A.ferrooxidans对高硫煤矸石去除酸性水体中Cr(VI)的强化作用

本研究考察了Acidithiobacillus ferrooxidans（A.ferrooxidans）联合高硫煤矸石（富含FeS₂）对模拟煤矿酸性水体中Cr（VI）的去除效果.结果表明,处理Cr（VI）初始浓度为50mg/L的模拟煤矿酸性废水（pH=2.5）时,投配率为6.67~33.33g/L高硫煤矸石可使Cr（VI）去除达到良好效果.50mg/LCr（VI）在24h内即可完全被高硫煤矸石中的FeS₂还原成Cr（III）,且在反应终点时（120h）,6.67,13.33,33.33g/L高硫煤矸石对还原产物Cr（III）的吸附去除率分别为7.1%、20.2%、29.1%.然而,在高硫煤矸石的还原和吸附作用下,大部分的Cr仍以Cr（III）形式残留在酸性水体中,且高硫煤矸石的大量投加也给水体带来了Fe²⁺、Fe³⁺、SO₄^2-等二次污染物.在高硫煤矸石-Cr（VI）体系中引入A.ferrooxidans和9K培养基后,A.ferrooxidans介导的Fe²⁺生物氧化及产物Fe³⁺水解矿化过程可促进部分Fe²⁺、Fe³⁺、SO₄^2-等向次生铁矿物（包括施氏矿物和黄钾铁矾）转变,从而使模拟酸性水体中残留的Cr（III）通过次生铁矿物的吸附或共沉淀作用被清除.在A.ferrooxidans强化作用下,模拟煤矿酸性废水中Cr（VI）在96h即可达到99.4%的去除率.     

半胱氨酸亚铁溶液吸收一氧化氮的研究

在鼓泡吸收瓶中,对半胱氨酸亚铁[Fe²⁺(CyS^-)₂]溶液络合吸收一氧化氮(NO)进行了研究.考察了不同[Fe²⁺]和[CySH]的配比、pH值、模拟烟气中的氧含量、SO₃^2-浓度等对NO吸收的影响.结果表明,Fe²⁺:CySH=1:4配比的溶液能达到较大的吸收容量.Fe²⁺(CyS-)2吸收剂在pH=8条件下的吸收效果明显优于偏酸条件下的效果.当氧气含量达到5.5%时,NO的吸收容量约下降48%.当SO₃²/Fe²⁺(CyS-)2为1时吸收剂的吸收容量约为不含SO₃^2-的溶液的1.5倍.模拟烟气中氧气含量越高,SO₃^2-对NO吸收容量的影响越明显.相同浓度的亚铁络合吸收剂,Fe²⁺(CyS-)2的NO吸收容量略高于常用吸收剂Fe²⁺(EDTA^2-),并且Fe²⁺(CyS-)2的抗氧化性能优于Fe²⁺(EDTA^2-).     

乙基黄药对施氏矿物吸附Cr（Ⅵ）的影响研究

选矿药剂在矿产资源开发中被大量使用,环境中残留的选矿药剂及其衍生物对重金属的迁移、转化等环境行为产生重要影响.施氏矿物是广泛存在于酸性矿山废水中的一种典型的羟基硫酸盐铁矿物,对重金属具有明显的吸附作用.然而,浮选药剂对施氏矿物富集重金属的影响有待深入研究.本研究采用快速化学法合成施氏矿物,通过批量吸附实验法系统探究典型浮选药剂乙基黄药存在条件下,反应体系pH、接触时间、浮选药剂浓度、Cr（VI）初始浓度等因素对施氏矿物吸附Cr（VI）的影响规律.结果表明：在酸性条件下,乙基黄原酸钠抑制施氏矿物对Cr（Ⅵ）的吸附作用;在碱性条件下,乙基黄原酸钠对施氏矿物吸附Cr（Ⅵ）具有明显的促进作用.在初始pH条件为8.5时,施氏矿物对Cr（VI）的最大去除容量达到56.96 mg?g^-1,与最佳条件下施氏矿物对Cr（VI）的吸附容量 （40.4 mg?g^-1） 相比,吸附容量提升了41%.乙基黄原酸钠存在条件下施氏矿物对Cr（Ⅵ）的吸附符合准二级动力学,表明该吸附过程以化学吸附机制为主.在Cr（VI）的吸附过程中,黄原酸基将Cr（Ⅵ）还原为Cr（Ⅲ）,从而增强了了施氏矿物在碱性条件下对Cr（VI）的去除能力.研究结果表明乙基黄药的存在能够显著影响施氏矿物对Cr（VI）的吸附过程及吸附机制.     

