decolorization of azo dyes by a salt-tolerant Staphylococcus cohnii strain isolated from textile wastewater

The salt-tolerant Staphylococcus cohnii strain, isolated from textile wastewater, has been found effective on decolorizing several kinds of azo dyes with different structures. The optimal conditions for azo dye acid red B (ARB) decolorization by S. cohnii were determined to be pH = 7.0 and 30°C. The decolorization efficiency increased with the increase of the salinity concentration, and around 90% of ARB (100 mg·L^?1) could be decolorized in 24 h when the salinity concentration was up to 50 g·L^?1. Moreover, the strain could still decolorize 19% of ARB in 24 h even when the NaCl concentration was increased to 150 g·L^?1. Meanwhile, the dependence of the specific decolorization rate by S. cohnii on the ARB concentration could be described with Michaelis-Menten kinetics (K _m = 585.7mg·L^?1, V _max = 109.8 mg·g cell^?1·h^?1). The addition of quinone redox mediator, named 2-hydroxy-1,4-naphthoquinone and anthraquinone-2,6-disulfonate, significantly accelerated the decolorization performance of S. cohnii. Furtherly, the activities of azoreductase (0.55 ??mol·mg protein^?1·min^?1) and Nicotineamide adenine dinucleotide-dichlorophenol indophenol (NADH-DCIP) reductase (8.9 ??mol·mg protein^?1·min^?1) have been observed in the crude cell extracts of S. cohnii. The decolorization products of ARB were analyzed by HPLC-MS, and the results indicated the reductive pathway was responsible for azo dye decolorization by S. cohnii.     

Trace analysis of off-flavor/odor compounds in water using liquid-liquid microextraction coupled with gas chromatography—positive chemical ionization-tandem mass spectrometry

A rapid, inexpensive and laboratory friendly method was developed for analysis of off-flavor/odor compounds in fresh and salt water using gas chromatography with chemical ionization-tandem mass spectrometry. Off-flavor/odor compounds included geosmin, 2- methylisoborneol (MIB), 2-isobutyl-3-methyoxypyrazine (IBMP), and 2-isopropyl-3-methoxypyrazine (IPMP). Using this method, a single sample can be extracted within minutes using only 1 mL of organic solvent. The ion transitions for IPMP, IBMP, MIB, and geosmin were 153>121, 167>125, 152>95, and 165>109, respectively. The linearity of this method for analyzing MIB ranged from 4 to 200 ng·L^–1, and from 0.8 to 200 ng·L^–1 for the other analytes. Method recoveries ranged from 97% to 111% and percent relative standard deviations ranged from 3% to 9%, indicating that the method is accurate, precise, and reliable.     

A novel ligand for cloud point extraction to determine gold content in ore samples

Gold is a valuable metal occurring usually at very low concentrations in complex natural samples. Gold analysis thus needs preconcentration methods. Classical liquid–liquid extraction involves hazardous organic solvents. Alternatively, cloud point extraction involves non-toxic and nonvolatile surfactants. Here, we analyzed ore samples. The complex of Au(III) with sulphapyridylazo resorcin was extracted by the cloud point method. Concentrations were measured by flame atomic absorption spectrometry. We tested the effects of pH, reagent concentration, Triton X-100 surfactant concentration, equilibration temperature and time. Results show that the best detection limit of the method was 0.48 µg L^?1 for Au with a preconcentration factor of 31 times. Calibration is linear in range of 6.4–2,000 µg L^?1, and relative standard deviations are lower than 5 %. Quantum chemical computations reveal the plausible structure of the gold–ligand complex. This report represents the first determination of gold using sulphapyridylazo resorcin as a ligand.     

Dispersive solid phase extraction of chlorophenols using carbon-coated magnetic nanoparticles

Abstract

Carbon-coated magnetic nanoparticles were modified with cationic surfactant and used for the dispersive solid phase extraction of chlorophenols from aqueous samples. Surfactant adsorbed on the surface of the nanoparticles resulted in mixed hemimicelles for high extraction efficiency of chlorophenols. Under optimized conditions, calibration curves were linear from 0.5–20?mg L^?1 for analytes with limit of detection between 0.2 and 0.4?mg L^?1. The method was applied to extraction of chlorophenols from tap water, well water and industrial effluent. Recoveries were in the range of 94.0–99.4%, suggesting that sample matrix had little effect on the yields of extraction.     

