Sb(V)在三种矿物表面的吸附行为

用研究了蒙脱土、高岭土和针铁矿在不同的pH与离子强度的介质条件下对Sb(V)的吸附及解吸行为。3种矿物对Sb(V)的吸附能力差别较大,蒙脱土的吸附量远大于针铁矿和高岭土,针铁矿与高岭土的吸附能力相近。pH对Sb(V)在3种矿物表面的吸附行为影响显著。随pH的升高,Sb(V)的吸附均减弱。吸附在高岭土表面的Sb(V)易解吸,而针铁矿和蒙脱土表面的Sb(V)不易解吸。随离子强度升高,高岭土对Sb(V)的吸附减弱;离子强度对Sb(V)在针铁矿和蒙脱土表面吸附的影响较小。     

五种填料对磷酸盐的等温吸附-解吸特性

研究了5种土地处理系统中的常用填料(天然沸石、陶粒、北京土壤、蛭石和砾石)对磷酸盐的吸附和解吸特征,结果表明蛭石与土壤对磷酸盐的吸附效果明显(吸附量分别为1.38 mg/g和1.24 mg/g),陶粒与沸石的磷酸盐吸附效果次之(分别为1.12 mg/g和1.18 mg/g),砾石的磷酸盐吸附效果最差(0.9 mg/g).5种填料在振荡12 h均达到吸附平衡,吸附量随初始磷浓度的增加而增加.砾石的解吸率最高,北京土壤与沸石的次之,蛭石与陶粒的最低.在所研究的五种填料中,从磷吸附量和解吸率来看,蛭石是较好的磷吸附填料.     

锑/磷在膨润土和高岭土的竞争吸附

采用批处理法研究了锑/磷(Sb/P)在膨润土和高岭土上的竞争吸附等温线和动力学,并考察了pH的影响。结果表明:Sb和P吸附符合Langmuir或Freundlich方程(R~2=0.945 0~0.998 3,P0.000 1),存在极强的竞争吸附:P共存时Sb吸附容量(Q_(max))显著降低,分别从0.86和10.21 mmol/kg(先Sb后P)降低到0.64和2.61 mmol/kg(先P后Sb);Sb共存时P吸附亲合性(K)明显降低,分别从1.47和7.47 L/mmol(先P后Sb)降低到0.68和2.34 L/mmol(先Sb后P)。Sb和P的吸附总体随pH升高而降低,但相比高岭土,膨润土上的吸附受pH影响更大,意味着高岭土有更多配位吸附、膨润土有更多电性吸附。准二级动力学方程很好地拟合它们的竞争吸附(R~20.994,P0.000 1),并且在Sb/P共存下,膨润土对P吸附弱而慢(q_e=0.36 mmol/kg,,k_2=0.064 6 kg/(mmol·min))、对Sb吸附虽弱但快(q_e=0.19 mmol/kg,k_2=0.076 9 kg/(mmol·min));高岭土对P吸附强更快(q_e=0.66 mmol/kg,k_2=0.591 kg/(mmol·min))、对Sb吸附虽强但慢[q_e=0.39 mmol/kg,k_2=0.052 4 kg/(mmol·min)]。因此,Sb对P吸附的抑制在膨润土上更明显(主要是静电吸附竞争),P对Sb吸附的抑制则在高岭土上更突出(主要是配位吸附竞争)。     