集约化猪场废水SBR法脱氮除磷的研究

探讨了集约化猪场废水厌氧消化后,SBR法生物脱氮除磷效果及限制因子.SBR法操作参数为8h/周期,30℃恒温,SRT 10d, HRT 1d.废水初始NH⁺₄-N浓度1682mg/L,PO₄^3-浓度185mg/L,氨氮和PO₄^3-去除率分别为94.3%和96.5%.温度系列8,10,12,14,16,18,20,22,25,30℃批试验证实18℃以上能获得较好的脱氮除磷效果,温度不再是限制因子.由活性污泥实验消耗曲线斜率取得氨氮利用率(AUR)、硝态氮利用率(NUR)、氧气利用率(OUR)3个参数,可以有效评价SBR污泥生物活性.     

潜流水平湿地对农业灌溉径流氮磷的去除

构建了潜流水平芦苇湿地,对农业灌溉径流(TN约为7mg/L,TP约为0.5mg/L)中氮磷进行了为期1年的去除研究.在水力停留时间(HRT)为2,4,6d时,TP和TN的去除率均大于87%和68%.湿地对TN、NH₄⁺-N和TP的去除受HRT的影响较大(P<0.05),对PO₄^3--P的去除受HRT的影响较小.在不同HRT情况下,NH₄⁺-N、NO₂^--N、NO3--N和PO₄^3--P的去除率均高于93%,出水浓度一般均小于0.04mg/L.且出水中的TP和TN主要为有机态,存在一个TP和TN背景浓度.TN去除率与负荷之间具有很好的相关性(R2=0.9968),但是TP去除率与负荷之间相关性较差(R²=0.5987).以HRT为2d计算,1m²的芦苇床处理该农业灌溉径流的能力为0.1m³/d,出水TN和TP浓度可控制在0.50mg/L和0.154mg/L以下.     

紫外活化甲酸产二氧化碳阴离子自由基还原Cr (VI)的研究

研究高效还原技术是去除废水中Cr（VI）的有效手段,本研究提出了一种新颖有前景的基于紫外（UV）活化甲酸（HCOOH）产还原性二氧化碳阴离子自由基（CO₂^•;-）去除Cr（VI）的方法.通过对比UV、HCOOH、UV/HCOOH三种体系对Cr（VI）还原效率和电子自旋共振（EPR）对体系中自由基的检测研究了其活化原理和还原机制.结果表明UV能显著活化HCOOH产生CO₂^•-（α_H=19.08G,α_N=15.86G,g=2.0036）.此外,试验考察了主要影响因素对Cr（VI）去除效果的影响,包括初始Cr（VI）浓度、甲酸投加量、初始pH值、反应温度、有机污染物以及水中常见阴离子.结果显示当甲酸浓度为40mmol/L,Cr（VI）初始浓度为10mg/L,反应时间在60min内,UV/HCOOH体系对Cr（VI）的去除率能达到100%.在酸性条件下（pH≤3.5）能显著促进Cr（VI）的还原,且Cr（VI）去除效率随着初始HCOOH浓度和反应温度升高而增加.进一步研究表明,该体系下NO₃^-对Cr（VI）的还原有着显著的促进作用,而Cl^-、HCO₃^-和对硝基苯酚（pNP）则有抑制作用.不同温度下Cr（VI）去除率与时间关系的拟合结果表明,当反应时间t³;40min,UV/HCOOH体系去除Cr（VI）过程遵循准一级反应动力学,根据不同温度下对应的反应速率常数k,结合阿伦尼乌斯方程,计算求得准一级反应的活化能为15.9kJ/mol.     

