纳米TiO2对菲律宾蛤仔消化腺中Cd的蓄积与生化响应的影响

随着纳米科技的发展及纳米颗粒在纺织、食品、太阳能及水处理等各行业的应用,进入水生环境的纳米颗粒对其中痕量金属的生物地球化学循环及其生物学效应的影响受到关注。本文研究了水环境中分布最广泛的纳米二氧化钛(n-TiO2)对镉(100μg·L^-1)在海洋双壳类菲律宾蛤仔体内生物利用性及生物效应的影响,通过14d的暴露实验,在环境真实浓度下研究Cd在蛤仔体内的蓄积量及毒性。暴露期间测定了蛤仔消化腺中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、谷胱甘肽S-转移酶(GST)、丙二醛(MDA)和金属硫蛋白(MT)等生物标志物的活性或含量,同时分析了消化腺中Cd的蓄积。暴露3d后,Cd处理组及n-TiO2+Cd处理组均观测到蛤仔消化腺内Cd含量显著升高(p<0.05),并随时间延长而不断升高。各处理组SOD活性在整个暴露周期内与同期对照组相比均无显著差异。CAT(3d)和GST(7、14d)活性仅在Cd处理组出现显著升高(p<0.05)。Cd处理组在暴露结束时出现MDA含量的显著增加;n-TiO2单独及联合处理组MDA含量显著上升出现在7d后,至暴露结束时与对照组无显著差异。随暴露时间的延长,只有Cd处理组中蛤仔消化腺MT的含量呈现显著升高。结果表明,相同浓度条件下,Cd对蛤仔的亚致死毒性高于n-TiO2,而n-TiO2能够通过抑制Cd的生物积累而减轻后者对蛤仔的毒性,这种影响与n-TiO2对Cd的吸附作用有关。     

Improving estuarine net flux estimates for dissolved cadmium export at the annual timescale: Application to the Gironde Estuary

Dissolved Cd (Cd_D) concentrations along the salinity gradient were measured in surface water of the Gironde Estuary during 15 cruises (2001–2007), covering a wide range of contrasting situations in terms of hydrology, turbidity and season. During all situations dissolved Cd concentrations displayed maximum values in the mid-salinity range, reflecting Cd addition by chloride-induced desorption and complexation. The daily net Cd_D fluxes from the Gironde Estuary to the coastal ocean were estimated using Boyle's method. Extrapolating Cd_D concentrations in the high salinity range to the freshwater end member using a theoretical dilution line produced 15 theoretical Cd concentrations (Cd_D⁰), each representative of one distinct situation. The obtained Cd_D⁰ concentrations were relatively similar (201 ± 28 ng L⁻¹) when freshwater discharge Q was >500 m³ s⁻¹ (508 ≤ Q ≤ 2600 m³ s⁻¹), but were highly variable (340 ± 80 ng L⁻¹; 247–490 ng L⁻¹) for low discharge situations (169 ≤ Q ≤ 368 m³ s⁻¹). The respective daily Cd_D net fluxes were 5–39 kg day⁻¹, mainly depending on freshwater discharge. As this observation invalidates the existing method of estimating annual Cd_D net fluxes, we proposed an empirical model, using representative Cd_D⁰ values and daily freshwater discharges for the 2001–2007 period. Subsequent integration produced reliable Cd_D net flux estimates for the Gironde Estuary at the annual timescale that ranged between 3.8–5.0 t a⁻¹ in 2005 and 6.0–7.2 t a⁻¹ in 2004, depending on freshwater discharge. Comparing Cd_D net fluxes with the incoming Cd_D fluxes suggested that the annual net Cd_D addition in the Gironde Estuary ranged from 3.5 to 6.7 t a⁻¹, without any clear temporal trend during the past seven years. The annual Cd_D net fluxes did not show a clearly decreasing trend in spite of an overall decrease by a factor 6 in Cd gross fluxes during the past decade. Furthermore, in six years out of seven (except 2003), the annual Cd_D net fluxes even exceeded river borne total (dissolved + particulate) gross Cd fluxes into the estuary. These observations were attributed to progressive Cd desorption from both suspended particles and bottom sediment during various sedimentation–resuspension cycles induced by tidal currents and/or continuous dredging (navigation channel) and diverse intra-estuarine sources (wet deposition, urban sources, and agriculture). Provided that gross fluxes remain stable over time, dissolved Cd exportation from the Gironde Estuary to the coastal ocean may remain at the present level for the coming decade and the estuarine sedimentary Cd stock is forecast to decrease slowly.     

Speciation of dissolved copper and cadmium in the Loire estuary and over the North Biscay continental shelf in spring

Dissolved cadmium and copper species were measured in the Loire estuary and the North Biscay Bay continental shelf (France) in spring 2002. Metal behaviours along the salinity gradient, metal fluxes from the Loire system and surface distributions on the continental shelf were described and compared with the ones obtained at a period of higher discharge (i.e., winter 2001). Vertical distributions at different stations were also examined with the aim to assess whether the Loire inputs affect the Cu and Cd speciation over the continental shelf. In the Loire estuary, different metal behaviours were observed from winter. Cu and its various species mostly followed a theoretical dilution line whereas a Cd addition composed of chloro- and organic complexes was observed. According to our estimations, the Cu flux was composed, as in winter, of 40% hydrophobic organic complexes. On the other hand, Cd organic complexes accounted for less in the total dissolved metal flux than they did in winter (55 and 78% for spring and winter, respectively). On the continental shelf, a C₁₈Cu-to-TDCu ratio of 40% was observed in the stratified area under Loire influence. For Cd, the organic fraction was relatively important in the surface waters near the mouth of the estuary and decreased deeper and seaward. Thus, the Cu and Cd speciation on the North Biscay Bay continental shelf are firstly determined by the extent of the estuarine plume. Beyond the estuarine influence, biological processes appeared to be the origin of the observed variations.     