Measuring dissolved organic carbon δ13C in freshwaters using total organic carbon cavity ring-down spectroscopy (TOC-CRDS)

This article reports the first application of coupled total organic carbon cavity ring-down spectroscopy (TOC-CRDS) for the analysis of the ??¹³C signature of dissolved organic carbon (DOC) in freshwater samples. DOC represents a major, dynamic component of the global carbon cycle. The export of DOC from soils into rivers and groundwaters may be highly climate sensitive, and much of this export may occur in ephemeral fluxes. Thus, a robust, simple and inexpensive method for the continuous determination of DOC concentration and quality is urgently needed. We detail recent advances made in the analysis of the ??¹³C signature of DOC using a TOC-CRDS system optimised for the analysis of DOC with natural abundances greater than 2.5?mg?L^?1 with no sample pre-concentration required and sample volumes of 40?mL. Precision between replicated samples was comparable to conventional analysis by gas-source isotope ratio mass spectrometry, yielding ??¹³C values with standard deviations of?±?0.5??? for DOC concentrations higher than 1.5?mg?L^?1. The utility of this technique for the analysis of DOC in samples with a broad range of compositions and concentrations (2.5?C25?mg?L^?1 DOC) is demonstrated. Since DOC ??¹³C can be measured continuously, ca. 45?min per measurement, this method enables the online monitoring of DOC in river water, water intakes and treated waters, allowing changes in DOC fluxes to be monitored in real time.     

21种杀菌剂对家蚕的急性毒性与风险评价

旨在为桑园及周围农田合理选择和使用农药提供科学依据,采用食下毒叶法测定了农业生产上常用的21种杀菌剂对家蚕的急性毒性,并进行了风险评价.急性毒性测定结果表明:20％苯醚甲环唑微乳剂、10％氟硅唑水乳剂、12.5％腈菌唑水乳剂、12.5％烯唑醇可湿性粉剂和70％嗯霉灵可湿性粉剂对家蚕的96 h-LC50值为46.5(41...     

Effective degradation of tetracycline by mesoporous Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> under visible light irradiation

Bi₂WO₆ was synthesized with a hydrothermal method at different pHs and used for the degradation of tetracycline (TC) in water. The mesoporous Bi₂WO₆ prepared at pH 1 (BWO-1) displayed the highest adsorption and degradation capacity to TC due to its large surface area and more efficient capacity to separate photogenerated electrons and holes. 97% of TC at 20 mg·L^?1 was removed by BWO-1 at 0.5 g·L^?1 after 120 min irradiation under simulated solar light. Only 31% of the total organic carbon (TOC) was removed after 360 min irradiation although the TC removal reached 100%, suggesting that TC was mainly transformed to intermediate products rather than completely mineralized. The intermediates were identified by high-performance liquid chromatography-time of flight-mass spectrometry (HPLC-TOF-MS) and possible photodegradation pathways were proposed.     

Biocatalytic dechlorination of hexachlorocyclohexane by immobilized bio-Pd in a pilot scale fluidized bed reactor

Lindane (??-hexachlorocyclohexane, ??-HCH) is a recalcitrant and toxic organochlorine insecticide. Due to its non-selective production process and widespread use, HCH isomers and their degradation products have been detected frequently in soils and groundwater. An innovative technology using microbial produced Pd(0) nanoparticles, i.e. bio-Pd, was developed to treat groundwater containing a mixture of HCHs and chlorobenzenes. In a first step, the groundwater was de-ironized and most of the chlorobenzenes were removed in a biological trickling filter. The ??g?L^?1 levels of HCHs and chlorobenzenes were removed in a second step by the bio-Pd-based technology. Therefore, a 200-L pilot scale reactor was developed with 100?mg?L^?1 bio-Pd encapsulated in alginate beads. Hydrogen gas was bubbled at the bottom of the reactor and served to charge the bio-Pd catalyst. The reactor influent contained 5.2???g?L^?1 HCHs and 51.1???g?L^?1 chlorobenzenes. During a test period of 10?days, 29% of the HCH isomers and 63% of the chlorobenzenes were removed applying a nominal hydraulic residence time of 4?h. These removal percentages could be increased to 75 and 68% by doubling the nominal hydraulic residence time to 8?h. This study demonstrated that biologically produced nanoparticles of Pd can be applied for the large-scale remediation of groundwater contaminated with HCHs.     

