Migration of manganese and iron during the adsorption-regeneration cycles for arsenic removal

Fe-Mn binary oxide incorporated into porous diatomite (FMBO-diatomite) was prepared in situ and regenerated in a fixed-bed column for arsenite [As(III)] and arsenate [As(V)] removal. Four consecutive adsorption cycles were operated under the following conditions: Initial arsenic concentration of 0.1 mg·L^-1, empty bed contact time of 5 min, and pH 7.0. About 3000, 3300, 3800, and 4500 bed volumes of eligible effluent (arsenic concentration≤0.01 mg·L^-1) were obtained in four As(III) adsorption cycles; while about 2000, 2300, 2500, and 3100 bed volumes of eligible effluent were obtained in four As(V) adsorption cycles. The dissection results of FMBO-diatomite fixed-bed exhibited that small amounts of manganese and iron were transferred from the top of the fixed-bed to the bottom of the fixed-bed during As(III) removal process. Compared to the extremely low concentration of iron (<0.01 mg·L^-1), the fluctuation concentration of Mn²⁺ in effluent of the As(III) removal column was in a range of 0.01–0.08 mg·L^-1. The release of manganese suggested that manganese oxides played an important role in As(III) oxidation. Determined with the US EPA toxicity characteristic leaching procedure (TCLP), the leaching risk of As(III) on exhausted FMBO-diatomite was lower than that of As(V).     

Modified pretreatment method for total microbial DNA extraction from contaminated river sediment

Extraction of high-quality microbial DNA from contaminated environmental samples is an essential step in microbial ecological study. Based on previously published methods for soil and sediment samples, a modified pretreatment method was developed for extracting microbial DNA from heavily contaminated river sediment samples via selection of optimal pretreatment parameters (i.e., reagent solution, reaction duration, and temperature). The pretreatment procedure involves washing the river sediment sample for three times with a solution containing 0.1 mol·L^-1 ethylene diamine tetraacetic acid (EDTA), 0.1 mol·L^-1 Tris (pH 8.0), 1.5 mol·L^-1 NaCl, 0.1 mol·L^-1 NaH₂PO₄, and Na₂HPO₄ at 65°C with 180 r·min^-1 for 15 min to remove humic materials and heavy metals prior to the employment of standard DNA extraction procedures. We compared the results of standard procedure DNA extraction following pretreatment, without pretreatment, and with using a commercial PowerSoil^TM DNA Isolation Kit. The results indicated that the pretreatment significantly improved the DNA quality based on DNA yield, DNA fragment length, and determination of prokaryotic diversity. Prokaryotic diversity exhibited in the DNA with the pretreatment was also considerably higher than that extracted with the PowerSoil^TM DNA Isolation Kit only. The pretreatment method worked well even with a small amount of sediment sample (0.25 g or even lower). The method provides a novel, simple, cost-effective tool for DNA extraction for microbial community analysis in environmental monitoring and remediation processes.     

Effect of illumination on the hydrogen-production capability of anaerobic activated sludge

To investigate the influence of illumination on the fermentative hydrogen production system, the hydrogen production efficiencies of two kinds of anaerobic activated sludge (floc and granule) from an anaerobic baffled reactor were detected under visible light, dark and light-dark, respectively. The 10 mL floc sludge or granular sludge was respectively inoculated to 100 mL diluted molasses (chemical oxygen demand of 8000 mg·L^-1) in a 250 mL serum bottle, and cultured for 24 h at 37°C under different illumination conditions. The results showed that the floc was more sensitive to illumination than the granule. A hydrogen yield of 19.8 mL was obtained in the dark with a specific hydrogen production rate of 3.52 mol·kg^-1MLVSS·d^-1 (floc), which was the highest among the three illumination conditions. Under dark condition, the hydrogen yield of floc sludge reached the highest with the specific hydrogen production rate of 3.52 mol·kg^-1MLVSS·d^-1, and under light-dark, light, the specific hydrogen production rate was 3.11 and 2.21 mol·kg^-1MLVSS·d^-1, respectively. The results demonstrated that the illumination may affect the dehydrogenase activity of sludge as well as the activity of hydrogen-producing acetogens and then impact hydrogen production capacity.     

