同步辐射技术在环境纳米金属组学研究中的应用

随着我国工业的发展,在工业产值不断提升的同时,向环境中释放出的各类污染物也逐渐增加,其中包括多种金属纳米颗粒物。这些金属纳米颗粒物进入大气、水源及土壤中,累积到一定程度引起环境安全问题;进一步可被动植物所吸收,经过食物链富集和传递,造成直接或间接人体暴露,危害人体健康。环境纳米金属组学,研究的范畴主要涉及自然或人为因素产生的金属纳米颗粒在环境介质和生物有机体中的生物/化学行为、转化归趋,并且据此评价金属纳米颗粒物的环境安全性及其生物健康效应。随着对金属纳米颗粒环境效应研究的不断深入,对传统的研究方法提出了更多的挑战。同步辐射具有高亮度、高准直和宽频谱等特性,在金属元素分析方面具有无可比拟的优势。本文主要介绍了同步辐射技术,如同步辐射X射线荧光分析技术(SR-XRF)和同步辐射X射线吸收光谱技术(SR-XAS)等,在金属纳米颗粒物的环境行为及其生物健康效应研究中的应用;结合本实验室及国内外的一些研究工作,阐述了同步辐射技术应用于环境纳米金属组学研究领域所取得的一些新进展,以期为拓展同步辐射技术在环境金属纳米颗粒物分析的应用研究提供参考价值。     

环境样品中汞形态分析技术的进展

汞的毒性、环境行为、生物有效性不仅跟其浓度有关,还决定于其化学形态,因此汞的形态分析在环境科学中具有重要意义。样品前处理几乎是汞形态分析研究中不可或缺的步骤,而色谱和光谱/质谱联用技术是目前普遍采用的分离检测方法。文章对近十年来这些方面的研究进展进行了综述,主要包括样品的前处理方法如酸/碱溶剂萃取、微波辅助萃取、固相萃取、固相微萃取、单滴微萃取、分散液液微萃取等,以及色谱(液相色谱、气相色谱)和毛细管电泳与光谱/质谱(紫外可见光谱、原子吸收光谱、原子荧光光谱、等离子体质谱等)的联用技术在汞化合物形态分析中的应用情况。最后提出今后应重点研究建立高效、简便的前处理方法,发展高分离度、高灵敏度、高速度的分离检测联用技术,以便更好地对汞的形态进行分析监测。     

基于同步辐射的硬X射线荧光技术分析污染土壤中重金属分布

基于同步辐射技术的微束X射线荧光(μ-XRF)分析具备原位分析样品的元素组分,化学特性,物质结构及其二维分布等的能力,可更加直观地揭示目标元素在复杂体系中的分布状态.利用传统的化学消解与原位μ-XRF技术相结合的方法,探测锡矿山土壤中多种元素的含量和空间分布,采用线性回归方法分析各元素的相关性.结果表明,供试土壤Sb和As含量较高,分别为6 681和878 mg·kg-1,μ-XRF分析表明土壤中Fe、Mn分别与As的空间分布相关性较好,决定系数(R2)分别达0.225 8和0.181 1,更直观地揭示了As在土壤中以铁锰结合态为主.μ-XRF技术的应用原位直观地揭示了土壤中多种元素的分布关系,为综合评价和预测土壤中重金属的环境行为以及发展污染土壤修复技术等提供理论支持.     

Research progress on occurrence forms and microbial transformation of mercury北大核心CSCD

汞是一种高毒性且具有持久性的重金属污染物,汞污染的治理与修复在近几十年一直是国内外研究热点.了解微生物对汞赋存形态的转化作用,对汞污染的治理与修复具有重要意义.总结汞的不同赋存形态、毒性及对应的常用分析方法,其中甲基汞(methyl mercury,MeHg)是毒性最强的汞形态之一.环境中汞的化学形态能发生转化,尤其以微生物驱动的汞的甲基化、MeHg的去甲基化和汞的氧化还原最为常见.依据汞转化类型将汞转化相关微生物分为汞甲基化、MeHg去甲基化、汞还原、汞氧化等类群,将对应的汞转化作用机制分为基于hgcAB基因的汞甲基化、基于mer操纵子基因的MeHg去甲基化和Hg2+还原、胞内过氧化氢酶介导的Hg0氧化.微生物汞转化过程不仅受到pH和温度的显著影响,而且还受到汞的赋存形态和游离汞的浓度、微生物种/群结构与功能、矿物种类、中间体和次生产物及其交互作用的影响,基于此,提出正确客观表征汞的微生物转化过程需要综合分析微生物组和矿物组的变化规律及其交互作用的综合效应.针对酸性矿山废水(AMD)极端环境微生物汞转化研究的不足,未来的工作将聚焦结合多组学手段、同步辐射谱学和密度泛函理论(DFT)计算等分析技术研究汞赋存形态的微生物转化过程,分析和阐明汞转化中间体的键合作用方式和转化机制,从而为AMD汞污染的预防、治理和修复提供依据.(图2表2参107)     

