Uranium speciation in coal bottom ash investigated via X-ray absorption fine structure and X-ray photoelectron spectra

Similar to chromium contamination, the environmental contamination caused by uranium in radioactive coal bottom ash (CBA) is primarily dependent on the chemical speciation of uranium. However, the relationship between uranium speciation and environmental contamination has not been adequately studied. To determine the relationship between uranium speciation and environmental contamination, X-ray absorption fine structure (XAFS) and X-ray photoelectron spectra (XPS) analyses were performed to determine the uranium speciation in CBA exposed to different chemical environments and simulated natural environments. The leachability of the different forms of uranium in the CBA was studied via a simulated acid rain leaching experiment, and the results showed that 57.0% of the total uranium was leached out as U(VI). The results of a linear combination fit (LCF) of the X-ray absorption near edge structure (XANES) spectrum revealed that in the raw CBA, the uranium mainly occurred as U3O8 (71.8%). However, in the iron-rich particles, the uranium mainly occurred as UO2 (91.9%) after magnetic separation. Magnetite is a ubiquitous ferrous-bearing oxide, and it was effective for the sorption of U(IV). The result of FeSO4 leaching experiment indicated that 96.57% of total uranium was reduced from U(VI) to U(IV) when infiltrated with the FeSO4 solution for 6 months. This result clearly demonstrated the changes in chemical valence of uranium in the coal ash and provided a conceptual principle for preventing uranium migration from ash to the surrounding soil and plants.     

Application of ultrasonic to speciation analysis of heavy metals in soil

In order to reduce the operation time and improve the extraction efficiency, ultrasonic energy by means of ultrasonic bath was used to the modified Tessier sequential extraction for speciation analysis of heavy metals in soil. Extractable contents of Cu, Fe, Mn, Ni,Pb and Zn were measured by atomic absorption spectroscopy(hAS). The merit of the ultrasonic extraction (UE) applied to the modified Tessier method is not only that the operation time for the first 4 fractions was reduced from ca. 18 h to 8 h, comparing with conventional extraction(CE), but also the extraction efficiency was higher. The results for both of UE and CE were consistent. The extractable Cu, Ni and Zn in the sample No. 1 were mainly associated with the third fraction (Fe-Mn oxides fraction), and fourth fraction (organic matter fraction) in the sample No.2. The extractable Fe and Mn were all mainly associated with the third fraction, and Pb the fourth fraction in both of the samples. The effects of concentration of hydroxylamine chloride on the capability for the extraction of studied metals were also studied.     

Particle size distribution and characteristics of heavy metals in road-deposited sediments from Beijing Olympic Park

Due to rapid urbanization and industrialization, heavy metals in road-deposited sediments (RDSs) of parks are emitted into the terrestrial, atmospheric, and water environment, and have a severe impact on residents' and tourists' health. To identify the distribution and characteristic of heavy metals in RDS and to assess the road environmental quality in Chinese parks, samples were collected from Beijing Olympic Park in the present study. The results indicated that particles with small grain size (< 150 μm) were the dominant fraction. The length of dry period was one of the main factors affecting the particle size distribution, as indicated by the variation of size fraction with the increase of dry days. The amount of heavy metal (i.e., Cu, Zn, Pb and Cd) content was the largest in particles with small size (< 150 μm) among all samples. Specifically, the percentage of Cu, Zn, Pb and Cd in these particles was 74.7%, 55.5%, 56.6% and 71.3%, respectively. Heavy metals adsorbed in sediments may mainly be contributed by road traffic emissions. The contamination levels of Pb and Cd were higher than Cu and Zn on the basis of the mean heavy metal contents. Specifically, the geoaccumulation index (I_geo) decreased in the order: Cd > Pb > Cu > Zn. This study analyzed the mobility of heavy metals in sediments using partial sequential extraction with the Tessier procedure. The results revealed that the apparent mobility and potential metal bioavailability of heavy metals in the sediments, based on the exchangeable and carbonate fractions, decreased in the order: Cd > Zn ≈ Pb > Cu.     

沈阳市新城子铬渣堆存区土壤铬污染分布及形态分析

采用Tessier A连续提取法,研究分析了沈阳市新城子铬渣堆存区土壤中重金属铬的污染分布和迁移转化规律,土壤中重金属铬的5种形态分布,主要以残渣态和碳酸盐结合态为主,分别占总量的49.74%和21.4%,而有机结合态含量最低,占总铬含量的6.25%。不同的功能区域铬的形态分布有所不同。总体的分布特征是残渣态>碳酸盐结合态>交换态>铁猛氧化态>有机态。     

湘江株洲段沉积物中铅的形态分析及污染评价研究

采用Tessier五步浸提法,对湘江株洲段的枫溪、白石、霞湾、马家河四个断面沉积物样品进行分析,分别提取可交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态和残渣态五种形态,并采用电感耦合等离子体发射光谱法测定铅的各种形态含量.这四个断面的表层沉积物中铅形态含量最低的均为碳酸盐结合态,次低的为可交换态,铁锰氧化物结合态和残渣态是含量相对较高的形态.选择风险评价准则、地累积指数法和潜在生态危害指数三种方法对铅的污染状况进行了评价.     