Zn和Cd胁迫作用对长梗白菜形态和生理性能的生态毒理影响

本文以不同Cd、Zn浓度胁迫下的长梗白菜为研究对象,采用盆栽实验,分析了Cd和Zn胁迫下长梗白菜形态参数(重量、长度、表面积、叶的分形维数)、生理性能的影响以及从土壤中提取Cd和Zn的能力.结果 表明,Cd、Zn胁迫对长梗白菜的生长具有"低促高抑"效应,且共同胁迫对生长的影响大于单一胁迫.在0.6 mg·kg-1 Cd...     

新型溴系阻燃剂环境污染现状研究进展

新型溴系阻燃剂(NBFRs, novel brominated flame retardants)作为传统溴系阻燃剂的替代品已广泛应用于电子产品、纺织品、家具等商品中,随着这些商品的生产、使用和处置,NBFRs不可避免地释放到环境中,给环境和人体带来潜在的危害.部分NBFRs可通过摄食和呼吸作用进入人体对人体产生一定危害,已被证明具有潜在的生物毒性.而NBFRs的环境污染现状研究对控制NBFRs的污染具有重要意义.近年来有不少研究者对不同环境基质中的NBFRs进行了定量测定.基于这些研究成果,本文综述了近年来环境中NBFRs的研究现状、进展,重点介绍了水体、沉积物和大气中NBFRs的含量分布.多种类型水体中NBFRs的浓度水平在ng·L^-1至μg·L^-1之间,浓度受地区工业生产和季节等因素影响,且不同污水处理系统对水体中NBFRs的去除效率具有一定差异;NBFRs倾向于分布在富含有机碳的介质中,沉积物中NBFRs的含量在ng·g^-1至μg·g^-1级别,浓度与地区工业生产、化合物性质以及总有机碳含量等因素有关;大气中的NBFRs倾向吸附于颗粒相中,在两相中的含量分别为pg·m^-3和ng·g^-1级别,其含量受环境因素影响较为复杂.     

高效液相色谱-串联质谱法同时检测水体中26种药物及个人护理品

通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了可以同时检测地表水和地下水中26种典型药物及个人护理品(pharmaceuticals and personal care products,PPCPs),包括磺胺类、大环内酯类、喹诺酮类、酰胺醇类、精神类、消炎止痛类以及个人护理品的检测方法.通过将水样pH值调节至7,利用HLB固相萃取柱对水样中PPCPs进行富集,以甲醇和含0.005%甲酸的水溶液作为正离子模式流动相,甲醇和含0.5 mmol·L^-1乙酸铵的水溶液作为负离子模式流动相进行梯度洗脱,采用多反应监测的质谱扫描模式(MRM)分析测定.26种PPCPs的检出限为0.007—1.78 ng·L^-1,定量限为0.02—5.68 ng·L^-1,回收率为52.28%—115.24%.利用该方法检测北京潮白河地表水和地下水中PPCPs的浓度,结果表明,地表水中PPCPs的含量普遍高于地下水,磺胺甲恶唑、舒必利、咖啡因、卡马西平和布洛芬在地表水和地下水中的含量相对较高,检测浓度分别高达147.83、52.48、78.35、166.58、30.63 ng·L^-1.     