环境样品中汞形态分析技术的进展

汞的毒性、环境行为、生物有效性不仅跟其浓度有关,还决定于其化学形态,因此汞的形态分析在环境科学中具有重要意义。样品前处理几乎是汞形态分析研究中不可或缺的步骤,而色谱和光谱/质谱联用技术是目前普遍采用的分离检测方法。文章对近十年来这些方面的研究进展进行了综述,主要包括样品的前处理方法如酸/碱溶剂萃取、微波辅助萃取、固相萃取、固相微萃取、单滴微萃取、分散液液微萃取等,以及色谱（液相色谱、气相色谱）和毛细管电泳与光谱/质谱（紫外可见光谱、原子吸收光谱、原子荧光光谱、等离子体质谱等）的联用技术在汞化合物形态分析中的应用情况。最后提出今后应重点研究建立高效、简便的前处理方法,发展高分离度、高灵敏度、高速度的分离检测联用技术,以便更好地对汞的形态进行分析监测。     

环境中汞化学形态分析研究进展

作为一种剧毒元素,汞的毒性与其化学形态密切相关.环境介质中汞的化学形态监测分析主要涉及样品的采集、保存、前处理、分离和测定等步骤.本文综合国内外相关文献,系统介绍了开展环境介质中汞化学形态监测分析的相关测试技术和方法,并阐述了我国开展汞化学形态监测存在的问题及其意义.     

九龙江河口潮间带表层沉积物汞污染分布、赋存形态与生态风险

研究九龙江河口汞污染情况可为该地区汞污染防治提供科学依据,测定九龙江河口潮间带表层沉积物中总汞含量及不同形态汞的含量,分析了汞的分布特征、赋存形态及生物有效性和潜在生态风险。结果表明:九龙江河口潮间带表层沉积物中总汞含量范围0.112~0.259 mg·kg-1,平均值0.172 mg·kg-1,部分采样点汞含量超过中国海洋沉积物质量第一类标准限值(0.20 mg·kg-1);沉积物中各形态汞平均比例顺序:残渣态(61.8%)可氧化态(27.8%)弱酸溶态(7.8%)可还原态(2.6%),可提取态占有相当的比例,对水体汞污染具有一定贡献。潜在生态风险指数法评价结果可知,该河口区潮间带沉积物中汞污染程度和生态风险程度均为中等~较高水平,需对汞污染进行综合防治。     

珠三角某垃圾焚烧厂周边植物叶片汞含量空间格局影响因素影响因素

为研究珠三角某城市生活垃圾焚烧厂周边汞污染空间格局及影响因素,于2014年1月,采集了马占相思、荔枝和芒萁等优势种的叶片样品192份,并同步采集相应表层土壤样品64份,采用冷原子吸收法测定样品总汞含量,并运用ADMS模型对2013年大气汞年均浓度进行模拟,分析了植物叶片汞含量与土壤和大气汞浓度之间的关系。结果表明,植物叶片的汞含量范围为0.0029~0.1741 mg·kg-1,荔枝叶片汞含量最高,为(0.0766±0.0395)mg·kg-1,其次为芒萁((0.0599±0.0370)mg·kg-1)和马占相思((0.0556±0.0396)mg·kg-1)。植物叶片汞含量与土壤汞含量无显著相关性,而受风向和距污染源的距离影响显著,与ADMS模拟的大气年均汞浓度存在显著相关性。研究表明,植物叶片汞含量变化与烟气扩散浓度的空间分异格局基本吻合,叶片对大气中汞的吸收在植物与环境的汞交换中占据主导地位,对叶片的生物监测可以反映城市生活垃圾焚烧厂汞排放对生态环境的实际影响。     

