采用离石黄土原位修复煤矸石渗滤液污染地下水

为以较好的技术手段和较低的经济成本治理煤矸石淋滤液、矿坑废水对地下水的污染,通过土柱淋滤试验、PRB (permeable reactive barrier)模拟试验以及场地修复试验,对煤矸石淋滤液中重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)及As的吸附性进行了研究. 土柱淋滤试验结果表明:离石黄土(粒径0.05~0.10mm)、亚砂土(粒径0.05~0.10mm)和细沙(粒径>0.10~0.25mm)对煤矸石淋滤液中的重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)及As的吸附能力为离石黄土>亚砂土>细沙,其中离石黄土对As的分配系数为2.26L/kg.模拟槽试验表明,在地下水流速为0.20m/d、m(煤矸石):m(离石黄土)分别为5和7的情况下,淋滤液中的As能够全部被黄土墙吸附;m(煤矸石):m(离石黄土)为10时,部分As透过黄土墙向下游迁移. 5个月的场地修复试验表明,利用离石黄土作为PRB的吸附材料能够较好地去除地下水中的重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)和As,厚约0.5m的离石黄土墙对被煤矸石淋滤液污染的地下水中Cr的去除率最高,达到70.97%,对Pb的去除率最低,为43.14%.      

不同施磷量(KH2PO4)作用对Cu、Zn在红壤中的迁移转化

为了比较不同施磷量对土壤中重金属Cu、Zn迁移转化的影响,采用土壤柱进行室内淋溶实验,研究常见的磷肥磷酸二氢钾在少量5 mg·kg-1,适量15 mg·kg-1以及过量25 mg·kg-1条件下对Cu、Zn在红壤中的淋溶效应.结果表明土壤施用磷酸二氢钾降低了土壤渗滤液的pH,不同施磷量对土壤渗滤液pH影响不大,在整个淋滤过程,渗滤液pH呈现上升的趋势.磷酸盐作用下重金属Cu在土壤中的迁移主要集中表层土壤中,而Zn逐渐向深层土壤中迁移.土壤深层渗滤液中Cu、Zn浓度均比较低,对浅层地下水的危害性不大.淋滤结束后,重金属主要以残渣态存在土壤中,重金属Cu残渣态的比例为60%左右,重金属Zn残渣态比例为40%左右.高浓度磷酸二氢钾作用下有利于重金属Zn从残渣态及有机结合态向交换态转化.     

重金属和有机氯农药在沈阳郊区农田土壤中的吸附和迁移

采用静态吸附和土柱淋溶实验研究了重金属和有机氯农药在沈阳郊区农田土壤中的迁移转化规律.吸附实验结果表明,土壤对Pb和Cd阳离子的吸附大于对Cr(VI)和As(V)阴离子的吸附,对Cr(VI)的吸附大于对有机氯农药六六六(BHC,包括α-BHC、β-BHC、γ-BHC、δ-BHC)和滴滴涕(DDT,包括o,p'-DDT、p,p'-DDT)的吸附能力.土柱淋溶实验结果表明,Cr(VI)和As(V)在耕层土壤中的迁移速度远大于Pb、Cd的迁移速度,α-BHC由于淋溶液初始浓度较低,因而迁移速度较慢.淋溶实验后,具有较高生物可利用性和迁移性的可交换态重金属的相对含量增加了1.2%～5.4%,从而增加了Pb、Cd、Cr和As等重金属对生态系统的威胁.结合吸附和迁移实验结果可知,所研究污染物中,Cr(VI)和As(V)对地下水的威胁较大,Pb和Cd对农业生产的威胁较大,而目前有机氯农药已被国家明令禁止使用,土壤中的部分残留有机氯农药由于土壤的吸附作用,使得其对农业生产的威胁逐渐减小,对地下水的威胁性也较小.     

污泥堆肥施用对土壤及地下水影响研究

为探究北京市污泥堆肥产品施用对土壤和地下水的影响,采用原状土柱模拟降雨试验方法,研究了在污泥堆肥产品年施用量为3、6、12kg/m²的条件下,Cu、Cr、Ni、Zn、Pb、Cd、As、Hg 8种重金属元素的迁移和淋溶特征.结果表明,Cd淋溶后残留最少（6.1%~11.9%）,进入淋溶水最多（4.5%~7.3%）;Hg淋溶残留最多（16.0%~22.1%）,进入淋溶水最少（<0.1%）.Hg、Pb、Ni、Cd、Cu在0~20cm土壤层积累最多（52.0%~78.7%）;Cr、Zn、As则在20~40cm层积累最多（42.7%~53.2%）.8种元素在土壤中的含量均符合《土壤环境质量农用地土壤污染风险管控标准（试行）》（GB 15618-2018）限值.淋溶水中测得的6种重金属浓度由大至小依次为Zn > As > Cd > Cu > Pb > Cr,受堆肥施用量及降雨量共同影响.淋溶水中Cu、Cr、Ni、Zn、Pb 5种元素的浓度始终在《地下水质量标准》（GB/T 14848-2017）Ⅰ类水质范围内,Cd、As、Hg在Ⅲ类范围内.     

