Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid, sensitive, and cost-effective analytical method was developed for the analysis of selected semi-volatile organic compounds in water. The method used an automated online solid-phase extraction technique coupled with programmed-temperature vaporization large-volume injection gas chromatography/mass spectrometry. The water samples were extracted by using a fully automated mobile rack system based on x-y-z robotic techniques using syringes and disposable 96-well extraction plates. The method was validated for the analysis of 30 semivolatile analytes in drinking water, groundwater, and surface water. For a sample volume of 10 mL, the linear calibrations ranged from 0.01 or 0.05 to 2.5 μg·L⁻¹, and the method detection limits were less than 0.1 μg·L⁻¹. For the reagent water samples fortified at 1.0 μg·L⁻¹ and 2.0 μg·L⁻¹, the obtained mean absolute recoveries were 70%–130% with relative standard deviations of less than 20% for most analytes. For the drinking water, groundwater, and surface water samples fortified at 1.0 μg·L⁻¹, the obtained mean absolute recoveries were 50%–130% with relative standard deviations of less than 20% for most analytes. The new method demonstrated three advantages: 1) no manipulation except the fortification of surrogate standards prior to extraction; 2) significant cost reduction associated with sample collection, shipping, storage, and preparation; and 3) reduced exposure to hazardous solvents and other chemicals. As a result, this new automated method can be used as an effective approach for screening and/or compliance monitoring of selected semi-volatile organic compounds in water.     

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.     

Preparation of hapten-specific monoclonal antibody for cadmium and its ELISA application to aqueous samples

High-affinity and specific monoclonal antibodies against cadmium-ethylene diamine tetraacetic acid (EDTA) complex have been produced using the hybridoma technique. A hapten was synthesized and characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and UV-Vis. Competitive enzyme-linked immunosorbent assay (ELISA) for quantitative detection of cadmium in aqueous sample was developed. The monoclonal antibody with high level of binding affinity for Cd-IEDTA-BSA and high specificity for soluble Cd-EDTA complex showed less than 0.99% cross-reactivity with other 11 metals. The limit of detection was 0.10 μg·L⁻¹, and the effective linear range was 10⁻¹–10³ μg·L⁻¹. The intra- and inter-assay coefficient variations were 1.5%–6.3% and 3.2%–7.4%, respectively. The spike recovery in different water samples were between 98.5% and 110.3%. The detection limit of this assay was well below the allowable concentration of cadmium (3 μg·L⁻¹), and the working range was wider than that of other methods which showed the range of 2.19–86.38 and 0–10³ μg·L⁻¹. The competitive ELISA established in this paper was sensitive and accurate in the screening of cadmium in aqueous samples. The results will lay a solid foundation for construction of an immunoassay kit for cadmium.     

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 μg·L⁻¹ Cu exposure and depressed the Zn clearance rate significantly (p<0.05). However, the presence of 100 μg·L⁻¹ and 300 μg·L⁻¹ Zn hardly affected the Cu clearance rate. The 300 μg·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.     

A hybrid membrane process for simultaneous thickening and digestion of waste activated sludge

A hybrid membrane process for simultaneous sludge thickening and digestion (MSTD) was studied. During one cycle (15 d) of operation under a hydraulic retention time of 1 d, the concentration of mixed liquor suspended solids (MLSS) continuously increased from about 4 g·L⁻¹ to 34 g·L⁻¹, and the mixed liquor volatile suspended solids (MLVSS) increased from about 3 g·L⁻¹ to over 22 g·L⁻¹. About 42% of the MLVSS and 39% of the MLSS reduction were achieved. The thickening and digestion effects in the MSTD were further analyzed based on a mass balance analysis. Test results showed that biopolymers and cations of biomass were gradually released to the bulk solution during the process. It was also found that the capillary suction time, colloidal chemical oxygen demand, soluble microbial products, viscosity, and MLSS had significant positive correlations with the membrane fouling rate, whereas extracellular polymeric substances, polysaccharides, and proteins extracted from biomass had negative impacts on membrane fouling.     

