珠江下游河段沉积物中重金属含量及污染评价

为了解珠江下游出海河道沉积物中重金属含量及各污染物的潜在生态危害程度,用电感耦合等离子质谱法和原子荧光法测定了21个样点沉积物中13种元素的总量,及对底泥中主要重金属污染状况和潜在生态风险进行了评价.结果表明,珠江下游河道总Fe、总Mn含量分别为41 658.73 mg.kg-1和1 104.73 mg.kg-1,微量元素Cr、Co、Ni、Cu、Zn、As、Se、Cd、Sb、Pb和Hg的平均值分别为86.62、18.18、54.10、80.20、543.60、119.55、4.28、10.60、20.26、104.58和0.520 mg.kg-1,地积累指数评价结果显示,表层沉积物重金属污染程度顺序为：Cd〉As≈Zn〉Hg〉Pb≈Cu≈Cr,潜在生态风险程度大小顺序：Cd〉Hg〉As〉Cu〉Pb〉Zn〉Cr,Cd是该水域污染和潜在生态风险最大的元素,单项潜在生态风险与区域综合潜在生态风险一致.珠江下游河道底泥Cd、Hg和Pb污染受输入影响北江大于西江和东江.聚类分析结果表明,研究站位潜在生态风险可分5类,基本反映了站位分布及沉积物环境污染变化特征.总体而言,重金属污染和生态风险程度较高的江段有陈村-沙湾段、陈村-顺德港段及外海-虎跳门段,北江及相关河道污染程度和潜在生态风险指数高于区域其他江段.     

Multivariate characterization of elements accumulated in Wolfiporia extensa mushroom from Yunnan province of China

ABSTRACT

Dried sclerotia of Wolfiporia extensa have been used as medicine in Asia from Eastern Han Dynasty, and also used as traditional snack called “fulingjiabing” in Beijing, China. In this paper, 18 macro and trace elements (Ag, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, Li, Mn, Ni, Pb, Rb, Se, Sr, V, and Zn) in both flesh and peel of Wolfiporia extensa from seven sites of Yunnan province in China were determined by inductively coupled plasma mass spectrometer. The average recovery rates of certified reference materials for GBW10015 (spinach leaves) ranged from 90.5 to 113%, for GBW10028 (citrus leaves) from 92.8 to 106%, and for GBW07603 (bush branch and leaves) from 83.3 to 114.6%. Generally speaking, the concentration of all elements determined was at common level. The results of this survey indicate that mineral compositions in peel were higher than in flesh. In peel, the contents of investigated trace metals in mushroom samples were found to be in the range of 1,660–13,400 µg·g^?1 dry matter (dm) for Fe and 29.6–710 µg·g^?1 dm for Mn. The mean contents of Cr, Cu, Rb, V, and Zn in peel were between 10 and 20 µg·g^?1 dm, followed by As, Co, Li, Ni, Pb, Se, and Sr with mean contents between 1 and 10 µg·g^?1 dm, while Ag, Cd, and Cs had mean contents of <1 µg·g^?1 dm. In flesh, the concentration of Fe was in the range of 54–900 µg·g^?1 dm, and it was 1.5–49 µg·g^?1 dm for Mn, followed by Ba, Cu, Rb, and Zn in the range of 1 to 10 µg·g^?1 dm, while for Ag, As, Cd, Co, Cr, Cs, Li, Ni, Pb, Se, Sr, and V it was <1 µg·g^?1 dm. The concentration of toxic elements, such as As, Cd, and Pb, in both flesh and peel was below the permissible limits of World Health Organization. However, As and Pb contents in peel were higher than the limits permitted in the Chinese Pharmacopoeia. The results of principal component analysis showed that the flesh of Wolfiporia extensa from all the seven sites of the Yunnan province tend to cluster together, most probably because the origin of mineral elements in both flesh and peel is wood substrate (old and dead pine trees).     

