活性炭吸附处理电镀废水中的EDTA

采用颗粒活性炭对模拟废水中EDTA进行批式吸附实验,在实验中考察了恒温振荡器的振荡速度、温度、pH值等因素对吸附的影响,同时探讨了吸附等温线模型和吸附动力学模型。实验结果表明,在25％时活性炭对EDTA的吸附平衡时间为40h。在pH值为5．0、温度为25℃、振荡器振荡速度为200r／min、活性炭粒径为1～2mm、活性炭加入量为10g／L的情况下,EDTA的浓度在48h内由368．8mg／L降低至76．34mg／L,对应的COD值从305．9mg／L降低为67．21mg／L,去除率达到了79．3％。活性炭对EDTA的吸附符合Langmuir吸附等温线模型,其吸附行为可以用准二级吸附动力学模型来描述。     

固定化微生物强化处理对甲苯胺模拟废水的研究

采用新型固定化载体大孔吸附树脂X-5固定化微生物强化SBR处理对甲苯胺模拟废水，与对照组相比，通过投加大孔吸附树脂X-5固定化微生物可以有效提高反应器的处理效率。在进水TOC浓度为434．8mg／L，对甲苯胺浓度为326．9mg／L的条件下，强化组可在100min左右将TOC和对甲苯胺基本去除完全，去除率在99％以上。对照组则需要300min才能达到相近的去除效果。强化组对氨氮同样具有较好的硝化效果，出水氨氮浓度在10mg／L以下。     

饮用水源水无机金属污染的应急处理

根据密云水库供水现状,针对突发性无机金属污染事件,采用聚合氯化铝辅助化学沉淀法进行应急处理。选用Cu2＋、Fe2＋、Zn2＋和Cd2＋ 4种金属离子为目标污染物,首先通过小试实验确立了最佳混凝处理条件。结果表明,调节pH值为8．0左右,可使初始浓度为5mg／L和10mg／L的Cu2＋浓度降至0．96mg／L和0．67mg／L;初始浓度为1．5mg／L和3mg／L的Fe2＋浓度降至0．27mg／L和0．24mg／L;初始浓度为0．05mg／L和0．1mg／L的Cd2＋浓度降为0．0089mg／L和0．0078mg／L;调节pH值为9．0时,可使初始浓度为5mg／L和10mg／L的Zn2＋浓度降至0．57mg／L和0．48mg／L。4种污染物出水浓度均低于国家饮用水标准。在小试基础上,在北京第九水厂开展无机金属污染处理的中试实验,结果表明所选用的聚合氯化铝辅助化学沉淀法简便易行,可实现污染物快速、有效去除。     

饮用水源中有机磷农药的应急预处理技术研究

有机磷农药的大量生产和使用对饮用水安全造成了潜在的巨大威胁。为了在饮用水源突发有机磷农药污染时保证饮用水安全,在水源水中进行了高锰酸钾氧化、粉末活性炭（PAC）吸附、臭氧氧化、O3／PAC和O3／H2O2 5种预处理技术对4种有机磷农药（乐果、敌敌畏、马拉硫磷和甲基对硫磷）的去除效果对比研究。实验结果表明,当水中乐果、敌敌畏浓度为266肛g／L、3．6μg／L时,0．5mg／L的高锰酸钾不能将其去除达标（国家生活饮用水卫生标准,GB5749—2006）;PAC对乐果和敌敌畏的吸附效果良好,20mg／L的PAC能将低浓度的乐果（241μg／L）和中低浓度的敌敌畏（3．0～9．3μg／L）去除达标;臭氧对4种农药均有较好的去除效果,当CT（浓度×时间）值为17mg·min／L时,除高浓度的乐果（729μg／L）和甲基对硫磷（276μg／L）外,其余农药均可以去除达标;采用O3／PAC和O3／H2O2高级氧化预处理,高浓度的乐果（629～710μg／L）和甲基对硫磷（364～428μg／L）均可迅速去除达标。     