万庄金矿田土壤重金属的垂直分布及形态研究

利用等离子体发射光谱法、原子荧光光谱法等研究了北京水源涵养区上游万庄金矿田4个土壤剖面样品中的Cu、Zn、Ni、Pb、Cd、Cr、Hg和As共8种重金属元素在剖面上的分布特征,以及Cu、Zn、Pb、Cd、Cr、Ni元素的形态分布特征,并对重金属元素污染现状进行了评价。结果表明部分重金属元素在土壤表层有明显的富集现象,Cd、As、Pb、Zn、Cu、Hg 6种重金属基本都随深度的增加,含量大体呈现逐渐减小的趋势,Cr、Ni有较相似的迁移和富集规律;相关性分析发现Zn、Ni、Cd、Cr、和As的相关性显著可能具有同源性。形态分析可知重金属Zn、Cd的迁移能力相对较高。地累积指数评价结果可见,土壤中Pb、As、Cd环境生态污染较严重。     

天津污灌区菜地土壤团聚体中有机碳和重金属含量特征

以天津某污灌菜地土壤为研究对象,分析干筛法所得不同粒径土壤团聚体颗粒中有机碳及重金属含量特征.结果表明,土壤团聚体粗大颗粒(2 mm)含量最大,约为70%.0.25～0.5 mm粒级团聚体中Cu、Zn、Cd和Pb含量最高,Cr含量在5～8 mm粒径团聚体中最高,As在不同颗粒中含量差异较小,不同重金属元素含量随土层深度增加而减小.污灌土壤中重金属富集因子表现为Cd Pb Zn Cu Cr As,在0.25～0.5 mm粒级团聚体颗粒中Cu、Zn、Cd和Pb分布因子最高,而5～8 mm粒径团聚体中重金属负载因子最大.土壤有机碳含量整体上随团聚体粒径增加表现为先增加后降低,不同粒径团聚体中Cu、Cd、Pb和As含量与有机碳含量呈显著正相关(p0.05).     

典型铅锌矿流域土壤重金属累积与分布的影响因素分析

以桂北地区阳朔铅锌矿流域为研究对象,对其流域内表层土壤中9种重金属元素(Zn、 Pb、 Cd、 Fe、 Mn、 Cu、 Cr、 Sb和As)的全量和形态,以及5种土壤性质指标(pH、电导率、阳离子交换量、有机质和粒径)进行分析测定.综合运用相关性分析、冗余分析(RDA)和地理探测器揭示土壤重金属累积与分布的主控因素.在土壤样本分析数据中,As、 Cd、 Fe、 Cu、 Mn、 Pb和Zn含量平均值均超过背景值,其中Cd、 Mn、 Pb和Zn分别是背景值的4.01、 3.15、 5.53和9.72倍,表明其在表层土壤中明显富集;在分布上具有较为明显的空间差异,在冲洪积扇堆积区(1～6号)高于其他区域(7～9号). Pb和Mn可利用态占比(K)分别为48.8%和57.2%,生物可利用性较大,潜在迁移能力一般(PMI分别为0.015～0.068和0.036～0.082);Zn和Cu可利用态占比(K)分别为30.9%和16.8%,且中等利用态占比(Z)分别为10.9%和13.6%,有一定生物可利用性,但Zn迁移能力较强(PMI为0.160～0.203),Cu潜在迁移能力一般(PMI为0.017...     