黄褐土与水稻田沙土对Mn(Ⅱ)和Ni(Ⅱ)的吸附

为探明陕南矿区典型土壤(黄褐土和水稻田沙土)对Mn(Ⅱ)和Ni(Ⅱ)的吸附特性,采用振荡平衡法研究黄褐土与水稻田沙土对Mn(Ⅱ)和Ni(Ⅱ)的等温吸附过程,并用数学模型模拟其吸附动力学过程,结合红外光谱(FTIR)分析,探讨2种土壤吸附Mn(Ⅱ)和Ni(Ⅱ)的机理及其影响因素。结果表明:Mn(Ⅱ)和Ni(Ⅱ)在2种土壤中的吸附均在120min达到平衡,黄褐土对Mn(Ⅱ)和Ni(Ⅱ)的吸附能力远远高于水稻田沙土,黄褐土对Mn(Ⅱ)和Ni(Ⅱ)的最大吸附量分别为2.12,1.19mg/g,沙土对Mn(Ⅱ)和Ni(Ⅱ)的最大吸附量为1.32,0.78mg/g;准一级动力学模型、双常数模型和内扩散模型均适合于表征Mn(Ⅱ)和Ni(Ⅱ)的吸附动力学特征,黄褐土吸附动力学特性的模型吻合度高于水稻田沙土;Langmuir吸附等温方程可较好地模拟Ni(Ⅱ)在2种土壤中的等温吸附过程,Freundlich吸附等温方程可很好模拟Mn(Ⅱ)黄褐土吸附等温过程;在研究pH范围内,Mn(Ⅱ)的吸附率随pH的增加变化不大,Ni(Ⅱ)的吸附率均随pH的增加而增加,土壤pH对重金属离子解吸影响较大,当pH小于3时有利于重金属离子解吸;通过土壤基本理化性质与吸附参数相关分析,结合吸附前后土壤的红外光谱分析,说明土壤有机质含量对重金属Mn(Ⅱ)和Ni(Ⅱ)的吸附起重要作用,有机质所含官能团对重金属起到一定的化学吸附作用。     

可变电荷土壤对As(Ⅲ)和As(Ⅴ)的吸附及二者的竞争作用

三种可变电荷土壤对砷的吸附实验结果表明,在pH3~7范围内,As(Ⅲ)的吸附量随pH的升高而增加,三种土壤对As(Ⅲ)吸附能力的大小顺序为砖红壤>黄壤>红壤。红壤和砖红壤对As(Ⅴ)的吸附量随pH的升高而降低,黄壤中呈相反的变化趋势,三种土壤对As(Ⅴ)吸附能力的大小顺序是黄壤>砖红壤>红壤。三种可变电荷土壤对As(Ⅴ)的吸附能力较对As(Ⅲ)大得多,砷的吸附量既与土壤游离氧化铁的含量有关,又与氧化铁的结晶形态密切联系,由于黄壤中水化氧化铁在游离铁中所占比例较高,其对As(Ⅴ)吸附能力较砖红壤和红壤大。As(Ⅲ)与As(Ⅴ)共存体系的研究结果表明,两种形态的砷可以竞争可变电荷土壤表面的吸附位,但在酸性条件下As(Ⅴ)较As(Ⅲ)有更强的竞争能力,因为As(Ⅴ)使土壤对As(Ⅲ)的吸附量显著减小,而As(Ⅲ)对红壤和砖红壤吸附As(Ⅴ)有一定的影响,对黄壤中As(Ⅴ)的吸附几乎没有影响。     

α-氧化铝–细菌二元复合胶体对锑的吸附研究

锑(Sb)在土壤胶体微界面的吸附解吸深刻影响其迁移、转化和归趋。土壤矿物、有机物、微生物等胶体组分多结合在一起,形成复杂的矿物–有机复合体。目前,锑在单一土壤组分上的吸附研究颇多,但较少有学者关注锑在土壤矿物–有机复合胶体界面的吸附过程和机制。通过宏观吸附以及光谱学技术探究锑在典型铝氧化物–细菌复合胶体上的吸附行为,结果表明:α-Al_2O_3纳米级颗粒覆盖在蜡状芽孢杆菌表面,形成一层不完整的"矿物膜"。朗格缪尔(Langmuir)模型可以很好地拟合Sb(Ⅴ,Ⅲ)的等温吸附数据(R~20.98);α-Al_2O_3对Sb的吸附量远大于细菌;Sb在Al_2O_3–细菌复合胶体上的吸附不符合"组分相加"原则,存在显著的促进效应。扫描电镜-能谱分析显示Sb主要结合在复合胶体的矿物组分上。X-射线光电子能谱结果表明铝羟基、羧基和氨基参与了Sb的吸附,且细菌会抑制Sb(Ⅲ)在α-Al_2O_3表面的氧化。本研究证实,细菌不仅影响锑在矿物界面的吸附量,还影响其氧化还原反应,因此,在预测锑在土壤中的形态转化、迁移和归趋时必须考虑矿物–微生物相互作用。     