麦草畏除草剂厌氧降解可生化性测定

苯环由¹⁴C标记合成的麦草畏除草剂,厌氧降解反应至第7天,转化率达64%,有¹⁴C标记的CO₂产生;第16天,转化率达91%,出现一种主要的中间代谢产物,有CH₄产生;第27天,转化率达95%,仍然只有一种主要的中间代谢产物.麦草畏苯环的断裂量仅占总量的2.96%,转化成CO₂的为0.74%,转化成CH₄的为0.11%.在降解27d中,主要中间代谢产物是3,6-二氯水杨酸,占麦草畏总量的92.04%.3,6-二氯水杨酸的苯环没有被打开,可生化性极低,仍然继续污染环境研究结果为控制麦草畏对人体健康危害,进行生物修复工程,提供了重要的参考依据.     

黄石沿江土壤镉的形态特征及生物可利用性

为了解黄石市沿长江冲积土壤中重金属镉直接和潜在的危害程度,为重金属污染防治提供科学依据,采用总量测定、Tessier连续提取法,分析研究了湖北黄石市沿江冲积土壤中重金属镉的总量及不同形态含量,镉含量采用火焰原子吸收分光光度法测定。结果表明,研究区土壤Cd全量都大于2mg/kg,不同形态Cd含量相对大小依次为残渣态铁锰氧化物结合态碳酸盐结合态有机物结合态离子交换态。其中残渣态占全量比例为58%,铁锰氧化物结合态为26%,碳酸盐结合态、有机物结合态、离子交换态分别为8%、4%和3%。可见研究区Cd的生物可利用态含量低,生物潜在可利用态较高,生物不可利用态含量最高;现有环境条件下的土壤Cd比较稳定,生物可利用性较低,对农作物的危害性较小。     

西北干旱地区地下水放射性环境污染及防治研究--以内蒙古东乌旗地区为例

以东乌旗地区为例，研究了西北地区地下水放射性环境问题。结果表明：东乌旗地区地下水存在严重的放射性污染，花岗岩裂隙水、砂岩承压水和潜水达标率分别为8％、14％和45％；放射性铀、氡污染主要原因为铀矿化扩散成因、淋漓花岗岩成因和蒸发浓缩成因；处理本地区地下水铀污染的合理方法为阴离子交换树脂吸附法；地下水中氡有两面性，一方面饮用水中氡含量超标，给人体带来危害，只需将其露天放置一星期或加温煮沸即可达到饮用水标准；另一方面氡浴又有利于人体的健康。     

简化连续提取法评价污染土壤中Zn、Cd的植物有效性

以0.01 mol·L^-1CaCl₂和0.005 mol·L^-1 DTPA作为提取剂,用简化的3步连续提取法对贵州省赫章县土法炼锌污染土壤中Zn、Cd的形态进行了分析.结果显示,污染土壤中Zn、Cd主要以残渣态的形式存在,CaCl₂提取态和DTPA提取态Zn、Cd平均仅占全量的0.63%、3.91%和10.94%、10.13%.土壤中不同形态Zn、Cd含量与玉米中Zn、Cd含量的相关分析结果显示,CaCl₂提取态金属与玉米中金属含量没有显著的相关关系,而DTPA提取态、残渣态以及总量Zn、Cd与玉米根、茎叶中Zn、Cd含量显著正相关.这些结果表明CaCl₂提取态Zn、Cd对土壤中该元素的植物有效态可能不具重要贡献,而DTPA提取态金属和金属总量在一定程度上能作为评价土壤中元素植物有效性的标准.     

基于表面增强拉曼光谱技术的饮用水中痕量恩诺沙星和环丙沙星快速检测

近年来,抗生素的滥用引发抗生素抗性基因在环境中的传播和扩散,对生态系统与人类健康构成潜在威胁,特别是饮用水中抗生素污染事件的相关报道引发社会极大关注.因此,如何实现应急公共卫生事件中的痕量抗生素快检成为研究热点.基于表面增强拉曼光谱（SERS）技术,并结合磁性固相萃取（MSPE）样品前处理方法,构建了饮用水水样中ng ·L^-1水平喹诺酮类抗生素的快速检测方法.借助于磁性氧化石墨烯复合纳米材料（Fe₃ O₄@SiO₂-GO）的高吸附容量所提供的高富集能力,成功实现了饮用水中1.0 ng ·L^-1恩诺沙星（ENR）和5.0 ng ·L^-1环丙沙星（CIP）的加标检出,回收率在77.5%~91.5%之间,满足当前饮用水水质检测的要求.对于有机基质复杂的湖水等环境水样,萃取材料的选择性尚有待于进一步提升.     