Arsenic (V) removal from groundwater by GE-HL nanofiltration membrane: effects of arsenic concentration, pH, and co-existing ions

A laboratory-scale investigation was performed to study arsenic (As (V)) removal by negatively charged GE-HL nanofiltration (NF) membrane in simulated drinking water. Effects of As (V) concentration (0–200 μg·L⁻¹), pH, and co-ions and counter-ions were investigated. The NF membrane presented good stability, and the rejection rates exceeded 90%. The rejection rates of As (V) decreased with the increase of As (V) concentration, while it increased with the increase of pH (reached 96% at pH 6.75). Moreover, a negative relationship was observed between the co-existing ions of Cl⁻, Na⁺, SO₄²⁻, and Ca²⁺ and the removal of As (V), in which bivalent ions presented more significant effects than monovalent ions.     

Evaluate HAA removal in biologically active carbon filters using the ICR database

The effects of biologically active carbon (BAC) filtration on haloacetic acid (HAA) levels in plant effluents and distribution systems were investigated using the United States Environmental Protection Agency’s Information Collection Rule (ICR) database. The results showed that average HAA5 concentrations in all locations were 20.4 μg·L⁻¹ and 29.6 μg·L⁻¹ in ICR plants with granular activated carbon (GAC) and ICR plants without GAC process, respectively. For plants without GAC, the highest HAA levels were observed in the quarters of April to June and July to September. However, for plants with GAC, the highest HAA levels were observed in the quarters of April to June and January to March. This HAA level profile inversely correlated well with water temperature, or biologic activity. For GAC plants, simulated distribution samples matched well with distribution system equivalent samples for Cl₃AA and THMs. For plants with and without GAC, simulated distribution samples overestimated readily biodegradable HAAs in distribution systems. The study indicated that through HAA biodegradation, GAC process plays an important role in lowering HAA levels in finished drinking water.     

Development of pretreatment protocol for DNA extraction from biofilm attached to biologic activated carbon (BAC) granules

The biologic activated carbon (BAC) process is widely used in drinking water treatments. A comprehensive molecular analysis of the microbial community structure provides very helpful data to improve the reactor performance. However, the bottleneck of deoxyribonucleic acid (DNA) extraction from BAC attached biofilm has to be solved since the conventional procedure was unsuccessful due to firm biomass attachment and adsorption capacity of the BAC granules. In this study, five pretreatments were compared, and adding skim milk followed by ultrasonic vibration was proven to be the optimal choice. This protocol was further tested using the vertical BAC samples from the full-scale biofilter of Pinghu Water Plant. The results showed the DNAyielded a range of 40 μg·g⁻¹ BAC (dry weight) to over 100 μg·g⁻¹ BAC (dry weight), which were consistent with the biomass distribution. All results suggested that the final protocol could produce qualified genomic DNA as a template from the BAC filter for downstream molecular biology researches.     

Technical feasibility study of an onshore ballast water treatment system

To fulfill the requirements of Guidelines for approval of ballast water management system (G8), a set of onshore ballast water treatment equipment utilizing micro-pore ceramic filtration (MPCF) and UV radiation (MPCF&UV) system was designed and set up with a maximum flow rate of 80 m³·h⁻¹. Technical feasibilities of MPCF&UV system were evaluated in three areas: removal efficiencies of indicator organism and oceanic bacteria, perdurability of a ceramic filter, and application on native seawater. The results showed that no indicator organism (Dunaliella) or oceanic bacteria was detected after treatment of 20 L MPCF and UV radiation at 1.3×10⁴ μW·s·cm⁻². A 20 L ceramic filter can run continuously for 5.3 h at the flow rate of 15 m³·h⁻¹ before its pressure drop up to 0.195 MPa. The removal percentage of total plankton amounts were 91.9% at a flow rate of 70 m³·h⁻¹ by 80 L MPCF and UV radiation at 1.3×10⁴ μW·s·cm⁻².     