应急处理苯胺污染水源水的粉末活性炭吸附工艺的研究

以浑河水为原水,模拟突发苯胺污染,通过投加粉末活性炭(PAC)进行应急处理的试验研究.试验结果表明:PAC对苯胺的吸附在30 min内能达到80%～90%的吸附容量;PAC对苯胺的吸附等温线符合弗兰德里希(Freundlich)吸附模式,在苯胺的平衡质量浓度为0.030 mg/L时,PAC对其吸附容量约为5 mg/g;比表面积较大的木屑炭对苯胺的吸附效果比煤质炭好,但粒度以300目左右为宜;炭浆浓度越小对苯胺的吸附效果越好;溶液pH以不小于5为最好;絮凝剂最佳的投加顺序是先投加炭浆然后投加絮凝荆;对突发的浑河水苯胺污染,在取水口处投加PAC是十分有效的应急处理措施.     

介孔纳米γ-Al2O3对稀土元素锎、铈的吸附性能

以介孔纳米γ-Al2O3为吸附材料,重点研究了吸附剂投加量、溶液pH、吸附时间及温度对介孔纳米γ-Al2O3吸附稀土元素镧、铈的影响。通过正交实验优选出介孔纳米γ-Al2O3对稀土元素镧铈吸附的最优参数,采用10mg／L的La^3＋、Ce^4＋标准溶液,选择投加量、pH、吸附时间为影响因素,进行3因素3水平的正交实验。通过正交实验与单因素实验综合分析表明最佳实验方案为：投加量为0．20g,pH为7,吸附时间为15min。在初始浓度为10～100mg／L时,介孑L纳米γ-Al2O3对La^3＋、Ce^4＋的吸附符合Langmuir等温吸附式。拟合得到的理论饱和吸附量分别为22．32mg／g和23．75mg／g。     

BCO+BAF工艺深度处理洗涤剂废水

采用生物接触氧化(BCO)+曝气生物滤池(BAF)组合工艺深度处理洗涤剂废水,研究了溶解氧浓度(DO)、水力停留时间(HRT)对其处理性能的影响。实验结果表明,随着DO浓度的提高,组合工艺对COD和LAS的去除率都随之增加;水力停留时间的增加有利于对COD与LAS的去除,最佳停留时间选为21.2h为宜;在BCO段DO为3.0 mg/L,HRT为20.0 h,BAF段DO为4.0 mg/L,HRT为1.2 h的运行条件下,COD与LAS的去除率分别为90.5%和94.3%,出水COD和LAS均能达到排放标准。     

废弃核桃壳粉对模拟微污染水中总铁的静态吸附特性研究

采用废弃核桃壳粉对总铁质量浓度约为3 mg/L的模拟微污染水进行了静态吸附实验研究.结果表明,采用产地为新疆、粒径为1.6～2.5 mm的废弃核桃壳粉1.0 g、水样初始pH为7.0、吸附时间为240 min时,总铁去除率可以达到92.69%.吸附后,水样中总铁浓度满足<生活饮用水卫生标准>(GB 5749-2006)...     

蒽降解菌T2的最佳培养条件及其对蒽的生物降解动力学研究

从长期被石油污染的土壤中筛选得到一株以蒽为惟一碳源的混合菌T2,在接种量为1％,pH为7,温度为30℃,摇床转速为120r／min,蒽的初始浓度为100mg／L的条件下培养5d后,其对蒽的降解率可以达到56．6％。通过单因素实验和正交实验对菌种T2的培养条件进行研究,得到菌种T2的最佳培养条件为：接种量为5％,pH为6,温度为35℃,蒽的初始浓度为40mg／L时,最适合菌种生长。另外,菌种T2对蒽的降解动力学实验的结果表明,蒽的残留浓度Y（mg／L）与时间t（h）符合方程y=2．544e（-0.00275）t.     

