1999年与2014年贡嘎山峨眉冷杉枝和叶中常见重金属的生物富集特征对比

经济的快速发展使得生态环境的承载力日益接近上限,而关于偏远地区森林系统的重金属污染的时间变化趋势却鲜有报道.本文测定了贡嘎山1999年与2014年采集的峨嵋冷杉枝、叶中的Pb、Hg、Cr、As、Cd、Mn、Cu、Zn与Ba.结果表明：11999年枝、叶样品中Pb、Hg、As、Cd、Mn与Cu显著高于2014年的量,而2014年枝、叶样品中Cr、Zn和Ba高于1999年的量;2枝中Pb、Hg、Cr、As、Cd、Mn、Cu、Zn和Ba与生长龄无统一的变化趋势,而在叶中的含量随着生长龄的增加有增加的趋势;3Hg易在叶中富集,而其它元素更易在枝中富集;通过在主成分分析的基础上进行多元线性回归判断常见重金属元素的来源,枝、叶中的Pb、Cr、As、Cd、Cu、Zn和Ba有42.3%~92.2%的含量来自于土壤,而枝、叶中的Hg有70.6%的含量来自于大气.这说明Hg存在与其他重金属在森林系统不同的累积机制.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

典型河谷城市儿童土壤与灰尘铅暴露风险

为定量评价河谷型城市土壤与灰尘铅对城市儿童健康的影响与风险,结合野外调查的基础上,以陕西渭河谷地典型工业城市宝鸡、西安、渭南和铜川为研究区域,以定量分析河谷型城市儿童环境铅暴露为核心,收集4个城市土壤与灰尘分析样品总计243个。利用X射线荧光光谱法测定了4个城市土壤与灰尘铅的含量;采用BCR连续形态分级法探究了城市土壤与灰尘重金属铅地球化学形态分布与迁移特征;根据US EPA污染物暴露与健康风险评价模型对城市儿童铅暴露进行了评价。研究结果表明渭河谷地典型城市宝鸡、铜川、西安和渭南城市土壤与灰尘铅浓度(X±SD)分别为(409.2±52.54)和(624.70±66.15)mg·kg-1、(357.47±41.37)和(592.60±36.78)mg·kg-1、(61.4±13.31)和(78.42±14.89)mg·kg-1、(46.71±12.11)和(64.7±13.76)mg·kg-1,均高出陕西省土壤铅背景值;污染水平依次为宝鸡铜川西安渭南。4个河谷型城市土壤与灰尘重金属铅发生整体迁移的趋势为:宝鸡城市灰尘(90.71%)西安城市灰尘(84.74%)≥宝鸡城市土壤(83.12%)渭南城市灰尘(74.89%)≥西安城市土壤(74.50%)铜川城市灰尘(72.49%)铜川城市土壤(57.50%)渭南城市土壤(53.79%)。可见,铅在均在城市灰尘中的迁移趋势远大于相应的城市土壤。4个城市土壤与灰尘均表现出较大的儿童暴露致癌风险,宝鸡和铜川城市儿童土壤与灰尘铅暴露也分别存在非致癌风险,风险程度依次为宝鸡铜川西安渭南。儿童铅暴露致癌与非致癌风险程度与其城市土壤和灰尘中铅可氧化态分布呈相似的规律,表明碱性的城市土壤与城市灰尘(p H7)中可氧化态铅可能是导致河谷型城市儿童铅暴露风险和儿童血铅污染的主要形态和因素。由此,城市燃煤排放与含铅制品的加工等活动可能是渭河谷地河谷型城市儿童血铅与铅暴露最主要的贡献源,必须采取长期有效的监测与控制措施。     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

顶空／气相色谱-质谱法测定水中四乙基铅

建立了顶空,气相色谱-质谱法测定水中四乙基铅方法。水样中的四乙基铅直接顶空进样,质谱分析。实验结果表明,在0．10-5．00μg几范围内线性关系良好,方法检出限为0．02μg/L,得到了良好的分离效果与较高的灵敏度和精密度。方法简便快捷,能达到《生活饮用水卫生规范》（GB/T5750．8—2006）中规定的要求。     