湛江红树林湿地沉积物中多溴联苯醚(PBDEs)的污染特征与生态风险评价

近年来,红树林有机污染物(POPs)污染逐渐加重,其生态环境保护压力日趋加大。湛江红树林保护区是中国面积最大的红树林自然保护区,对生态系统稳定具有重要作用,准确评估湛江红树林湿地多溴联苯醚(PBDEs)的污染现状及潜在生态风险,对了解湛江红树林有机污染物的污染状况、红树林的生态环境保护等具有重要意义。采用索氏抽提法和气相色谱-质谱法测定了湛江红树林湿地12个采样位点沉积物中的PBDEs质量分数,分析了多溴联苯醚(PBDEs)的污染水平、空间分布特征及其潜在风险。结果表明,湛江红树林表层沉积物中共检测到14种PBDEs,BDE-209质量分数占比最高,为53.58%—77.66%。12个采样点的∑PBDEs质量分数均值为23.30 ng·g^?1。按地理位置划分为6个研究区域,各研究区域的∑PBDEs质量分数均值变化为:湛江市区(33.06 ng·g^?1)>廉江西(29.68 ng·g^?1)>徐闻(19.29 ng·g^?1)>雷州东(16.47 ng·g^?1)>遂溪(15.72 ng·g^?1)>雷州西(11.92 ng·g^?1);BDE-209、∑13PBDEs(除BDE-209外)质量分数的分布规律与∑PBDEs质量分数的变化趋势一致。与国内外其他红树林湿地沉积物相比,湛江红树林沉积物中∑PBDEs质量分数处于中等水平。湛江红树林沉积物中的PBDEs污染主要源自商业五溴、八溴及十溴联苯醚产品的使用,高溴联苯醚的降解也是其来源之一。环境中的降雨量、TOC、pH值等对沉积物中PBDEs的影响不大。风险熵数法的生态风险评价结果表明,湛江红树林沉积物中PBDEs的综合生态风险水平较高,尤其是penta-BDEs和deca-BDEs处于高风险水平,应引起关注。     

水中天然含氮有机物的形成、迁移转化及分布

天然含氮有机物是水环境中的重要组成部分,其在天然水体中的形态及分布对环境质量有显著影响.本文围绕水中天然含氮有机物在氮循环中的地位、迁移转化以及其在国内主要水域中的分布情况,对天然含氮有机物的研究现状进行了梳理.我国不同水域中溶解性含氮有机物(DON)浓度相差较大;其中水体中DON浓度一般在1.0 mg·L^-1以下;沉积物中DON浓度通常为几十至几百mg·kg^-1.水体DON以分子量<1 kDa的有机物为主,主要成分是尿素、氨基酸等物质.沉积物DON以分子量<1 kDa和>30 kDa的有机物为主,其中前者主要由芳构化程度较高的氨基酸等小分子有机物构成,后者以腐殖质类为主.水体中部分胺类物质本身具有一定毒性,游离氨基酸等DON还是卤乙腈、卤代酰胺、卤代硝基甲烷、卤化氰和亚硝胺等含氮消毒副产物的重要前体物.由于水体中许多含氮有机物具有生物可利用性,有机氮可能是引起水体富营养化的重要原因之一.     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography–tandem mass spectrometry

Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction (SPE) by passing 1000 mL of water through hydrophilic lipophilic balanced (HLB) SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE (strong anion exchange (SAX) + HLB) clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer (80:20, v/v) solution, and cleaned by SPE. Liquid chromatography–tandem mass spectrometry (LC-MS/MS) with multiple reaction monitoring (MRM) detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%–95.8%, 48.1%–105.3%, and 59.8%–103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification (LOQ) to 713.6 ng·L^-1 (ofloxacin) in surface water and from less than LOQ to 344.8 μg·kg^-1 (sulphamethoxazole) in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfloxacin was the highest (up to 38.5 μg·kg^-1), but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.     

Rapid method for on-site determination of phenolic contaminants in water using a disposable biosensor

A disposable biosensor was fabricated using single-walled carbon nanotubes, gold nanoparticles and tyrosinase (SWCNTs-AuNPs-Tyr) modified screen-printed electrodes. The prepared biosensor was applied to the rapid determination of phenolic contaminants within 15 minutes. The SWCNTs-AuNPs-Tyr bionanocomposite sensing layer was characterized with scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry methods. The characterization results revealed that SWCNTs could lead to a high loading of tyrosinase (Tyr) with the large surface area and the porous morphology, while AuNPs could retain the bioactivity of Tyr and enhance the sensitivity. The detection conditions, including working potential, pH of supporting electrolyte and the amount of Tyr were optimumed. As an example, the biosensor for catechol determination displayed a linear range of 8.0 × 10^-8 to 2.0 × 10^-5 mol·L^-1 with a detection limit of 4.5 × 10^-8 mol·L^-1 (S/N = 3). This method has a rapid response time within 10 s, and shows excellent repeatability and stability. Moreover, the resulting biosensor could be disposable, low-cost, reliable and easy to carry. This kind of new Tyr biosensor provides great potential for rapid, on-site and cost-effective analysis of phenolic contaminants in environmental water samples.     