Dichloromethane emissions from automotive manufacturing industry in Iran: case study of the SAIPA automotive manufacturing company

The primary data about the role of automotive manufacturing industry in emitting dichloromethane (DCM) to the environment in Iran are provided by a case study of SAIPA Automotive Manufacturing Company in 2012. The average emission rate and emission factor of DCM in the stack exhaust air streams of the solvent-based automotive painting plant were 6.8 kg·d^?1 and 19.5 g per car, respectively. The spray booths had the highest portion (about 85%) of DCM emission in the stack exhaust air streams. The average concentration of DCM (± standard deviation) in the generated wastewater of the factory was 64 ± 12 μg·L^?1, but in the effluent of the factory wastewater treatment plant, it was reduced to a nondetectable level. DCM was also observed in three groundwater wells out of five monitored water resources. To control DCM emission and prevent pollution, the replacement of solvent-based paints with water-based paints is highly recommended.     

Arsenic contamination of natural waters in San Juan and La Pampa, Argentina

Arsenic (As) speciation in surface and groundwater from two provinces in Argentina (San Juan and La Pampa) was investigated using solid phase extraction (SPE) cartridge methodology with comparison to total arsenic concentrations. A third province, Río Negro, was used as a control to the study. Strong cation exchange (SCX) and strong anion exchange (SAX) cartridges were utilised in series for the separation and preservation of arsenite (As^III), arsenate (As^V), monomethylarsonic acid (MA^V) and dimethylarsinic acid (DMA^V). Samples were collected from a range of water outlets (rivers/streams, wells, untreated domestic taps, well water treatment works) to assess the relationship between total arsenic and arsenic species, water type and water parameters (pH, conductivity and total dissolved solids, TDS). Analysis of the waters for arsenic (total and species) was performed by inductively coupled plasma mass spectrometry (ICP-MS) in collision cell mode. Total arsenic concentrations in the surface and groundwater from Encon and the San José de Jáchal region of San Juan (north-west Argentina within the Cuyo region) ranged from 9 to 357 μg l^?1 As. Groundwater from Eduardo Castex (EC) and Ingeniero Luiggi (LU) in La Pampa (central Argentina within the Chaco-Pampean Plain) ranged from 3 to 1326 μg l^?1 As. The pH range for the provinces of San Juan (7.2–9.7) and La Pampa (7.0–9.9) are in agreement with other published literature. The highest total arsenic concentrations were found in La Pampa well waters (both rural farms and pre-treated urban sources), particularly where there was high pH (typically > 8.2), conductivity (>2,600 μS cm^?1) and TDS (>1,400 mg l^?1). Reverse osmosis (RO) treatment of well waters in La Pampa for domestic drinking water in EC and LU significantly reduced total arsenic concentrations from a range of 216–224 μg l^?1 As to 0.3–0.8 μg l^?1 As. Arsenic species for both provinces were predominantly As^III and As^V. As^III and As^V concentrations in San Juan ranged from 4–138 μg l^?1 to <0.02–22 μg l^?1 for surface waters (in the San José de Jáchal region) and 23–346 μg l^?1 and 0.04–76 μg l^?1 for groundwater, respectively. This translates to a relative As^III abundance of 69–100% of the total arsenic in surface waters and 32–100% in groundwater. This is unexpected because it is typically thought that in oxidising conditions (surface waters), the dominant arsenic species is As^V. However, data from the SPE methodology suggests that As^III is the prevalent species in San Juan, indicating a greater influence from reductive processes. La Pampa groundwater had As^III and As^V concentrations of 5–1,332 μg l^?1 and 0.09–592 μg l^?1 for EC and 32–242 μg l^?1 and 30–277 μg l^?1 As for LU, respectively. Detectable levels of MA^V were reported in both provinces up to a concentration of 79 μg l^?1 (equating to up to 33% of the total arsenic). Previously published literature has focused primarily on the inorganic arsenic species, however this study highlights the potentially significant concentrations of organoarsenicals present in natural waters. The potential for separating and preserving individual arsenic species in the field to avoid transformation during transport to the laboratory, enabling an accurate assessment of in situ arsenic speciation in water supplies is discussed.     