次氯酸钠处理终冷水中氰化物硫化物的研究

以次氯酸钠为氧化剂,用正交实验研究了次氯酸钠处理终冷水中氰化物和硫化物,得出正交实验中各因素的主次关系及对除氰除硫的影响。研究结果表明,反应体系的pH是影响脱氰脱硫的重要因素。在最佳处理条件,即pH为10．0,反应温度为25℃,投氯量系数为1．4,反应时间为45min．能使氰化物的质量浓度降至0．267mg／L,脱氰率高达99．8％,硫化物的质量浓度降到0．387mg／L,脱硫率达92．0％,达到≤0．5mg／L的国家排放标准。文章还对工业化提出了一些设想。     

Structure-activity relationships for association of linear alkylbenzene sulfonates with activated sludge

Sorption of linear alkylbenzene sulfonates (LAS) on sludge particles from wastewater treatment plants was studied. The effect of alkyl chain length and the water hardness were investigated. Sorption on sludge increases with increasing alkyl chain length in the LAS molecules. The results are interpreted in terms of a hydrophobic bonding mechanism being the critical micelle concentration a good index of the surfactant hydrophobicity. The increase in free energy of adsorption for the addition of successive methylene groups to the alkyl chain was estimated as 2.4 kJ/mol. Water hardness clearly enhances the sorption of LAS homologues on sludge and seems to promote cooperative sorption at high surfactant and calcium ion concentrations. An empirical equation was provided that allow to estimate the partition coefficient between aqueous and solid phases for LAS homologues as a function of the alkyl chain length and the water hardness.     

A comparison of river water quality sampling methodologies under highly variable load conditions

When river water quality fluctuates over relatively short periods of time with respect to the sampling frequency, the collection of grab samples may be inappropriate for characterising average water quality. This paper presents the results of a water quality monitoring study carried out on a stretch of the river Lambro (northern Italy) dominated by a periodically overloaded sewage treatment works (STW) located near its upstream end. Water quality was strongly influenced by a pronounced diurnal cycle in pollutant loads caused by the regular emission of untreated waste water during periods of high domestic flow (daytime). Two different sampling techniques were employed: grab sampling and 24-h composite sampling using automatic samplers. Samples were collected at the plant overflow and at several sites along the river and analysed for two common ingredients of household detergents, linear alkylbenzene sulphonate (LAS) and boron (B) and for routine water quality variables. The results obtained show that: (1) The diurnal variability of point-source-derived chemical concentrations in the river downstream of the undersized STW increased with increasing removal efficiency in sewage treatment. (2) The shape of the diurnal concentration signal remained relatively intact for a considerable distance downstream of the STW for several water quality variables, suggesting that hydrodynamic dispersion plays a relatively minor role in controlling concentration patterns in this river. (3) In-stream degradation of LAS was consistent with first order kinetics with a rate constant of 0.05-0.06 h(-1). (4) Grab sampling is a relatively inefficient methodology for capturing mean concentrations for rivers subjected to highly variable loads, especially when it is restricted to office hours. The inefficiency of grab sampling is more marked for substances (e.g. LAS) which are effectively removed during sewage treatment than for substances which are not. (5) For LAS, diurnal variability in the concentration signal decreases with distance downstream, making grab sampling an increasingly reliable methodology for estimating mean concentrations. (6) 24-h composite sampling is an efficient way of eliminating the effect of diurnal variations in load strength.     

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.     