Gold modified microelectrode for direct tetracycline detection

The residues of tetracycline antibiotics in water have attracted many concerns due to their harmful impact to human health. This paper reports an electrochemical sensor for the determination of tetracycline (TC) by the microelectrode, which was fabricated by electrodeposited gold colloids on tungsten tip. Cyclic voltammerty was used to study the electrochemical behavior of TC on the microelectrode. Well anodic wave was obtained at about 1.5 V in acidic solutions. Electrochemical determination of tetracycline was investigated using microelectrode by cyclic voltammetry. Under optimized conditions, the calibration curves for TC were obtained. The oxidation peak currents were linearly related to TC concentrations in the range of 1–10 mg·L^-1 and 10–100 mg·L^-1, respectively. The detection limit was 0.09 mg·L^-1 (S/N = 3).     

Abatement of sulfide generation in sewage by glutaraldehyde supplementation and the impact on the activated sludge accordingly

Hydrogen sulfide emission in sewer systems is associated with toxicity, corrosion, odour nuisance and high costs treatment. In this study, a novel method to inhibit sulfide generation from sewage by means of glutaraldehyde supplementation has been suggested and evaluated under anaerobic conditions. Different concentrations of glutaraldehyde at 10, 15, 20, 30 and 40 mg·L^-1 have been investigated. Besides, the possible impacts of glutaraldehyde supplementation on an activated sludge system and an appraisal of the economic aspects are presented as well. As observed from the experimental results, a dosage of 20 mg·L^-1 glutaraldehyde resulted in a significant decrease of the sulfide production by 70%–80% in the simulated sewage. Moreover, the impacts of additional glutaraldehyde at 20 mg·L^-1 on activated sludge, in terms of chemical oxygen demand removal and oxygen uptake rates, were negligible. From an economical point of view, the cost of the commercial glutaraldehyde products required in the operation, which was calculated on the basis of activated sulfide removal avoidance, was around €3.7–4.6 S·kg^-1. Therefore it is suggested that glutaraldehyde supplementation is a feasible technique to abate the sulfide problems in sewer systems. Yet further research is required to elucidate the optimum “booster” dosage and the dosing frequency in situ accordingly.     

A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils

An optimized procedure based on gas chromatography-mass spectrometry (GC-MS) combined with accelerated solvent extraction (ASE) is developed for the analysis of six phthalic acid esters (PAEs), which are priority soil pollutants nominated by United States Environmental Protection Agency (USEPA). Quantification of PAEs in soil employs ultrasonic extraction (UE) (USEPA 3550) and ASE (USEPA 3545), followed by clean up procedures involving three different chromatography columns and two combined elution methods. GC-MS conditions under selected ion monitoring (SIM) mode are described and quality assurance and quality control (QA/QC) criteria with high accuracy and sensitivity for target analytes were achieved. Method reliability is assured with the use of an isotopically labeled PAE, di-n-butyl phthalate-d4 (DnBP-D4), as a surrogate, and benzyl benzoate (BB) as an internal standard, and with the analysis of certified reference materials (CRM). QA/QC for the developed procedure was tested in four PAE-spiked soils and one PAE-contaminated soil. The four spiked soils were originated from typical Chinese agricultural fields and the contaminated soil was obtained from an electronic waste dismantling area. Instrument detection limits (IDLs) for the six PAEs ranged 0.10–0.31 μg·L^-1 and method detection limits (MDLs) of the four spiked soils varied from a range of 20–70 μg·kg^-1 to a range of 90– 290 μg·kg^-1. Linearity of response between 20 μg·L^-1 and 2 mg·L^-1 was also established and the correlation coefficients (R) were all>0.998. Spiked soil matrix showed relative recovery rates between 75 and 120% for the six target compounds and about 93% for the surrogate substance. The developed procedure is anticipated to be highly applicable for field surveys of soil PAE pollution in China.     