中国南方两类典型土壤对五价锑的吸附行为研究

研究我国南方两类典型土壤(红壤和棕色石灰土)对五价锑[Sb(V)]的等温吸附、动力学吸附-解吸过程,比较常用动力学方程对吸附动态曲线的拟合效果,采用分级提取方法分析锑在土壤中的结合形态。试验结果表明,酸性红壤对Sb(V)的吸附量(13.8μmol g-1)和吸附速度(0.58μmol g-1h-1)均大于棕色石灰土(9.19μmol g-1;0.38μmol g-1h-1),Sb(V)在红壤表面吸附是一个快速不可逆过程。锑主要以结合较强的Fe、Al氧化物结合态和残渣态存留在两种土壤中,专性和非专性吸附形态含量很低,也说明锑在土壤中以不可逆吸持为主。比较4种动力学吸附方程对实验结果的拟合程度发现,对于红壤而言,浓度较高的情况下Elovich方程(R2=0.96)的拟合性较好,浓度较低的情况下拟二阶动力学方程(R2=0.97、1.00)的拟合性较好;而对于棕色石灰土,在3种浓度下,双常数方程(R2=0.96、0.94、0.93)的拟合性均较好。     

水钠锰矿对Cr(Ⅲ)离子的吸附解吸及氧化行为

采取等温吸附热力学方法,探讨了锰氧化合物(水钠锰矿)对Cr(Ⅲ)离子的吸附解吸和氧化特征及温度、pH等因素对其影响。研究结果表明,随着Cr(Ⅲ)初始加入量的增加,总铬吸附量逐渐增大,用Langmuir方程可以很好地描述吸附等温线数据;达到反应平衡时,水钠锰矿对Cr(Ⅲ)离子的氧化量与加入初始Cr(Ⅲ)的浓度呈极显著线性正相关,而水钠锰矿对Cr(Ⅲ)的氧化率,随初始Cr(Ⅲ)浓度增加而减小;温度是影响水钠锰矿对Cr(Ⅲ)的吸附和氧化的重要因素,35℃时的吸附量显著低于25℃时的吸附量,而35℃时的氧化量、氧化率明显高于25℃时的氧化量、氧化率,表明升温对吸附反应不利,而对氧化反应有利;溶液酸度对于Cr(Ⅲ)的吸附和氧化有着不同的影响,随着pH的升高,Cr(Ⅲ)离子氧化量、氧化率增大,然而,水钠锰矿对总Cr的吸附量则随着pH的升高而减小,表明pH的升高有利于氧化反应,而对吸附反应不利。     

三种铁氧化物对As(Ⅲ)和As(Ⅴ)的吸附研究

采用批量吸附试验,研究实验室制备的水铁矿、磁铁矿和纤铁矿对As(Ⅲ)和As(Ⅴ)的吸附性能。结果表明,在p H中性条件下,结晶差的水铁矿吸附砷的能力明显优于结晶较好的磁铁矿和纤铁矿,准二级动力学方程拟合效果较好,说明存在多种吸附过程,并可能涉及专性吸附作用;在酸性条件下,三种铁氧化物对As(Ⅲ)和As(Ⅴ)的吸附能力大小顺序均为水铁矿磁铁矿纤铁矿,铁氧化物吸附As(Ⅴ)的能力优于As(Ⅲ),Langmiur方程和Freundlich方程拟合效果均较好,说明铁氧化物对砷的吸附为均匀介质表面的单层吸附或非均匀介质表面的多层吸附;在弱酸至弱碱范围内,三种铁氧化物对As(Ⅲ)的吸附效果均较好且吸附量变化不大,强酸和强碱条件都会引起铁氧化物吸附As(Ⅲ)量的降低,三种铁氧化物对As(Ⅴ)的吸附均随着p H升高而逐渐减少;由于竞争吸附作用,磷酸盐浓度的增加使三种铁氧化物对As(Ⅲ)和As(Ⅴ)的吸附显著减少;随着腐殖酸浓度的增加,三种铁氧化物对As(Ⅲ)的吸附能力逐渐减小,低浓度的腐殖酸微弱地促进铁氧化物对As(Ⅴ)的吸附,高浓度的腐殖酸抑制As(Ⅴ)的吸附。     