外源磷素对药用植物三七吸收砷的微区及形态分布特征影响

三七是中国特有的珍稀药用植物,其生长环境受地域、气候、土壤等条件的限制,仅云南省文山州三七产量高、品质好。但由于矿业开采、工业生产等因素使得土壤砷的背景值超标,逐渐威胁三七的正常生长及其产品质量。因此,如何降低三七砷污染是目前迫切需要解决的问题。磷与砷具有相似的结构和理化性质,利用磷与砷在土壤中的拮抗效应,达到控制土壤砷危害的效果。本研究利用同步辐射X射线荧光方法(SRXRF)和高效液相色谱-原子荧光联用技术(HPLC-HG-AFS)相结合对参试三七植株进行分析测定,从细胞微区组织层面揭示药用植物三七在外源磷素作用下吸收As和P的相对含量分布规律和三七植株各部位的砷形态及含量特征,以及各部位的生物转运系数及富集系数的变化。结果表明:磷和砷在三七主根部的相对含量荧光分析中保持分布规律一致的特性,说明三七根部吸收磷和砷的点位相同;添加外源磷素处理可以有效降低三七各部位三价砷和五价砷的含量,最大降幅达50%,同时可以降低根部对砷的吸收富集系数;试验中仅添加五价砷元素,但在三七植株各部位均检出三价砷,说明三七体内存在着砷还原机制;其中茎部的三价砷的含量均高于五价砷,推测茎是三七体内砷还原反应的主要场所。     

五里河水体甲基汞污染及沉积物中甲基汞释放速度的初步研究

河流水体的汞污染,主要来源于工业生产中所排放的含汞废水。环境监测报告表明,生产氯碱的化工厂的含汞废水排入河流后,会使水体造成严重的汞污染。五里河就是这样一条被汞严重污染的河流,它是构成锦州湾海域汞污染的主要污染源。 从汞的化学形态来看,五里河水体的汞污染,可分为无机汞污染和有机汞(主要是甲基汞)污染。而处于水生生态环境中(主要是沉积物中)的无机汞,可以转化为甲基汞。由于甲基汞污染比无机汞污染对环境和人类具有更大的危害性,所以五里河水体中甲基汞     

Potential application of sludge produced from coal mine drainage treatment for removing Zn(II) in an aqueous phase

Various analyses of physico-chemical characteristics and batch tests were conducted with the sludge obtained from a full-scale electrolysis facility for treating coal mine drainage in order to find the applicability of sludge as a material for removing Zn(II) in an aqueous phase. The physico-chemical analysis results indicated that coal mine drainage sludge (CMDS) had a high specific surface area and also satisfied the standard of toxicity characteristic leaching procedure (TCLP) because the extracted concentrations of certain toxic elements such as Pb, Cu, As, Hg, Zn, and Ni were much less than their regulatory limits. The results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the CMDS mainly consists of goethite (70%) and calcite (30%) as a weight basis. However, the zeta potential analysis represented that the CMDS had a lower isoelectric point of pH (pH(IEP)) than that of goethite or calcite. This might have been caused by the complexation of negatively charged anions, especially sulfate, which usually exists with a high concentration in coal mine drainage. The results of Fourier transform infrared (FT-IR) spectrometry analysis revealed that Zn(II) was dominantly removed as a form of precipitation by calcite, such as smithsonite [ZnCO?] or hydrozincite [Zn?(CO?)?(OH)?]. Recycling sludge, originally a waste material, for the removal process of Zn(II), as well as other heavy metals, could be beneficial due to its high and speedy removal capability and low economic costs.     

Mercury source zone identification using soil vapor sampling and analysis

Development and demonstration of reliable measurement techniques that can detect and help quantify the nature and extent of elemental mercury (Hg(0)) in the subsurface are needed to reduce uncertainties in the decision-making process and increase the effectiveness of remedial actions. We conducted field tests at the Y-12 National Security Complex in Oak Ridge, Tennessee, USA, to determine if sampling and analysis of Hg(0) vapors in the shallow subsurface (<0.3 m depth) can be used to as an indicator of the location and extent of Hg(0) releases in the subsurface. We constructed a rigid polyvinyl chloride push probe assembly, which was driven into the ground. Soil gas samples were collected through a sealed inner tube of the assembly and were analyzed immediately in the field with a Lumex and/or Jerome Hg(0) analyzer. Time-series sampling showed that Hg vapor concentrations were fairly stable over time, suggesting that the vapor phase Hg(0) was not being depleted and that sampling results were not sensitive to the soil gas purge volume. Hg(0) vapor data collected at over 200 push probe locations at 3 different release sites correlated very well to areas of known Hg(0) contamination. Vertical profiling of Hg(0) vapor concentrations conducted at two locations provided information on the vertical distribution of Hg(0) contamination in the subsurface. We conclude from our studies that soil gas sampling and analysis can be conducted rapidly and inexpensively at large scales to help identify areas contaminated with Hg(0).     