绿色合成纳米氧化铁对污染土壤中镉的钝化研究

虽然绿色合成纳米材料已成功地用于去除废水中的重金属,但利用绿色合成纳米材料钝化土壤中重金属的报道很少.本文利用植物叶提取液制备纳米氧化铁(GION),并将其用于钝化土壤中重金属镉的研究,观察中、短培养周期下对镉钝化的稳定性.实验室条件下设置50%田间最大持水量培养,对照、1%、3%、9%GION 4个处理.分别于第60、120 d采样分析土壤中镉、pH、铁、酶等相关指标的变化.结果表明,GION对土壤中镉有较好的钝化效果,60 d与120 d之间有效态镉的含量无显著差异,说明GION对土壤中镉的钝化作用随时间增长相对稳定.120 d的数据显示,相比对照组,1%、3%、9%GION处理下有效态Cd(0.1 mol·L~(-1) CaCl_2)分别降低了19.1%、16.7%、66.7%,交换态Cd(Tessier法)分别降低了12.5%、18.8%、56.3%.GION能够显著提高土壤的pH和铁的含量.pH提高能够显著降低Cd的有效性.(NH_4)C_2O_4-Fe则分别增加了0.7、1.1、1.9倍,DCB-Fe分别增加了0.4、2.9、6.0倍.另外,随培养时间的延长,(NH_4)C_2O_4-Fe和DCB-Fe增加而HCl-Fe~(2+)含量降低.说明GION影响土壤中铁物种的活性,增强其生物化学过程而转化为更加稳定的形态,该过程将改变镉在土壤中的赋存形态.通过扫描电镜-能谱(SEM-EDS)发现,GION处理残渣态中Fe的含量远高于对照组,说明镉可能随铁进入残渣态.土壤中脲酶和转化酶活性升高而过氧化氢酶则没有显著的变化.该结果说明GION降低了土壤中镉的生物有效性,土壤得以恢复,从而提升了土壤酶活性.综上所述,GION具有环境友好的特点,且对镉具有稳定的钝化作用,可作为一种良好的中低污染重金属污染土壤的修复剂.     

影响镍在新疆荒漠土壤中形态分布因素研究

选择新疆荒漠区某石化污水库周边土壤作为研究对象,采用室内静态吸附和Tessier连续提取技术对影响供试土壤中镍的形态分布和生物有效性因素进行研究。实验结果表明,在100-400 mg/L浓度范围内,随着土壤中加入镍离子量的增加,镍的碳酸盐结合态和铁锰氧化态比例降低,生物有效性系数K呈递减的趋势,当浓度大于250 mg/L时,这种递减趋势趋于平缓;土壤pH值增大,镍的残渣态比例升高,在pH值小于8范围内,生物有效性系数K减小趋势不明显,当pH值大于8时,生物有效性系数K急剧下降;土壤环境离子强度小于0.01 mol/L时,镍的形态分布变化较小,但当离子强度大于0.01 mol/L时,镍向不易被植物吸收的形态转化。     

铀尾矿库渗漏地下含水层中六价铀的几种吸附反应运移模型对比

在铀尾矿地区,溶解态U(Ⅵ)渗漏到含水层中会对周围环境造成严重的威胁.使用反应运移软件PHT3D对U(Ⅵ)在含水层中的迁移和吸附过程进行模拟.结果表明,相比于不考虑吸附情形,考虑吸附的U(Ⅵ)反应迁移阻滞现象明显.线性和Langmuir吸附等温线模型在水动力条件复杂、地球化学条件多变时的模拟效果与表面络合模型相比较差,甚至有时得到与实际相反的结果,这说明了传统Kd吸附经验模型的局限性.由表面络合模型计算得出的分配系数Kd值是时空变化的,其更能反映实际中多变水化学条件下的吸附过程,适合描述复杂的不同水文地球化学条件.     