施氏矿物的化学合成及其对含Cr(Ⅵ)地下水吸附修复

采用简单快速的化学合成方法在实验室人工合成施氏矿物,研究了合成的施氏矿物对地下水中Cr(Ⅵ)的吸附动力学、吸附能力以及环境条件对施氏矿物吸附Cr(Ⅵ)的影响.结果表明,合成的施氏矿物对水溶液中Cr(Ⅵ)具有较强的吸附作用,24 h后反应达到平衡,吸附动力学过程符合Lagergren二级速率方程;而吸附等温方程符合Langmiur方程,pH值在4.5~6之间时Cr(Ⅵ)的去除效果最佳,最大吸附能力达到40.4 mg·g-1.溶液中Cr(Ⅵ)的去除率随施氏矿物投加量的增大而升高.Cl-对施氏矿物吸附地下水中Cr(Ⅵ)无明显影响,而HCO_3~-、SO_4~(2-)会对施氏矿物吸附Cr(Ⅵ)产生较为显著的抑制作用;有机物和Ca~(2+)、Mg~(2+)等无机阳离子对施氏矿物吸附Cr(Ⅵ)的影响受pH值的影响:pH=6时,有机物和无机阳离子基本对施氏矿物吸附Cr(Ⅵ)无影响;pH=8时有机物以及无机阳离子均会对施氏矿物吸附Cr(Ⅵ)产生明显的抑制作用.     

南方典型地区油-稻轮作下大气硫沉降动态

1998年11月～1999年10月间,利用中国科学院红壤站(江西鹰潭)农田小气候分站进行了全年逐时气象资料收集,通过阻力模式求算SO₂和SO₄^2-的干沉降速度,结合大气中SO₂、硫酸盐(SO₄^2-)粒子和雨水的收集和测定,定量研究了大气沉降向农田生态系统的硫输入.结果表明,12个月大气硫沉降总量为94.9 kg S/hm2,其中大气中硫干沉降量(SO₂+SO₄^2-粒子干沉降)占81.9%.大气中SO₂干沉降是大气干沉降的主要贡献者,占大气硫干沉降总量93%.并对不同季节及不同的作物生长期间硫的沉降动态进行了分析、比较.     

大气沉降向林地(小叶栎)输入硫素通量的观测

利用中国科学院红壤生态试验站森林小气候观测站(江西鹰潭)逐时气象梯度参数连续自动观测数据,采用阻力模式计算SO₂、硫酸盐(SO₄^2-)粒子的干沉降速率(Vd),结合大气SO₂、SO₄^2-粒子浓度现场测定,研究了该地2年大气硫沉降量.结果表明,2000年大气SO₂和SO₄^2-粒子时年Vd值分别为0.748cm/s、0.665cm/s;2002年分别为0.180cm/s、0.221cm/s.2000和2002年大气干沉降硫(SO₂+SO₄^2-粒子)通量分别为104.6kgS/(hm2a)和140.6kgS/(hm2a),SO2干沉降是大气干沉降主要贡献者,占98.38%和97.2%;大气沉降硫总量分别为150kgS/(hm2a)和185kgS/(hm2a);可见大气干沉降是大气硫沉降主要贡献者,分别占70%和76.2%.     

2001～2003年间北京大气降水的化学特征

为了了解北京大气降水的化学组成与时间变化特征,连续进行了2年的降雨采样与分析.在65个降雨样品中,12%的降水呈酸性;全年降水的酸度主要取决于夏季的降水.SO₄^2-、NH₄⁺与Ca²⁺是含量最丰富的组分,其平均浓度均接近或超过200礶q/L.比较分析表明,在近几年,SO₄^2-对降水酸度的贡献显著降低,降水的硫污染特征减弱,而No₃^-的贡献显著增加.人为污染元素和地壳元素的浓度均在冬春季较高,在夏季最低.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.