Ultrasound-assisted emulsification/microextraction based on solidification of trace amounts of thallium prior to graphite furnace atomic absorption spectrometry determination

In the present work, determination of ultratrace amounts of thallium in water samples was performed by ultrasound-assisted emulsification microextraction based on solidification of a floating organic drop as sample preparation method prior to furnace atomic absorption spectrometry. 1-(2-Pyridylazo)-2-naphthol was used as chelating agent. The factors influencing the complex formation and extraction, such as pH of the aqueous solution, the type and the volume of extraction solvent, the volume of chelating agent solution, and the extraction time were investigated. Under optimized conditions, the enrichment factor was 200. The calibration graph was linear from 0.2 to 10.0 μg L^?1 with a correlation coefficient of 0.9966, the detection limit was 0.03 μg L^?1 and reproducibility was ±3.3% (C = 5.0 μg L^?1, n = 8). The method was successfully applied for the determination of thallium in water samples.     

Spatial distribution of copper in relation to recreational boating in a California shallow-water basin

The overall effect of the number of boats on the copper (Cu) levels in the water column and sediment, along with their spatial variability within Shelter Island Yacht Basin (SIYB), San Diego Bay, California was examined. We identified a horizontal gradient of increasing dissolved Cu and Cu in sediment from outside to the head of SIYB which was coincident with the increasing number of boats. Spatial models of Cu distribution in water and sediment indicated the presence of ‘hotspots’ of Cu concentration. From outside to the head of SIYB, dissolved Cu ranged from 1.3 μ g L^?1 to 14.6 μ g L^?1 in surface water, and 2.0 μ g L^?1 to 10.2 μ g L^?1 in bottom water. Cu in sediment exceeded the Effect Range Low of 34 mg kg^?1 (i.e. where adverse effects to fauna may occur), with a peak concentration of 442 mg kg^?1 at the head of the basin. Free Cu⁺⁺ in surface water was several orders of magnitude higher than in sediment porewater. High-resolution data of Cu species together with probability maps presented in this paper will allow managers to easily visualise and localise areas of impaired quality and to prioritise which areas should be targeted to improve Cu-related conditions.     

Copper and zinc interaction on water clearance and tissue metal distribution in the freshwater mussel, Cristaria plicata, under laboratory conditions

Copper and zinc interaction on clearance from water and distribution in different tissues was investigated for the freshwater mussel, Cristaria plicata, under laboratory conditions. Clearance rate of Cu or Zn from water was highly dependent on exposure concentration. Interaction effect was most evident at 300 ??g??L^?1 Cu exposure and depressed the Zn clearance rate significantly (p<0.05). However, the presence of 100 ??g??L^?1 and 300 ??g??L^?1 Zn hardly affected the Cu clearance rate. The 300 ??g??L^?1 Cu presence enhanced Cu accumulation in each tissue most significantly (p<0.01), but caused Zn content to decrease in the gills by 62% (p<0.05), viscera by 49% (p<0.05) and foot by 31% (p<0.05), and increase in the mantle by 97% (p<0.05) and the muscles by 243% (p<0.05) for different Zn exposure treatments. The response of metal accumulation in various tissues of the test mussels indicated that Zn transferred from the gills, viscera and foot to the mantle and muscles might be one of the important characteristics of the Zn regulatory mechanism by leading to a narrow range of Zn concentration in the different tissues.     

The removal of arsenic from water with natural and modified clinoptilolite

The presence of increased arsenic concentrations in Eastern Croatia is a consequence of the geological composition of the soil. Because of its known harmful effects, arsenic removal is of high importance and adsorption represents an attractive and economically efficient approach to arsenic removal. The use of zeolites obtained from the Donje Jesenje deposit, Croatia (CZ) and the Zlatokop deposit in Vranjska Banja, Serbia (SZ) in Na- and Fe–Na-modified forms was investigated in order to effectively remove arsenate and arsenite from aqueous solutions. The adsorption kinetics of arsenic was studied as a function of the initial arsenate and arsenite concentrations (30–300 μg · L^?1), equilibration time (3–48 h), pH (5–10) and in the presence of sulfate and phosphate at initial concentrations of 0.2–0.5 mg · L^?1. In order to estimate sorption constants designating the sorption capacity and affinity of the zeolites samples, the experimental results were fitted to the Langmuir and Freundlich sorption isotherms. Desorption tests conducted with 1–3 mol · L^?1 HCl indicated that arsenate sorption was irreversible. The results obtained indicated that use of the Serbian zeolite in the Fe–Na-modified form (Fe–Na-SZ) was favourable for arsenate removal from water containing up to 30 μg As · L^?1.     