老冲积黄壤微团聚体对As(Ⅴ)与P竞争吸附—解吸特性

土壤微团聚体是土壤的最基本结构单元,不同粒径微团聚体的理化性质的差异不同使得重金属离子在各粒径微团聚体中的吸附—解吸能力大小不同。以名山河流域老冲积黄壤为研究对象,将其划分为4个粒径(2~0.25mm,0.25~0.053mm,0.053~0.002mm,0.002mm)。采用批培养法研究原土及不同粒径微团聚体对As(Ⅴ)与P的竞争吸附—解吸特性。结果表明:原土及不同粒径微团聚体对As(Ⅴ)、P的吸附—解吸特性相似,等温吸附均符合Langmuir和Freundlich方程,但Langmuir方程拟合效果最佳;动力学吸附均符合伪一级方程和伪二级方程,但伪二级方程拟合效果更好。原土及各粒径微团聚体对As(Ⅴ)、P的吸附均以专性吸附为主,非专性吸附为辅。原土及不同粒径微团聚体对As(Ⅴ)、P的最大吸附量不仅与粒径大小有关,与土壤有机质、CEC、游离氧化铁含量呈正相关。由于0.002mm粒径的土壤比表面积大,有机质、CEC、游离氧化铁含量高,故其对As(Ⅴ)、P有最大吸附能力和最高初始吸附速率。As(Ⅴ)、P在各粒径微团聚体上解吸量与其吸附量呈指数关系。当As(Ⅴ)与P共存时,明显互相抑制对方的吸附,促进对方的解吸。As(Ⅴ)与P在0.002mm粒径土壤中存在的竞争吸附—解吸能力最小。     

A novel allele of the Arabidopsis phytochelatin synthase 1 gene conferring high sensitivity to arsenic and antimony

To identify genes involved in arsenite [As(III)] tolerance, we screened for As(III)-sensitive mutants using ethyl methanesulfonate (EMS)-mutagenized seeds of Arabidopsis thaliana. One mutant with high sensitivity to As(III) was isolated from the screening. It had a mutation in Glu⁵² of phytochelatin synthase 1 (AtPCS1), and introduction of the wild-type AtPCS1 gene rescued the phenotype, confirming that the mutant represented a new allele of atpcs1 (termed as cad1-7). The expression of AtPCS1 from cad1-7 and cad1-3, a second allele of atpcs1, complemented As-sensitive yeast, but not plants. Our study suggests that AtPCS1 activity is differentially regulated between plants and yeast.     

湖南冷水江锑矿区苎麻对重金属的吸收和富集特性

通过野外调查采样,分析了湖南冷水江锑矿区土壤的重金属含量,以及矿区9个采样点的苎麻对Sb、Cd、As和Pb4种重金属的吸收与富集能力及其富集特征。结果表明,矿区土壤受Sb污染严重,9个采样点Sb含量超过全国土壤背景值40～11503倍;伴生有Cd、As、Pb污染,Cd平均含量（13.08mg·kg-1）和As平均含量（82.64mg·kg-1）明显高于土壤环境质量标准的三级警戒值,Pb平均含量（71.27mg·kg-1）明显高于全国土壤背景值。苎麻叶和花混合样中的Sb最高达到1103mg·kg-1;苎麻体内的Cd含量均高于一般植物2～10倍,Cd富集系数最高为2.1,转运系数最高为3;As富集系数最高为1.04,转运系数最高为12.42;苎麻地上部对重金属迁移能力较强,当季对Sb、Cd、As迁移量分别达796.55、11.20和31.34mg·m-2。本研究说明苎麻对复合重金属具有一定的耐性,为复合污染植物修复提供了一种新的种质资源。     