Degradation of organic pollutants in Mediterranean forest soils amended with sewage sludge

The degradation of two groups of organic pollutants in three different Mediterranean forest soils amended with sewage sludge was studied for nine months. The sewage sludge produced by a domestic water treatment plant was applied to soils developed from limestone, marl and sandstone, showing contrasting alkalinity and texture. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10–13 carbon alkylic chain, and nonylphenolic compounds, including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EO + NP2EO). These compounds were studied because they frequently exceed the limits proposed for sludge application to land in Europe. After nine months, LAS decomposition was 86–96%, and NP + NP1EO + NP2EO decomposition was 61–84%, which can be considered high. Temporal trends in LAS and NP + NP1EO + NP2EO decomposition were similar, and the concentrations of both types of compounds were highly correlated. The decomposition rates were higher in the period of 6–9 months (summer period) than in the period 0–6 months (winter + spring period) for total LAS and NP + NP1EO + NP2EO. Differences in decay rates with regard to soil type were not significant. The average values of decay rates found are similar to those observed in agricultural soils.     

European risk assessment of LAS in agricultural soil revisited: species sensitivity distribution and risk estimates

Linear alkylbenzene sulphonate (LAS) is used at a rate of approximately 430,000 tons/y in Western Europe, mainly in laundry detergents. It is present in sewage sludge (70-5,600 mg/kg; 5-95th percentile) because of its high usage per capita, its sorption and precipitation in primary settlers, and its lack of degradation in anaerobic digesters. Immediately after amendment, calculated and measured concentrations are <1 to 60 mg LAS/kg soil. LAS biodegrades rapidly in soil with primary and ultimate half-lives of up to 7 and 30 days, respectively. Calculated residual concentrations after the averaging time (30 days) are 0.24-18 mg LAS/kg soil. The long-term ecotoxicity to soil microbiota is relatively low (EC10 >or=26 mg sludge-associated LAS/kg soil). An extensive review of the invertebrate and plant ecotoxicological data, combined with a probabilistic assessment approach, led to a PNEC value of 35 mg LAS/kg soil, i.e. the 5th percentile (HC5) of the species sensitivity distribution (lognormal distribution of the EC10 and NOEC values). Risk ratios were identified to fall within a range of 0.01 (median LAS concentration in sludge) to 0.1 (95th percentile) and always below 0.5 (maximum LAS concentration measured in sludge) according to various scenarios covering different factors such as local sewage influent concentration, water hardness, and sewage sludge stabilisation process. Based on the present information, it can be concluded that LAS does not represent an ecological risk in Western Europe when applied via normal sludge amendment to agricultural soil.     

溶液中阴离子对UV/H2O2降解十二烷基苯磺酸钠的影响及其机理

研究了UV/H2O2工艺对十二烷基苯磺酸钠(LAS)的去除效果、溶液中阴离子对LAS降解的影响及机理.结果表明:UV/H2O2工艺可以有效地去除水中的LAS;在H2O2投加量为8 mg/L,14 W低压汞灯照射下,LAS在蒸馏水和自来水中的反应速率常数分别为0.018 0 、0.012 2 min-1;NO-3、Cl-、SO2-4和HCO-3对LAS光降解有抑制作用,当该4种离子摩尔浓度均分别为5、10、15 mmol/L时,对LAS光降解的抑制程度为HCO-3》NO-3》Cl-》SO2-4,且随着离子摩尔浓度的增大,抑制作用增强;LAS在自来水中的反应速率常数低于在蒸馏水中的反应速率常数是由于水中多种离子影响的结果.     

Aerosolization of an anionic surfactant (LAS) and dissolved organic carbon (DOC) under laboratory conditions.

Aerosolization of natural salt and brackish waters under laboratory conditions is responsible for the transfer of synthetic surfactants such as linear alkylbenzene sulphonate (LAS) from water to the atmosphere. Excluded the lagoon sample which stands apart, on the average ca. 45% of the LAS present at concentrations between 0.1 and 4.1 microg l(-1) in the tested coastal and offshore marine and lagoon waters was transferred to the aerosol extract. The distribution of the individual LAS homologs in the aerosol is very similar to that in water, which indicates no preferential removal from the bulk water of any LAS homolog. The fraction of dissolved organic carbon (DOC) undergoing aerosolization under the same conditions for each tested sample was on an average ca. 3.3%, corresponding to ca. 5.6 mg l(-1). On the average, the enrichment factor of the sea samples, resulting from the changing of the LAS/DOC ratio before and after aerosolization, was ca. 20.     