Seasonal variation of nitrogen and phosphorus in Xiaojiang River—A tributary of the Three Gorges Reservoir

A yearlong monitoring program in the backwater area of Xiaojiang River (XBA) was launched in order to investigate the eutrophication of backwater areas in tributaries of the Yangtze River in the Three Gorges Reservoir (TGR) in China, starting after the impoundment water level of the TGR reached 156 m. From March 2007 to March 2008, the average concentration of total nitrogen (TN) and total phosphorus (TP) were (1553±484) μg·L^?1 and (62±31) μg·L^?1, respectively. The mean value of chlorophyll was (9.07±0.91) μg·L^?1. The trophic level of XBA was meso-eutrophic, while the general nutrient limitation was phosphorus. The results indicated that XBA has a strong ability to purify itself and has non-point source pollution from terrestrial runoff. The variation of TN/TP ratio was caused by a variation in TN rather than in TP when TN/TP < 22. N-fixation from cyanobacteria occurred and became an important process in overcoming the nitrogen deficit under a low TN/TP ratio. When TN/TP ? 22, the variation of TP affected the TN/TP ratio more significantly than TN. The increase of TP in XBA was caused mainly by particulate phosphorus, which could originate from a non-point source as adsorptive inorganic forms after heavy rainfall and surface runoff. An increase in the river’s flow could also contribute to an unstable environment for the growth of phytoplankton.     

Automated indirect fluoride determination by ICP-OES using discontinuous-flow analysis

An automated method for the indirect determination of fluoride by inductively coupled plasma atomic emission spectrometry using discontinuous-flow analysis has been developed. A modified flow injection analysis system was used for sample preparation. The method is based on the determination of excess cerium(III) ion after precipitation of CeF₃. Separation of the precipitate is performed online on a syringe membrane filter that is cleaned each analysis cycle by 1 M nitric acid, ensuring a long life-time for the filter. As a result of the short reaction time, a detection limit of 9.5 mg L^?1 was obtained. The precision (RSD) of the proposed method is 1.02% at fluoride concentration of 28 mg L^?1. The applicability of the technique for groundwater monitoring of fluoride-contaminated area is demonstrated.     

Bioreduction of nitrate in groundwater using a pilot-scale hydrogen-based membrane biofilm reactor

A long-term pilot-scale H₂-based membrane biofilm reactor (MBfR) was tested for removal of nitrate from actual groundwater. A key feature of this second-generation pilot MBfR is that it employed lower cost polyester hollow fibers and still achieved high loading rate. The steady-state maximum nitrate surface loading at which the effluent nitrate and nitrite concentrations were below the Maximum Contaminant Level (MCL) was at least 5.9 g·N·(m²·d)^?1, which corresponds to a maximum volumetric loading of at least 7.7 kg·N·(m³·d) ^?1. The steady-state maximum nitrate surface area loading was higher than the highest nitrate surface loading reported in the first-generation MBfRs using composite fibers (2.6 g·N·(m²·d)^?1). This work also evaluated the H₂-utilization efficiency in MBfR. The measured H₂ supply rate was only slightly higher than the stoichiometric H₂-utilization rate. Thus, H₂ utilization was controlled by diffusion and was close to 100% efficiency, as long as biofilm accumulated on the polyester-fiber surface and the fibers had no leaks.     

纳米二氧化硅对秀丽线虫的毒性作用研究

为探讨二氧化硅纳米颗粒(SiNP)的毒性作用.以微米SiO2和空白做对照,将尺寸为20和60 nm的SiNP分别以0.2,1.0和5.0 g·L-13个浓度对模式生物秀丽隐杆线虫进行染毒.通过第一代和第二代线虫体长、身体弯曲频率、头部摆动频率以及第一代线虫后代数目、世代时间等发育、运动和生殖的相关评价指标,对SiNP毒...