锑胁迫对玉米生物量、光合特性及锑积累的影响

为了探讨锑污染对经济作物玉米的生长及光合生理的影响,以高产多抗玉米品种滑玉14为材料,通过盆栽试验的方法研究了不同浓度[0(CK)、50、250、500和1 000 mg·kg~(-1)]重金属锑(Sb)胁迫对玉米生物量、气体交换参数、叶绿素荧光参数以及锑积累特征的影响。结果表明,随着生长介质中Sb浓度的增加,玉米生物量、叶绿素含量、气体交换参数(净光合速率、气孔导度、蒸腾速率)和PSⅡ最大光能交换效率(Fv/Fm)均呈下降趋势,瞬时水分利用效率(i WUE)和丙二醛(MDA)含量均呈上升趋势。高浓度Sb(1 000 mg·kg~(-1))胁迫下,玉米的生物量,叶绿素含量、净光合速率和Fv/Fm显著减少(P0.05),分别比CK下降了47.90%、34.22%、52.70%和7.84%;iWUE和MDA显著升高(P0.05),分别比CK升高66.71%和34.02%。随着生长介质中Sb浓度的增加,玉米地下及地上部分锑含量均呈现增加的趋势,各处理之间的差异均达到显著水平(P0.05),转运系数也呈现逐渐增加的趋势,然而其值(在0.52~0.82之间)均小于1,表明高产多抗玉米品种滑玉14向地上部位转运锑相对较少,这可能有利于保护该玉米品种叶片的光合机构,增强植株对锑的耐受能力。本研究结果为经济作物玉米应用于重金属污染土壤修复提供了一定的参考依据。     

Sorption behavior of selenium and antimony in soils as a function of phosphate ion concentration

Abstract

Both selenium (Se) and antimony (Sb) are major soil and water pollutants. Their sorption behavior in a soil–plant system was studied. Soil–soil solution distribution coefficients (K _ds) for Se and Sb were measured, using a radiotracer, as an indicator of their sorption levels. Both Se and Sb behave as oxoanions (SeO^2? ₄, H₂PO^? ₄ and SO^2? ₄) in soil; thus, the effects of concentrations of two major oxoanions (SeO^2? ₄ and SeO^2? ₃) on Se and Sb sorption were also examined. The K _d values for Se for Japanese soils significantly correlated with the K _d values for Sb (n = 141). The K _ds of both Se and Sb similarly decreased with increasing SbO^? ₃ concentration. These results indicated that the sorption of Se and Sb was similarly controlled by a ligand-exchange mechanism such as phosphate sorption in soil. However, an increase in the concentration of SeO^2? ₃ did not decrease the K _ds of Se and Sb. Furthermore, the ligand-exchangeable fractions of stable Se and Sb in major Japanese soils were determined by extraction with 0.1 mol L^?1 Na₂HPO₄ solution. For both Se and Sb, the phosphate-extractable fractions were 10-fold higher for Se and fivefold higher for Sb than their water-soluble fractions. Although the total Se and Sb amounts in soils were the same, their ligand-exchangeable fractions were different. Approximately 0.9–12% of total Se and 0.2–1.3% of total Sb were extracted by the phosphate solution. These findings suggested that Se was more likely to be mobilized by the addition of phosphate than Sb. The effect of plant-available phosphate in the soil and the phosphate sorption capacity of soil on Se and Sb availabilities for plants were also examined using a pot experiment with soybean plants. The experimental results suggested that a high content of available phosphate and/or low phosphate sorption capacity of soil increased both Se and Sb availabilities to the plant. However, the results also suggested that the soil Se availability to the plant was higher than that of Sb even though the soil total Se and Sb amounts were the same.     