Potential application of sludge produced from coal mine drainage treatment for removing Zn(II) in an aqueous phase

Various analyses of physico-chemical characteristics and batch tests were conducted with the sludge obtained from a full-scale electrolysis facility for treating coal mine drainage in order to find the applicability of sludge as a material for removing Zn(II) in an aqueous phase. The physico-chemical analysis results indicated that coal mine drainage sludge (CMDS) had a high specific surface area and also satisfied the standard of toxicity characteristic leaching procedure (TCLP) because the extracted concentrations of certain toxic elements such as Pb, Cu, As, Hg, Zn, and Ni were much less than their regulatory limits. The results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the CMDS mainly consists of goethite (70%) and calcite (30%) as a weight basis. However, the zeta potential analysis represented that the CMDS had a lower isoelectric point of pH (pH_IEP) than that of goethite or calcite. This might have been caused by the complexation of negatively charged anions, especially sulfate, which usually exists with a high concentration in coal mine drainage. The results of Fourier transform infrared (FT-IR) spectrometry analysis revealed that Zn(II) was dominantly removed as a form of precipitation by calcite, such as smithsonite [ZnCO₃] or hydrozincite [Zn₅(CO₃)₂(OH)₆]. Recycling sludge, originally a waste material, for the removal process of Zn(II), as well as other heavy metals, could be beneficial due to its high and speedy removal capability and low economic costs.     

土壤重金属X射线荧光光谱非标样测试方法研究

采用粉末压片制样,用X射线荧光光谱非标样测试方法测定土壤中Ti、V、Cr、Mn、Fe、Ni、Cu、Zn、Ga、As、Cd、Sn、Sb、Pb、Hg等15种重金属元素。研究了样品制备方法和元素测量条件等影响测试准确度的因素。结果表明此方法不需对固体样品进行消化处理,无需制备标准样片,快速、简便、效率高,是一种非破坏性的分析方法,方法的检出限、准确度和精密度基本能够满足土壤中有毒有害重金属的快速筛查要求。     

贵州万山汞矿地区耐汞野生植物研究

在贵州万山地区废弃汞矿堆和矿山附近,受长期高剂量汞暴露的影响经过的自然选择,该地区出现了一些能耐受汞毒性的生态型植物。对汞耐受及汞富集植物的筛选对于汞污染土壤的植物修复具有一定的现实意义。通过对万山梅子溪地区汞污染土壤及汞耐受植物采样调查发现,该区域采样土壤中汞的含量均在50 mg·kg-1以上,达到重度汞污染水平。对该地区野生植物的采样分析发现,蔷薇科植物悬钩子不仅数量较多,单株植物生物量较大,表现出很强的耐汞毒性的能力,而且植株内可以很大程度地富集汞,在其植株中汞的含量可达20 mg·kg-1左右,属于汞富集植物,另外发现野蒿对汞也具有较强的富集能力,其植株中汞的含量可达10 mg·kg-1以上。该类型植物的发现将为植物的汞耐受以及汞富集机理研究提供新的素材,为汞污染土壤的植物修复技术提供新的植物类型,也为进一步开发汞污染土壤处理技术提供了一种可能。     

Action de métaux lourds à des doses sublétales sur les caractéristiques de la croissance chez la diatomée Skeletonema costatum

Sublethal effects of mercury, cadmium and copper on the diatom Skeletonema costatum (Grev.) Cleve, grown in batch and bacteria-free culture are studied. Division rate, maximum yield growth, mean cell volume, particulate carbon and nitrogen, and ¹⁴C-bicarbonate uptake are used as toxic impairment criteria. Division rate is the first-affected and most sensitive parameter, but algal responses vary according to the metal. Hg produces an acute decrease in division rate, followed by a temporary recovery of growth capacity within the first 48 h after metal addition. Cd, on the other hand, increases division rate, followed by an obvious decrease. Cu reduces division rate slowly or quickly, depending on the metal concentration. Cell synthesis capacity (culture biovolume, particulate carbon and nitrogen, carbon assimilation) is less affected than division rate, especially with Hg. The C:N cell ratio is unchanged at sublethal concentrations, even when production is reduced. The mean cell volume is slightly affected: the variations are not greater than those of the control during its growth phases. Markedly teratological forms are never observed. In the authors' opinion, these results confirm that many parameters and growth kinetic aspects must be considered to fully appreciate the effects of sublethal concentrations of heavy metals. It would also be of advantage to develop a better methodology for such research, applying, for example, techniques already employed in enzymology.     