霾与非霾期间汞在不同粒径颗粒物上的分布特征

在我国高速经济增长过程中,霾污染日趋突出,同时大气汞污染也十分严重,而颗粒汞对于汞在大气中的循环演化意义重大.为了探讨霾污染期间汞在不同粒径颗粒物中的分布特征,采用Nano-moudi 12级(6.2~9.9μm、3.1~6.2μm,1.8~3.1μm、1.0~1.8μm、0.56~1.0μm、0.32~0.56μm、0.18~0.32μm、0.10~0.18μm,0.056~0.10μm、0.032~0.056μm、0.018~0.032μm、0.010~0.018μm)大气颗粒物采样器,对上海霾与非霾期间不同粒径大气颗粒物中的汞进行分析.结果表明,颗粒态汞含量与颗粒物含量正相关;采样期间霾天颗粒态汞平均浓度0.31 ng·m-3是非霾天颗粒态汞平均浓度0.11 ng·m-3的2~3倍;霾和非霾天颗粒态汞浓度以及颗粒物质量浓度随粒径分布呈双峰型,霾期间峰值分别出现在0.56~1.0μm粒径段和3.1~6.2μm粒径段,而非霾期峰值分别出现在0.32~0.56μm和3.1~6.2μm粒径段;霾天较非霾天颗粒态汞和颗粒物的粒径分布均出现了向大粒径方向偏移;颗粒态汞主要分布在粒径≤1μm粒子上,能够长时间停留和长距离输送;非霾期间颗粒态汞在颗粒物中的平均含量为0.029 ng·μg-1,而霾期间为0.015 ng·μg-1;霾污染过程中其他污染物迅速成长,而汞成长较慢;霾天积聚核模态粒子中颗粒态汞质量浓度为2.06 ng·m-3,而非霾天为0.55 ng·m-3,积聚态颗粒物的大幅增加,是灰霾形成的主要原因.本地源燃煤等的排放以及风沙扬尘的增加和外地源的输送是导致霾天污染严重的重要原因.     

微波消解－ICP－MS法测定土壤中稀土元素的研究

建立了电感耦合等离子体质谱（ ICP－MS）测定土壤中稀土元素的分析方法。采用HNO3＋HF酸体系用微波消解对土壤样品进行处理,以混合内标（ In、Bi）校正基体干扰和信号漂移,用ICP－MS对其中的16种稀土元素进行了测定。在优化的实验条件下,16种稀土元素标准曲线的相关系数r＞0．9999,检出限为0.012 ng／ml～0.069 ng／ml,加标回收率为84.0％～110％,相对标准偏差（n＝6）RSD均小于3.5％。该方法可用于四种不同类型土壤中稀土元素含量的测定。     

ICP-MS法测定不同类型水体可滤态与总量结果比对分析

本文运用电感耦合等离子体质谱(ICP-MS)法对不用类型水体(地下水、地表水、水库水和污水)中的10种重金属元素进行了测定和比对分析。结果显示地下水除钴元素可滤态与总量测定结果相当之外总量均大于可滤态、地表水总量均大于可滤态、水库水除锰元素和镍元素可滤态与总量测定值有较差别外其它8种元素总量与可滤态测定值均无明显差异、污水除钛元素外其余9种元素总量与可滤态测定值均无明显差异。其中,地表水与污水钛元素可滤态均未检出,总量测定值为检出限的1倍至3倍,结果可信。此结果证明对于本次用于检测的样品中的钛元素,全部来源于悬浮于水中的直径大于0.45μm的微粒上,其它元素无此特性。     

电感耦合等离子体质谱法同时测定地下水中钴和钼

建立了一种用电感耦合等离子体质谱法同时测定水源地地下水中微量元素钴和钼的方法。与常规的元素测试方法相比,该方法可以同时快速有效地完成钴和钼测试,测试方法简单,结果准确可靠。     