基于氮掺杂碳量子点的制备及其对Hg2+的响应

以乙二胺和抗坏血酸为原料,通过一步水热法制备了水溶性的氮掺杂碳量子点(N-CQDs).研究了N-CQDs的形貌特征、光学性能和应用分析.表征结果说明,N-CQDs形态为均匀分散的球形,有明显的晶格条纹,抗光漂白性能良好,表面富有含氧官能团,具有良好的水溶性.此外发现N-CQDs还具有优良的荧光性能和荧光稳定性,量子产率可以高达12.29%.分析得出,Hg²⁺对N-CQDs在1.0—120μmol·L^-1范围内有一定的猝灭效应,可作为Hg²⁺的荧光探针,检出限达230 nmol·L^-1.     

Effects of humic acid on residual Al control in drinking water treatment plants with orthophosphate addition

This study aimed to investigate the effects of humic acid (HA) on residual Al control in drinking water facilities that used orthophosphate addition. The results showed that adding orthophosphate was an effective method for residual Al control for the raw water without HA. When orthophosphate was added at 1.0 min before the addition of poly aluminum chloride (PACl), the concentrations of soluble aluminum (Sol-Al) and total aluminum (Tot-Al) residue were 0.08 and 0.086 mg·L^-1, respectively; both were reduced by 46% compared with the control experiment. The presence of HA would notably increase the residual Al concentration. For the raw water with 5 mg·L^-1 of HA, the concentrations of Sol-Al and Tot-Al increased from 0.136 and 0.174 mg·L^-1 to 0.172 and 0.272 mg·L^-1, respectively. For water with a HA concentration above 5 mg·L^-1, orthophosphate was ineffective in the control of residual Al, though there were still parts of orthophosphate were removed in coagulation. The amounts of Al removal were positively correlated with the solids freshly formed in coagulation. Similar to the raw water without HA, the best Al control was obtained with orthophosphate salt added at 1.0 min before PACl. HA concentrations in the raw water, solution pH, and the orthophosphate dosage suitable for residual Al control by orthophosphate precipitation were also investigated.     

通过式固相萃取/超高效液相色谱-串联质谱法测定蔬菜中18种农药残留

建立了超高效液相色谱-串联质谱(UPLC-MS;MS)快速测定蔬菜中18种农药残留的方法.样品经乙腈提取后,经Oasis PRiME HLB固相萃取柱净化,采用ACQUITY UPLC HSS T3 C18(50 mm×2.1 mm,1.8μm)色谱柱进行分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定性和定量分析.结果表明,18种农药在0.5—50μg·L^-1范围内线性关系良好(r2>0.995),方法最低检出限为0.4—1.5μg·kg^-1,最低定量限为1.4—5.0μg·kg^-1.在韭菜、芹菜、番茄、白菜基质中,5、10、50μg·kg^-1添加水平下的加标回收率为60.2%—126.9%,相对标准偏差(RSD)为0.4%—21.6%(n=3).     