Potential bioavailability of mercury in humus-coated clay minerals

It is well-known that both clay and organic matter in soils play a key role in mercury biogeochemistry, while their combined effect is less studied. In this study, kaolinite, vermiculite, and montmorillonite were coated or not with humus, and spiked with inorganic mercury (IHg) or methylmercury (MeHg). The potential bioavailability of mercury to plants or deposit-feeders was assessed by CaCl₂ or bovine serum albumin (BSA) extraction. For uncoated clay, IHg or MeHg extraction was generally lower in montmorillonite, due to its greater number of functional groups. Humus coating increased partitioning of IHg (0.5%–13.7%) and MeHg (0.8%–52.9%) in clay, because clay-sorbed humus provided more strong binding sites for mercury. Furthermore, humus coating led to a decrease in IHg (3.0%–59.8% for CaCl₂ and 2.1%–5.0% for BSA) and MeHg (8.9%–74.6% for CaCl₂ and 0.5%–8.2% for BSA) extraction, due to strong binding between mercury and clay-sorbed humus. Among various humus-coated clay particles, mercury extraction by CaCl₂ (mainly through cation exchange) was lowest in humus-coated vermiculite, explained by the strong binding between humus and vermiculite. The inhibitory effect of humus on mercury bioavailability was also evidenced by the negative relationship between mercury extraction by CaCl₂ and mercury in the organo-complexed fraction. In contrast, extraction of mercury by BSA (principally through complexation) was lowest in humus-coated montmorillonite. This was because BSA itself could be extensively sorbed onto montmorillonite. Results suggested that humus-coated clay could substantially decrease the potential bioavailability of mercury in soils, which should be considered when assessing risk in mercury-contaminated soils.     

成都经济生态区大气降尘中镉赋存形态的研究

重金属的生物毒性不仅与其总量有关．更大程度上由其形态分布所决定，不同的形态产生不同的环境效应。为了解城市大气降尘中的镉污染，采用Tessier连续提取法对成都经济生态区内不同区域的24个大气降尘样中镉的赋存形态进行了研究。结果表明，大气降尘中的镉主要以残留态存在;各形态镉在总镉中所占的平均百分比含量的排列顺序依次为：残留态〉碳酸盐结合态〉交换态〉铁锰结合态〉有机结合态（78．907％、8．917％．6．420％、3．419％、2．365％）;交换态镉、碳酸盐结合态镉具有较高生物有效性，铁锰氧化物结合态．有机结合态、残留态这3种形态镉的生物有效性很低。分析得出：汽油和煤的燃烧，以及工厂排放镉能加大城市大气降尘的镉污染。     

污染土壤中重金属的超声波强化EDTA洗脱及形态变化

以EDTA为洗脱剂,对重金属污染土壤进行超声波强化洗脱正交实验,并用Tessier连续提取法研究了洗脱前后Cd、Cu、Pb、Zn的形态变化.结果表明,在EDTA浓度20 mmol·L-1、固液比1∶20、超声波作用时间16 min、超声波功率54%、洗脱次数4次的条件下,对4种重金属洗脱率最大,分别为:Cd 83.6%、Cu 58.8%、Pb 98.0%、Zn 43.0%.在实验所设浓度范围内,随着EDTA浓度的升高,重金属洗脱率均有降低.形态分析结果显示,超声波强化EDTA洗脱能显著降低土壤重金属的残渣态含量.除土壤中Zn残渣态去除率只有5.7%以外,超声波强化EDTA洗脱对土壤中Cd、Cu、Pb的残渣态去除率都很高,分别为81.6%、62.3%、93.8%.     

Changes of Cu, Zn, and Cd speciation in sewage sludge during composting

The potential toxicity risks from heavy metals depend on their chemical speciation. The four stages of the Tessier sequential extraction method were employed to investigate changes in heavy metal speciation （Cu, Zn, and Cd） of sewage sludge during forced aeration composting, and then to identify whether the composting process would reduce or enhance their toxicities. Throughout the composting process, the exchangeable, carbonate-bound, Fe-Mn oxide-bound, and organic matter-bound fractions of Cu were converted to the residual Cu fraction. The organic matter-bound Cu fraction greatly contributed to this transformation. Residual Zn fraction was transformed to the Fe-Mn oxide-bound and organic matter-bound fractions after composting. The residual Zn fraction was a major contributor to the organic matter-bound Zn fraction. The availability of Cu and Zn was reduced by composting such that the risk of heavy metal toxicity decreased with prolonged treatment times. Additionally, attention should be paid to the increased availability of Cd in sewage sludge after composting treatment.     

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO₂) and uranium tetrachloride (UCl₄) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415–475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480–560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Microbial reduction of uranium (VI) by Bacillus sp. dwc-2: A macroscopic and spectroscopic study

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China, was explored using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100 mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH 8.2 under anaerobic conditions at room temperature. Additionally, natural organic matter (NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states (U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy (HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall. These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur.     

膜组合工艺对地下水中铀的去除及其微生物群落特征

含铀地下水因具有放射性和化学毒性对人类健康构成严重威胁,常规工艺有时无法有效去除地下水铀故需增加处理工艺以满足饮用水水质要求.以我国某地膜组合工艺处理工程为研究对象,监测了6个月运行过程中铀去除效果及常规水质参数,并对各工艺阶段出水及生物膜进行样品采集.结合水质分析与高通量测序探讨了不同工艺段出水水质参数变化,微生物群...