Nonylphenols, nonylphenol-ethoxylates, linear alkylbenzenesulfonates (LAS) and bis (4-chlorophenyl)-sulfone in the German Bight of the North Sea.

Nonylphenols and nonylphenol-ethoxylates were detected in the water and sediment samples from the German Bight of the North Sea. Additionally bis (4-chlorophenyl)-sulfone and linear alkylbenzenesulfonates (LAS) were detected in marine waters. Proof of identification is given by comparison of spectral and chromatographic data from the compounds in sample extracts to those obtained from pure standards. In extracts obtained from water samples taken in 1990 and 1995 the concentrations of nonylphenols and bis-(4-chlorophenyl)-sulfone were compared for each year. The concentrations of nonylphenols in seawater varied from 0.7 to 4.4 ng/l while in the Elbe estuary about 33 ng/l were found. In water samples taken in 1998 nonylphenol-polyethoxylates could not be determined, whereas LAS concentrations of 30 ng/l were confirmed by HPLC-MS/MS. The concentrations of bis (4-chlorophenyl)-sulfone ranged from 0.18 to 2.2 ng/l. In sediment samples LAS concentrations of 39-109 ng/g dry weight were determined.     

Influence of water hardness on the bioavailability and toxicity of linear alkylbenzene sulphonate (LAS)

In the present work, the influence of Ca²⁺ concentration on the toxicity of single cut linear alkylbenzene sulfonate (LAS) homologues was studied. Precipitation boundary diagrams for each homologue were obtained, indicating turbid and clear zones depending on the LAS and Ca²⁺ concentrations. The separation between transparent and turbid zones is given by the so-called precipitation line. LAS toxicity to Daphnia magna was determined at concentrations close to this precipitation line. It was observed that when Ca(LAS)₂ precipitation progresses, LAS bioavailability decreases for test animals, and the toxicity diminishes even at high nominal LAS concentrations. According to the “free ion activity model” (FIAM), the toxicity of a given chemical compound is mainly due to the ionic species (Ca²⁺–LAS⁻) and not due to the precipitated molecule, Ca(LAS)₂. The significance of the present study is in connection with the assessment of LAS sorption/precipitation studies in soils and sediments, where in situ toxicity is strongly influenced by Ca²⁺/Mg²⁺ ions, according to the results presented in this work.     

Cytotoxic effect of linear alkylbenzene sulfonate on human intestinal Caco-2 cells: associated biomarkers for risk assessment

Linear alkylbenzene sulfonate (LAS) is a synthetic anionic surfactant widely present in the environment due to its intensive production and use in the detergency field. Admitting that current procedure of risk assessment has limits in providing realistic risk assessment data and predicting the cumulative effect of the toxicant mixtures, the incorporation of information regarding the mode of action and cell response mechanism seems to be a potential solution to overcome these limits. In this regard, we investigated in this study the LAS cytotoxicity on human intestinal Caco-2 cells, trying to unveil the protein actors implicated in the cell response using proteomics approach in order to give a better understanding of the toxicological effect and allow the identification of appropriate biomarkers reflecting the mode of action associated with LAS. As results, we demonstrated that LAS induces a time- and dose-dependent cytotoxicity in Caco-2 cells accompanied by an induction of oxidative stress followed by an excessive increase of intracellular calcium level. Proteomics approach helped in discovering three informative biomarkers of effect associated with LAS cytotoxic effect, reported for the first time: calreticulin, thioredoxin, and heat shock cognate 71 (HSP7C), confirmed by real-time PCR and western blot analysis. These biomarkers could serve for more reliable future risk assessment studies that consider the toxicants mode of action in order to help in the prediction of potential cumulative effects of environmentally coexisting contaminants.