汞和砷单一及联合暴露对日本沼虾的氧化应激效应

为深入探讨汞(Hg)和砷(As)对水生生物的慢性毒性效应,以日本沼虾(Macrobrachium nipponense)为受试生物,以超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、金属硫蛋白(MT)和丙二醛(MDA)为测试分子标志物,研究上覆水中不同浓度Hg和As单一及联合暴露对日本沼虾肝胰腺的氧化损伤及联合作用机制。结果表明:Hg和As单一及联合暴露对4种分子标志物均可产生不同程度的抑制或激活效应。其中,SOD活性均受到抑制,且高浓度As(1000μg·L-1)暴露10 d的抑制率最大,高达59.13%;而CAT活性整体被激活,Hg单独暴露下的激活效应要高于As,且在联合暴露组中随着暴露时间的增加呈现出显著的剂量效应关系(P0.05);MT和MDA含量在Hg和As的暴露下均显著增加(P0.05)。其中MT对Hg的螯合能力大于As,As单独暴露3 d后MDA变化较小,但10 d后其含量显著增加(P0.05)。析因方差分析发现,Hg-As对机体的联合作用机制主要表现为协同作用。综合生物标志物响应指数(IBR)评价证实,联合毒性要高于单独毒性,Hg与As在高浓度下联合暴露10 d的IBR值最大,毒性最强,高浓度As单独暴露处理组的毒性次之;同时,机体自身随暴露时间延长对Hg也表现出一定的解毒功能。     

Quantitative and structural analyses of hazardous elements in Chinese medicines and herbs

Thirty samples of Chinese medicines and herbs were analyzed using instrumental neutron activation analysis (INAA) and X-ray diffraction (XRD) methods, mainly noting on the hazardous elements arsenic (As), mercury (Hg), chromium, antimony and cobalt. The three Niuhuang Jiedu Pian samples contained 8.6%, 8.3% and 2.2% As. Two out of four Liushen Wan samples contained approximately7% of both As and Hg. Despite being identically named, the other two Liushen Wan samples did not contain such high concentrations. Japanese Liushen Wan for children contained 1.2 ± 0.03% As and 31 ± 12 mg/kg Hg, whereas Liushen Wan for adults manufactured by another Japanese company contained 550 ± 22 mg/kg As and 1.2 ± 0.05 mg/kg Hg. All the chemical structural formulas of As and Hg in the high-concentration Niuhuang Jiedu Pian and Liushen Wan were realgar (As₄S₄), uzonite (As₄S₅) and cinnabar (HgS). Although the human body is generally not believed to absorb sulphides, continuous intake of these Chinese medicines is potentially no good because it is possible that some arsenic-sulfides will dissolve in gastric acid and then alter their chemical structures. Additionally, many herbs contained low concentrations of Hg, and their chemical structures were unknown.     

Sulfonated cross-linked polyethylenimine for selective removal of mercury from aqueous solutions

Polymeric materials are among the most promising, effective, and increasingly important adsorbents for the removal of toxic metals from wastewater. This study was dedicated to the development of an insoluble, modified chelating polymer for use as an adsorbent for abstraction of Hg from aqueous solutions. Cross-linked polyethylenimine (CPEI) was sulfonated by 3-chloropropanesulfonyl chloride for selective removal of Hg. The binding affinity of the sulfonated CPEI (SCPEI) to Hg was assessed as well as its ability to be regenerated for reuse. It exhibited high removal percentage for Hg up to 87% in synthetic solutions, with high selectivity even in the presence of competing ions: “Mn, Ni, Fe, Pb, Zn, and Cr.” The removal mechanism followed was observed to be adsorption and precipitation at pH 3 and 8, respectively. High adsorption capacities were also observed for wastewater to which the polymer was applied. The Freundlich isotherm was found to be the best fit describing the adsorption process of Hg onto the SCPEI. The pseudo second-order equation was found to better explain the adsorption kinetics, implying chemisorption. The thermodynamic study of the adsorption revealed high activation energies which confirmed the chemisorption as the mechanism of adsorption. The polymer exhibited up to 72% removal efficiency after regeneration, thus showing potential for re-use.