Impact of solids on biphasic biodegradation of phenanthrene in the presence of hydroxypropyl-β-cyclodextrin (HPCD)

The consequence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of great concern. The hydrophobic properties of PAHs significantly impact phase distribution causing limited bioavailability. Enhanced biodegradation has been extensively carried out by surfactants and the redeployment effect was recognized. However, the quantitative relationship concerning the impact of solids was rarely reported. A batch of biphasic tests were carried out by introducing Mycobacterium vanbaalenii PYR-1 and hydroxypropyl-β-cyclodextrin (HPCD) into a mixture of phenanthrene solution and various glass beads (GB37-63, GB105-125, and GB350-500). The comparative results demonstrated that HPCD had little effect on microbial growth and was not degradable by bacterium. A model was proposed to describe the biodegradation process. The regression results indicated that the partition coefficient k _d (1.234, 0.726 and 0.448 L·g⁻¹) and the degradation rate k (0 mmol·L⁻¹: 0.055, 0.094, and 0.112; 20 mmol·L⁻¹: 0.126, 0.141, and 0.156; 40 mmol·L⁻¹: 0.141, 0.156 and 0.184 d⁻¹) were positively and negatively correlated with the calculated total surface area (TSA) of solids, respectively. Degradation enhanced in the presence of HPCD, and the enhancing factor f was calculated (20 mmol·L⁻¹: 15.16, 40.01, and 145.5; 40 mmol·L⁻¹: 13.29, 37.97, and 138.4), indicating that the impact of solids was significant for the enhancement of biodegradation.     

莠去津降解菌HB-5的最佳产酶培养基及发酵条件

从农药厂废水中分离到一株降解莠去滓的节杆菌(Arthrobacter sp.)HB-5,以从该菌中提取到的降解酶对莠去津的降解率为指标,进行最佳产酶培养基及发酵条件的优化研究,对其产酶量进行了评价.通过正交试验和均匀试验,对细菌HB-5的发酵培养基进行了优化研究.运用SAS软件进行结果分析,所获优化培养基配方为:蔗糖3.0g·L-1,莠去津0.38g·L-1,K2HPO40.5g·L-1,KH2PO41.2 g·L-1,MgSO4·7H2O 1.2g·L-1,NaCl 0.1g·L-1,微量元素溶液3.8mL·L-1.得到菌株培养的最佳优化条件为:菌株发酵液培养时间为48h.接种量为2%,发酵液初始pH值为9,250mL三角瓶中装液量为80mL经优化后,降解酶对莠去津的降解率(91.64%)比原培养基(40.67%)提高了125%.     

一种高效微生物絮凝剂产生菌的筛选及培养基优化

从某自来水处理厂的活性污泥中筛选得到了一株稳定高效的微生物絮凝剂产生菌MBF-33,所产絮凝剂对高岭土悬浮液体系有较好的絮凝作用.通过培养基优化,对高岭土的絮凝率从81.3%提高到95%.实验结果表明:(1)适宜的单一碳源为25 g·L-1葡萄糖;(2)复合碳源效果优于单一碳源,适宜的复合碳源为蔗糖5 g·L-1,葡萄糖20 g·L-1;(3)无机氮不利于该菌生长,适宜的氮源为单一有机氮,为1.5 g·L-1蛋白胨;(4)0.2 g·L-1的MgSO4有利于菌生长,但不利于絮凝剂产生.     

Dilution sampling and analysis of particulate matter in biomass-derived syngas

Thermochemical biomass gasification, followed by conversion of the produced syngas to fuels and electrical power, is a promising energy alternative. Real-world characterization of particulate matter (PM) and other contaminants in the syngas is important to minimize damage and ensure efficient operation of the engines it powers and the fuels created from it. A dilution sampling system is demonstrated to quantify PM in syngas generated from two gasification plants utilizing different biomass feedstocks: a BioMax?15 Biopower System that uses raw and torrefied woodchips as feedstocks, and an integrated biorefinery (IBR) that uses rice hulls and woodchips as feedstocks. PM_2.5 mass concentrations in syngas from the IBR downstream of the purification system were 12.8–13.7 μg·m⁻³, which were significantly lower than the maximum level for catalyst protection (500 μg·m⁻³) and were 2–3 orders of magnitude lower than those in BioMax?15 syngas (2247–4835 μg·m⁻³). Ultrafine particle number concentration and PM_2.5 chemical constituents were also much lower in the IBR syngas than in the BioMax?15. The dilution sampling system enabled reliable measurements over a wide range of concentrations: the use of high sensitivity instruments allowed measurement at very low concentrations (∼1 μg·m⁻³), while the flexibility of dilution minimized sampling problems that are commonly encountered due to high levels of tars in raw syngas (∼1 g·m⁻³).     