基于高密度采样的土壤重金属分布特征及迁移速率

重金属在土壤剖面中的垂直分布特征是土壤自身理化性质和外界条件影响下重金属迁移和积累的综合反映,也是了解土壤重金属污染程度和修复治理的基础.传统的用于农业土壤研究的层次采样技术和方法,只能粗略了解重金属在土壤层次中的分布状况,不足以确定污染物的垂直迁移距离和速度.本研究通过对钢铁厂周边3种不同利用类型土壤进行垂直方向的高密度采样分析,即在0～40cm深度内以2cm间隔,在40～80cm以5cm间隔,80cm以下以10cm间隔采样,对重金属元素Cu、Zn、Pb、Cr、Cd的剖面垂直分布进行了研究.结果表明,在几乎未受人为干扰的林地土壤中,可见重金属在土壤表层明显富集,证实其来源是大气沉降,其中Zn、Pb向下迁移的距离很小,Cu、Cd迁移稍快,Cr向下淋溶迁移的深度没有明显的界限;在受人为影响的旱地和水稻田中,重金属在耕层土壤中被人为扰动混合,但在耕层界面以下仍然有明显的向下迁移.研究表明,垂直方向高密度采样可以比较精确地理解重金属在土壤中的分布模式,通过重金属元素含量与稳定元素Ti含量的比值及其变化,还可以估计在特定时间内污染物的迁移距离和迁移速度,各种重金属具有不同的迁移能力,其相对顺序为Cd>Cu>Zn>Pb.     

模拟酸雨下铅锌冶炼废渣重金属的静态释放特征

以株洲某铅锌冶炼废水中和渣为研究对象,开展不同初始pH值（3.0,4.5,5.6和7.0）模拟酸雨静态浸出实验,研究22d浸泡过程中废渣Cd、Cu、Pb和Zn等重金属的动态释放规律及其化学形态变化和矿物相变特征.结果表明,废渣具有较强的酸缓冲潜力,浸出液pH值稳定在6.20~6.66.Cu和Pb在浸泡初期释放较快,Cd和Zn释放相对较慢.浸出液Cd浓度随浸出时间增加而上升,Zn浓度呈波动变化,Cu和Pb浓度变幅较小.提高雨水酸度促进废渣中重金属的释放,浸出液Cd、Cu、Pb和Zn浓度范围分别为1.38~8.70,0~0.02,1.21~2.26和27.2~135mg/L,其中Cd、Pb和Zn浓度分别超过我国《铅、锌工业污染物排放标准》（GB 25466-2010）限值的26.6~173倍、1.42~3.52倍和17.1~89.0倍..重金属BCR顺序提取表明,浸出液中较高Cd和Zn浓度与其赋存高活性态比例一致,且酸雨促使残渣态Cd和Pb向活性态转化.XRD分析显示,pH=3.0酸雨处理22d后原废渣中Cd和Zn的赋存矿物相消失,PbSO₄谱峰增强,表明废渣重金属的释放受其赋存矿物相及次生矿物形成的影响.重金属释放率呈现出Cd （2.50%~15.8%）> Zn （0.41%~2.13%）> Pb （0.06%~0.10%）> Cu （0.0003%~0.11%）的趋势.自然堆存酸雨作用下废渣中Cd、Pb和Zn具有较大环境风险,需加强降雨淋滤污染防治管控.     

承德市滦河流域土壤重金属地球化学基线厘定及其累积特征

选择承德市滦河流域为研究区,系统采集了351个表层土壤样品(0～20cm),测定了Cu、Ni、Cd、Cr、Pb、Zn、Hg、V、Ti、Mn、As和Co共12种重金属的含量,运用基于参比元素的标准化方法和累积频率曲线法确定了12种重金属元素的地球化学基线值,结合主成分分析法与地统计方法统计结果,分析了重金属的空间结构和分布特征,利用地累积指数法对不同土壤类型和土地利用方式表层土壤重金属累积程度进行了分类评价.结果表明,滦河流域表层土壤V、Ti、Cd、Pb、Mn和Co元素地球化学基线值高于河北省背景值,As、Zn、Cr、Cu、Ni和Hg元素地球化学基线值低于河北省背景值.表层土壤重金属总体累积程度由强至弱为:Cd Pb Cu Ti Mn Zn Cr Ni Co V Hg As,80%以上的土壤样品中Pb、Ti、V、As和Co元素属无累积-中度累积水平,70%以上土壤样品中Hg、Mn、Ni、Cu、As、Cd和Cr元素属无累积-中度累积水平.土壤重金属总体累积程度在棕壤、褐土和潮土中依次增大;在工矿用地、灌木林地中较高,林地、草地中相对最低.农用地表层土壤中Pb、Cd元素累积程度相对较高,分别有27. 69%和25. 38%的样品属中等以上累积水平.滦河流域表层土壤Ti、V、Co、Ni和Cr元素同源性较高,与原生高地质背景相关; Cd、Pb、Zn,Mn、Cu和As元素污染累积受成土母岩和人为因素共同作用影响,Hg元素累积则主要来源于人为活动.     

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.