茶叶基水合氧化铁吸附水体中Pb(Ⅱ)的性能

采用原位沉积技术将水合氧化铁(HFO)负载于废弃茶叶渣表面制备了复合材料茶叶基水合氧化铁(HFO-TW),研究了HFO-TW对水溶液中Pb(Ⅱ)的吸附特性,探讨了溶液pH值、时间、共存碱土离子、温度、Pb(Ⅱ)初始浓度等因素对Pb(Ⅱ)的吸附效果的影响.结果表明酸性范围内,Pb(Ⅱ)的吸附量随溶液pH升高而增大;Pb(Ⅱ)的吸附速度较快,100 min内便可达吸附平衡,且动力学曲线较好地符合伪一级和伪二级动力学模型,拟合系数可达98.8%;在竞争离子Ca(Ⅱ)/Mg(Ⅱ)的浓度高于Pb(Ⅱ)50倍时,HFO-TW对Pb(Ⅱ)仍具有较强的吸附能力,Pb(Ⅱ)的吸附量仅分别下降12.1 mg·g-1和8.1 mg·g-1;Pb(Ⅱ)的吸附过程较好地符合Langmuir等温模型,理论最大吸附容量为89.43 mg·g-1,远高于未经改性的茶叶渣和其他生物吸附剂.所有结果均证实HFO-TW在净化实际铅污染水体中有着较为广阔的应用潜力.     

石灰干化污泥稳定后土壤中Pb、Cd和Zn浸出行为的研究

以人工制备Zn、Pb、Cd污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP、SPLP、去离子水浸提和优化的BCR连续提取法对稳定化效果进行分析和评价.结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-99.54%、Pb-99.60%、Cd-99.85%.SPLP和去离子水浸出评价稳定效果时,Pb和Zn在加入质量分数10%和20%的干化污泥时浸出明显降低,但在加入30%和40%时由于在强碱条件Pb和Zn会再溶出,导致稳定效果变差.为了恢复植物生长功能,经过FeSO4和H3PO4调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时FeSO4和H3PO4有利于促进Pb和Zn的稳定效果.经稳定化后,土壤中的重金属可交换态降低,限制了土壤重金属的迁移.该研究结果表明石灰干化污泥可以再利用,应用于重金属污染土壤的稳定化修复中,并能改善稳定后土壤适宜植物生长的理化性质.     

NaCl改性沸石去除水中低浓度铅的研究

实验研究了NaCl改性沸石去除水中铅的效果,比较了沸石改性前后对铅的静态平衡吸附量变化,着重考察了吸附时间、pH值、竞争离子以及有机物对去除铅效果的影响。结果表明:NaCl改性沸石吸附铅速度快,对铅有很好的去除效果,平衡吸附量由改性前的28.57mg/g提高到了32.26mg/g。pH值对NaCl改性沸石去除水中铅的效果有较大影响,在pH=6～7时,去除效果最佳。水中竞争阳离子和有机物的存在,在一定程度上会降低铅的去除效果;随干扰物质浓度的升高,NaCl改性沸石对铅去除率出现了明显的下降,但当干扰物质和水样中铅浓度相当时,NaCl改性沸石可对铅保持很高的去除率。     

外源硅对不同pH水田土壤吸附铅的影响

通过等温吸附实验,研究了加硅对2种不同pH水田土壤吸附铅特性的影响。实验中用硝酸中和硅酸钠的碱性,各处理间钠离子和硝酸根离子的差异以硝酸钠补齐,消除了因硅酸盐的加入改变体系pH及伴随离子对土壤吸附铅可能产生的影响。结果表明,在本实验条件下,Langmuir方程、Freundlich方程和Temkin方程都能较好地描述不同硅浓度条件下两种土壤对铅的吸附特征,但以Freundlich模型为最优;加硅促进了酸性土壤对铅的吸附,抑制了碱性土壤对铅的吸附。     

EDTA reduces lead accumulation in Symphytum officinale L. (comfrey) roots

The addition of EDTA in phytoextraction studies has been reported to increase heavy metal accumulation in above-ground parts or to have no negative impact on the overall (root/shoot) accumulation levels in terrestrial plants. At a purely quantitative level, this study assessed the phytoextraction potential of a previously untested high-biomass terrestrial plant, Symphytum officinale L. (comfrey), in the presence of Pb and EDTA. In this hydroponic-based study, we report a small increase in shoot accumulation of Pb with EDTA but, conversely, the presence of EDTA in the nutrient medium markedly reduced the overall quantity of Pb in the plant root by at least 80%. The loss does not appear to be explained by EDTA acting alone, increased transport of Pb to the shoots, or anionic charge repulsion of the [PbEDTA]^2? complex. The elusive action and negative effect of EDTA on Pb accumulation in S. officinale provides additional reasons towards a growing trend away from the use of EDTA as a chelating agent in phytoextraction.