Physical and chemical processes of wintertime secondary nitrate aerosol formation

The UCD/CIT model was modified to include a process analysis (PA) scheme for gas and particulate matter (PM) to study the formation of secondary nitrate aerosol during a stagnant wintertime air pollution episode during the California Regional PM_2.5/PM₁₀ Air Quality Study (CRPAQS) where detailed measurements of PM components are available at a few sites. Secondary nitrate is formed in the urban areas from near the ground to a few hundred meters above the surface during the day with a maximum modeled net increase rate of 4 μg·m⁻³·d⁻¹ during the study episode. The secondary nitrate formation rate in rural areas is lower due to lower NO₂. In the afternoon hours, near-surface temperature can be high enough to evaporate the particulate nitrate. In the nighttime hours, both the gas phase N₂O₅ reactions with water vapor and the N₂O₅ heterogeneous reactions with particle-bound water are important for secondary nitrate formation. The N₂O₅ reactions are most import near the surface to a few hundred meters above surface with a maximum modeled net secondary nitrate increase rate of 1 μg·m⁻³·d⁻¹ and are more significant in the rural areas where the O₃ concentrations are high at night. In general, vertical transport during the day moves the nitrate formed near the surface to higher elevations. During the stagnant days, process analysis indicates that the nitrate concentration in the upper air builds up and leads to a net downward flux of nitrate through vertical diffusion and a rapid increase of surface nitrate concentration.     

N,N-双(二硫代羧基)乙二胺对微量络合镍的深度脱除特性研究

以柠檬酸镍(CA-Ni)、酒石酸镍(TA-Ni)、焦磷酸镍(SP-Ni)3种低浓度模拟络合镍废水为研究对象,选用自制的重金属捕集剂N,N-双(二硫代羧基)乙二胺(EDTC),对废水中的Ni进行深度脱除.重点研究了EDTC投加量、初始p H、反应时间对Ni去除效果的影响及螯合沉淀物的沉淀性能和溶出特性,同时分析了EDTC去除络合Ni的机理.研究结果表明,处理初始浓度5 mg·L~(-1)的CA-Ni、TA-Ni、SP-Ni,p H为4~8,EDTC最佳投加量分别为60 mg·L~(-1)、55 mg·L~(-1)和70 mg·L~(-1),PAM(聚丙烯酰胺)为1 mg·L~(-1),反应时间2 min,Ni的出水浓度均低于0.05mg·L~(-1),去除率达99%以上.螯合沉淀物沉降性能好且在弱酸弱碱条件下能稳定存在.红外光谱图和元素分析结果表明:EDTC与Ni发生螯合反应,即EDTC直接脱除络合镍中的Ni2+,并与Ni2+生成更稳定的螯合产物EDTC-Ni,进而有效地去除废水中Ni.     

1株分离自煤矿废水的铁硫氧化细菌LY01的鉴定及其氧化特性研究

从贵州省某煤矿废水中分离出1株嗜酸性的铁硫氧化细菌菌株LY01,经过对该菌株的形态特征、理化特征检测及16S rRNA序列分析,初步鉴定菌株LY01为嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans).在无机盐培养液中菌株LY01可以从氧化Fe2+、单质硫(S0)及黄铁矿(FeS2)获得能量生长,对Fe2+的氧化速率最快,反应30 h即可将44.2 g.L-1的FeSO4.7H2O完全氧化,菌体细胞达到4.2×107个.mL-1;反应21 d可将溶液中10 g.L-1含量的S0氧化6.7%,溶液中SO24-浓度达2 001 mg.L-1,菌体细胞达到8.9×107个.mL-1;反应20 d可将溶液中30 g.L-1含量的FeS2氧化10%,溶液中SO24-浓度达4 443 mg.L-1,菌体细胞达到3.4×108个.mL-1.研究重金属离子Ni2+、Pb2+对菌株LY01氧化FeS2活性的影响,结果发现10～100 mg.L-1的Ni2+对菌株LY01氧化FeS2活性有一定的影响,而10～100 mg.L-1Pb2+对菌株LY01氧化FeS2的活性无影响.     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r ² = 0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK _FOC values of 6.02 to 6.42 (μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C _e, the BC had higher K _oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C _e= 0.05 S _w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