贵州喀斯特山区锑冶炼厂对农业土壤污染特征的影响及风险评价

以贵州省晴隆县大厂镇喀斯特山区废弃锑冶炼厂周围的农田土壤为研究对象,研究了距离冶炼厂烟囱不同距离12个表层土壤样点和5个典型土壤剖面中重金属含量。结果表明表层土壤主要污染元素为Sb、Zn、Pb、Hg、As和Cu,分别是贵州省土壤背景值的58.58、11.96、7.99、7.45、6.70和1.60倍;土壤剖面中8种主要重金属元素垂直变化规律各异,不同层次重金属含量（(Pb除外）)均表现为：距离冶炼厂烟囱越近含量越高,平均含量由高到低依次为：Mn>As>Sb>Cu>Cr>Pb>Hg>Cd,均明显高于全国土壤背景值的平均水平。其中,As、Cr、Mn和Hg平均含量差异较大,与对照相比,主要污染元素为Sb、Hg和As,Hg和As分别为国家土壤环境质量Ⅱ级标准的4.7倍、4.4倍;其次是Cd和Cu,分别为国家Ⅱ级标准的3.0倍、2.7倍。相关分析和聚类分析表明,土壤主要受重金属Cr、Cd、Cu、Sb和As复合污染。采用单因子污染指数和内梅罗综合污染指数法对该地区农田土壤进行了环境风险评价,各层次Cr、Cd、Cu和As含量均超标,污染严重,综合污染指数在1.21 ~ 14.83之间,以重度污染为主;耕作层污染程度由高到低顺序为：大厂村（(冶炼厂）)>中心街村>碧康组>田坝组,均属于重度污染,表层污染土壤（(0 ~ 20 cm）)种植农作物存在一定的风险。     

Cabbage (Brassica oleracea var. capitata) as possible indicator of wartime metal and metalloid contamination in eastern Croatia (ICP-MS method)

Biomonitoring of the local population and environmental monitoring in eastern Croatia have revealed abnormalities in metal and metalloid distribution that could be related to war activities during the 1990s. The goal of this study was to determine whether there are differences in the concentrations of metals and metalloids by comparing locations of high and low-intensity combat activity; we also evaluated a possible connection between metal contamination in soil and in humans. We sampled 14 locations and measured the concentrations of 20 war related metals and metalloids (Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Ni, Pb, Sb, Si, Sr, U, V and Zn). The results of principal components analysis showed two main clusters: locations Dopsin and Dalj (both characterized by high-intensity combat activity), where the concentrations of most elements (except Hg) were increased. Although the concentrations of metals and metalloids in cabbage samples collected in eastern Croatia did not exceed the maximum allowed values, the results of our study confirmed existance of environmental ‘hotspot’ with higher concentrations of war metals and metalloids. Our findings indicate that there is a possible common source and mechanism of transferring metals from the environment to the population.     

“绿色革命”以来大气CO2浓度升高对C3作物营养品质的影响

自20世纪60年代"绿色革命"以来,育种技术和农耕技术的发展促进了农作物产量的大幅提升,然而作物的营养品质出现下降趋势。在相似的遗传背景下,大气CO_2浓度升高会使单位体积农作物产品的营养元素含量下降,因此"绿色革命"至今,农作物产品的营养元素下降可能受大气CO_2浓度升高影响。通过植物生长箱模拟"绿色革命"初期和目前的大气CO_2浓度水平(310μmol/mol和400μmol/mol),针对主要C_3作物水稻、小麦和大豆,研究"绿色革命"以来大气CO_2浓度升高对其籽粒的C、N、Fe、Zn元素含量的影响,结果表明:CO_2浓度升高对3种作物籽粒的C元素含量几乎没有影响,变化幅度在±1.5%之间;籽粒的N、Fe、Zn元素含量普遍呈现下降趋势,但均未达到显著水平。     

Potential of wild species for genetic enhancement of some semi-arid food crops

Discovery and incorporation of genes from wild species provide means to sustain crop improvement, particularly when levels of resistance in the cultigens are low and virulent strains of pests and pathogens overcome the host plant resistance. The extent of utilization and the potential of the wild genepool for genetic enhancement were reviewed in five important food crops viz. sorghum, pearl millet, chickpea, pigeonpea and groundnut grown in the semi-arid tropics. Introgression from compatible wild germplasm in the primary gene pool resulted in transfer of new cytoplasmic male sterility systems in pearl millet and pigeonpea, development of high protein, cleistogamous flower and dwarf pigeonpea lines and foliar disease resistant groundnut cultivars. Utilization of wild species in secondary and tertiary gene pools has been generally limited due to sterility, restricted recombination or cross incompatibility. Nevertheless, these species are extremely important as they contain high levels of resistance to several important biotic and abiotic stresses. Several of them, like those belonging to the Parasorghum section and the rhizomatous Arachis species are sources of multiple resistances and hold great promise to sustain crop productivity.