衡山PM_（2.5）中痕量金属元素的分析

建立了微波消解-电感耦合等离子体质谱法同时测定PM2.5中12种痕量金属元素的方法。对不同消解体系进行了讨论,确定采用HNO3＋H2O2消解体系。方法检出限在0.01～6.4 ng/m3之间,精密度为0.5%～8.9%,加标回收率在69.2%～92.6%之间。应用该方法测定了衡山PM2.5中痕量金属元素的含量,讨论了痕量元素的浓度分布特征,对各元素进行了相关性分析,并应用富集因子法对来源进行了分析。     

ASD—ICP—MS联合快速测定土壤中部分金属元素

土壤环境质量例行监测正在全国展开,如何准确快速分析土壤中的金属含量成为当务之急。采用HNO3-HCl-HF—HClO4体系在全自动消解仪（ASD）上对土壤进行前处理,以50．0μg／L的铑作内标,电感耦合等离子体-质谱仪同时测定《土壤环境质量标准》的7种元素：Cd、As、Cu、Ph、Cr、Zn、Ni。各元素的方法检出限为0．003～0．40mg／kg,相对标准偏差小于6．0％,土壤标样的测定值与标准值吻合。该方法简便快捷、灵敏度高、重现性好,为大批量土壤重金属元素含量的快速测定提供了可靠地消解-分析方法。     

珠江三角洲养殖鱼塘水体中重金属污染特征和评估

为了解珠江三角洲主要养殖环境中重金属含量及潜在生态危害程度,用电感藕合等离子质谱法和原子荧光法测定了肇庆、广州、惠州和茂名4市14个样点沉积物中7种元素的水体及底泥总量,并对底泥中主要重金属污染状况及潜在生态风险进行了评价。结果表明：养殖鱼塘水体中Cr质量浓度范围是nd-0.1011 mg·L-1,超标率为7.1%,Cu质量浓度范围为nd-0.1438 mg·L-1,超标率为64.3%,As质量浓度范围是0.0112-0.0812 mg·L-1,超标率为24.1%,Hg质量浓度范围是0.00004-0.00458 mg·L^-1,超标率为35.7%,Pb质量浓度范围为nd-0.0973 mg·L^-1,超标率为6.8%,其余Ni、Zn和Cd质量浓度范围分别为nd-0.0218、nd-0.0232和nd-0.00319 mg·L^-1,均未超渔业水质标准;底泥中重金属元素Cr、Cu、Zn、As、Hg、Cd和Pb的平均值分别为83.86、46.19、242.16、32.38、0.64、1.00和60.06 mg·kg^-1,地积累指数评价结果显示,表层沉积物重金属污染程度顺序为Cd＞Hg＞Zn＞Pb＞As＞Cu＞Cr,其中,Cd污染程度为中-强,是底泥污染最严重的元素。潜在生态风险指数分析,单项潜在生态风险指数生态风险均值排列顺序为 Hg＞As＞Cd＞Pb＞Cu＞Zn＞Cr。对区域综合潜在生态风险指数RI的贡献率最大的元素为Hg、As和Cd。4个市底泥潜在生态风险综合指数（RI）比较,惠州（290.13）＞广州（240.54）＞茂名（193.23）＞肇庆（116.40）。Hg和Cd是该水域污染和潜在生态风险最大的元素。     

Real time alteration of a nuclear waste glass and remobilization of lanthanide into an interphase

The development of predictive models for the long term evolution of nuclear waste glass requires the complete knowledge of the glass dissolution at the laboratory scale. A new approach was developed to determine the initial reaction during the first steps of experience, a new concept was developed, based on the combination of dynamic leaching test and the characterization of the altered materials. With this experimental set-up it is possible to follow in real time the glass alteration process at a fine temporal scale. The results put in evidence a singular behaviour of the lanthanide, shown by a concentration peak of La, Nd and Ce after 2 h and a quick decrease of their concentration measured on line in the solution during the leaching test. This fact is directly linked to the development of an interphase (altered layer which differs from the initial solid by its texture, structure and chemical composition) at the interface of the glass surface and the leaching solution. This work is an attempt to integrate the formation of the alteration products (here the interphase) during leaching into the dissolution mechanisms of a nuclear waste glass. A model is proposed and discussed.