生物淋滤-PAC与PAM联合调理城市污泥

采用生物淋滤-聚合氯化铝(PAC)与聚丙烯酰胺(PAM)联合使用工艺对城市污泥进行了调理研究.结果表明,在固定单质硫投量为3 g.L-1的条件下,投加亚铁离子能明显加快污泥生物淋滤速率;FeSO4.7H2O投量为8 g.L-1时,污泥pH降至2约需1.5 d.生物淋滤显著改善了污泥的脱水性能,生物淋滤后使污泥比阻从6.45×1010 s2.g-1降到1.45×1010 s2.g-1,降低了77.52%,但污泥仍属于难脱水污泥.回调淋滤污泥pH至6,投加PAC及PAM对淋滤污泥进行强化调理.结果表明,单独使用PAC与PAM的最佳投量分别为200 mg.L-1和50 mg.L-1;联合使用PAC与PAM时,PAC与PAM的最佳投量分别为100mg.L-1和25 mg.L-1,污泥比阻和滤饼含水率分别为2.02×108 s2.g-1和74.81%,污泥属于易脱水污泥.与单独使用PAC与PAM相比,PAC与PAM联合使用调理污泥费用低、处理效果好.     

改性玉米秸秆材料的制备及吸油性能的研究

以粉末状玉米秸秆(Raw corn stalks,RCS)为基体,甲基丙烯酸丁酯和苯乙烯为单体,采用悬浮聚合法制备高吸油复合材料(Butylmethacrylate and styrene grafted corn stalks,BMS-CS).实验确定的最佳制备条件为:在50℃,引发剂硝酸铈铵为2.0mmol·L-1,单体甲基丙烯酸丁酯和苯乙烯浓度分别为0.6mol·L-1、0.012mol·L-1,交联剂N,N’-亚甲基双丙烯酰胺质量分数为0.1%(相对于RCS的质量)的前提下反应25h.同时,实验考察了吸附时间、吸附温度及保油时间等对材料吸油性能的影响,并通过傅里叶变换红外光谱仪、X-射线衍射和扫描电镜对改性前后样品的结构进行表征.结果表明,BMS-CS表面变得粗糙且呈毛刺状,具有较多不规则的褶皱;结晶度的下降也印证了粗糙度的增加;红外图谱中新出现的酯基和苯乙烯基的吸收峰说明亲油单体被接枝到RCS表面;两种原因共同促进了改性材料吸油性能的增加.吸油数据显示,常温下RCS和BMS-CS的吸油量分别为5.23g·g-1和20.12g·g-1,后者是前者的3.85倍,即改性后的材料吸油性能明显增加.     

Carbon dioxide fixation by Chlorella sp. USTB-01 with a fermentor-helical combined photobioreactor

A promising microalgal strain isolated from fresh water, which can grow both autotrophically on inorganic carbon under lighting and heterotrophically on organic carbon without lighting, was identified as Chlorella sp. USTB-01 with the phylogenetic analysis based on 18S ribosomal ribonucleic acid (rRNA) gene sequences. In the heterotrophic batch culture, more than 20.0 g·L⁻¹ of cell dry weight concentration (DWC) of Chlorella sp. USTB-01 was obtained at day 5, and which was used directly to seed the autotrophic culture. A novel fermentor-helical combined photobioreactor was established and used to cultivate Chlorella sp. USTB-01 for the fixation of carbon dioxide (CO₂). It showed that the autotrophic growth of Chlorella sp. USTB-01 in the combined photobioreactor was more effective than that in the fermentor alone and the maximum DWC of 2.5 g·L⁻¹ was obtained at day 6. The highest CO₂ fixation of 95% appeared on day 1 in the exponential growth phases of Chlorella sp. USTB-01 and 49.8% protein was found in the harvested microalgal cells.