Haloacetic acids in swimming pool and spa water in the United States and China

The objective of this study is to investigate the occurrence of haloacetic acids （HAAs）, a group of disinfection byproducts, in swimming pool and spa water. The samples were collected from six indoor pools, six outdoor pools and three spas in Pennsylvania, the United States, and from five outdoor pools and nine indoor pools in Beijing, China. Five HAAs （HAA5）, including monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid were analyzed. Total chlorine, pH and total organic carbon concentration were analyzed as well. Results indicated that the levels of HAA5 in swimming pools and spas in the United States ranged from 70 to 3980μg·L^-1, with an arithmetic average at 1440μg·L^-1 and a median level at 1150μg·L^-1. These levels are much higher than the levels reported in chlorinated drinking water and are likely due to organic matters released from swimmers＇ bodies. The levels of HAA5 in swimming pools in China ranged from 13 to 332μg·L^-1, with an arithmetic average at 117μg·L^-1 and a median level at 114μg·L^-1. The lower HAA levels in swimming pools in China were due to the lower chlorine residuals. Results from this study can help water professionals to better understand the formation and stability of HAAs in chlorinated water and assess risks associated with exposures to HAAs in swimming pools and spas.     

土著细菌对江汉平原浅层含水层沉积物中砷迁移的影响

对江汉平原水文地质调查发现,该地区地下水砷含量已远超国家饮用水标准。以沉积物培养的土著细菌混合液为生物材料,以江汉平原高砷含水层沉积物为研究对象,在实验室内模拟地下水系统,研究厌氧环境条件下,不同生物量土著细菌和pH值对沉积物中砷迁移转化的影响,以及土著细菌活动下砷在不同沉积物中的迁移转化。结果表明,不同生物量菌悬液都能促进沉积物中As的释放,增加总As和As(III)的浓度,但150mL处理组,在研究后期,总As和As(III)的浓度呈现减缓趋势;在初始生物量一定的条件下,沉积物中As含量越高,细菌活动下总As相对释出量就越低,而且As(III)占所释出总As的比值就越高,但两个高砷含量沉积物组的差异较小;在初始pH值为5、7和9的培养条件下,细菌都能加速砷的迁移,但pH值为5的处理组(简称pH5处理组)最弱,在前8天,pH9处理组较pH7处理组的低,随后超过pH7处理组。研究表明,土著细菌悬液能加速As从沉积物中释出,并且释出的As以As(III)为主;在耐受的弱碱性环境条件下,细菌对砷的迁移和转化随环境的pH值增加而增强。     

Occurance and control of manganese in a large scale water treatment plant

The continuous variations of dissolved oxygen (DO), manganese (Mn), pH, and their effect on manganese removal by different water treatment processes are investigated. The results show that the declined DO concentration and pH value in the bottom of reservoir results in the increasing release of Mn from sediment to source water. Manganese concentration increased from 0.1 to 0.4 mg·L^-1 under the condition that DO concentration decreased from 12.0 to 2.0 mg·L^-1 in raw water. The different water treatment processes exhibited different efficiency on manganese removal. The processes with recycling of the suspended sludge, low elevation velocity in settling tank and slow filter rate, will benefit the manganese removal. During a high release of manganese in raw water, traditional coagulation-sedimentation and filtration could not completely remove Mn, although granular activated carbon filtration (GAC) had been applied. At that case, preoxidation with chlorine or potassium permanganate (KMnO₄) was necessary to address the high manganese concentration.     

Identification of cadmium-induced genes in maize seedlings by suppression subtractive hybridization

A maize variety, Huatian-1, had an unusually low translocation rate of cadmium (Cd) (59.6 mg·kg^-1 in the roots and 0.093 mg·kg^-1 in the grain) compared to 24 other varieties while being grown in soils with 16.50 mg·kg^-1 Cd. This indicates that this particular species may have special mechanisms that affect the absorption and translocation pattern of Cd. In this paper, the technique of suppression subtractive hybridization (SSH) was used to isolate and identify Cd-induced genes from Huatian-1 hydroponically ?exposed? to? 0.1 mM ?CdCl₂ ?for? 1 h,? 12 h, 24 h, and 48 h. We found a total of 15 differentially expressed genes in the four groups; 2, 3, 4, and 6 genes were from the groups of 1 h, 12 h, 24 h, and 48 h treatment, respectively. Phospholipase PLDb1 mRNA, adenosine triphosphate (ATP) phosphoribosyl transferase 2, and Sp17 were turned on in the maize in response to Cd stress, and it might provide new clues to explain the mechanism of maize tolerance to Cd.