镉同位素分馏及其在示踪土壤镉来源和迁移转化过程中的应用进展

土壤镉污染已成为危害人体健康的主要因素之一,要实现精准、快速和有效地防治土壤镉污染,首先必须厘清土壤中镉的来源及其迁移转化行为。近年来,随着镉同位素分析技术的进步及其分馏机制认识的深入,镉同位素在土壤镉示踪中展示出了巨大的应用潜力。本文在前人研究的基础上,归纳了土壤样品镉同位素分析前处理方法以及测试技术的研究进展。对于基质复杂的土壤样品,高温高压密闭消解和微波消解可以满足其镉同位素测试要求。在分离纯化镉回收率足够、干扰元素去除彻底的情况下,应用多接收电感耦合等离子体质谱(MC-ICP-MS)分析镉同位素并采用标准-样品匹配法、外标法或双稀释剂法进行质量歧视校正,均可获得较高精度的土壤镉同位素组成数据。同时,本文概括了土壤多个潜在镉源的镉同位素组成以及典型过程(风化淋滤、吸附、沉淀/共沉淀、络合)镉同位素分馏方向与程度。结合最新研究成果,总结了镉同位素在示踪土壤镉来源及其迁移转化过程中的应用。在未来的工作中,需进一步开发和优化高精度镉同位素分析方法,建立土壤镉同位素指纹图谱,揭示土壤多组分、多界面过程中的镉同位素分馏机制和特征。     

巯基改性蒙脱石对Cd(Ⅱ)的吸附机理研究

蒙脱石对镉有良好的吸附性,但吸附力较弱,巯基改性蒙脱石可增强对镉的吸附,而关于蒙脱石的巯基改性及改性后对镉的吸附机理研究少见报道.本文以(3-巯丙基)三甲氧基硅烷作为改性剂,采用简单的溶液法对蒙脱石原土(简称MMT)进行巯基改性,并探讨了改性蒙脱石(简称MMT-SH)对镉的吸附机理.红外和X射线衍射表征显示MMT被成功接上巯基.吸附条件实验表明,MMT-SH对Cd(Ⅱ)的吸附效果显著优于原土,对Cd(Ⅱ)的饱和吸附容量是原土的39倍;吸附容量受pH值影响大,受离子强度的影响较大;MMT-SH对Cd(Ⅱ)的吸附作用除了静电吸附、离子交换吸附、羟基配位吸附,还主要存在巯基配位吸附.热力学及动力学实验表明,MMT-SH吸附Cd(Ⅱ)的反应符合Langmiur等温模型和Lagergren二级动力学方程,是易于发生的化学反应;吸附过程的热力学参数(△H、△G、AS)表明此吸附是一个自发的吸热过程.     

福建龙岩中甲铁矿床中铟、镉赋存状态及其综合回收经济评价

福建龙岩中甲铁矿是上世纪60年代探明的海相火山沉积-热液叠加改造型多金属硫化物磁铁矿矿床。随着该矿难选铁矿石选矿技术的突破,最近发现矿石中共(伴)生的分散元素铟、镉含量超过综合利用工业最低品位要求,铟、镉的储量估算均可达大型规模。通过研究铟、镉的赋存状态,认为矿石中尚无铟、镉的独立矿物存在,铟、镉主要与锌呈类质同象存在于闪锌矿的晶格中;铟、镉综合回收经济评价表明,铟、镉在选矿流程中主要走向锌精矿,可在锌的冶炼过程中综合回收,并会获得很好的经济效益。永安—梅县凹陷带内有众多与该矿床类似的铁多金属矿,该矿床共(伴)生铟、镉含量及赋存状态的考察,对区域同类矿床伴生元素的综合利用、提升经济价值有重大意义。     

微波消解-电感耦合等离子体质谱测定玉米中铬、镉、铅

研究了微波消解-电感耦合等离子体质谱（ICP-MS）测定玉米中重金属元素的方法。详细讨论了微波样品溶液制备、质谱仪干扰扣除及校准等,在优化的试验条件下,根据国家标准参考物质（GBW10012）的分析结果评价方法的准确性。方法检出限为：Cd：0.003μg/g,Cr：0.04μg/g,Pb：0.1μg/g,相对标准偏差在2.5%-6.0%之间,加标回收率在90.9%-104.9%之间。     

溴、碘、砷、镉等有益有害元素形态分析技术及生态环境地球化学应用

率先在国土资源领域培育并形成相对稳定的元素化学形态(价态、金属有机化合物等)分析及其生态环境地球化学应用研究团队,采用高效液相色谱-电感耦合等离子体质谱联用技术,开展生态环境地球化学样品中痕量溴、碘、砷、镉、汞、锡、铅、铬、硒等有益有害元素的价态、金属有机化合物等形态分析方法研究,初步建立了有益有害元素形态分析体系。建立的形态分析方法灵敏度高、检出限低,具有创新性和实用性,工作成果在国内外期刊发表论文20篇。形态分析方法在我国环境地球化学研究中得到应用并取得了良好的应用成果,从形态分析水平上表征元素的环境地球化学及其健康效应在国内外属于探索性工作。     

广东省典型铅锌多金属矿床镉的分布特征

以广东省典型铅锌多金属矿床为例,探讨各矿区镉的含量特征及不同类型矿床闪锌矿中镉的含量及锌镉比值分布特点,结果显示,镉富集程度受不同矿区地球化学背景的影响较大;不同矿区镉与锌均表现出相关—强相关关系,表明两者在成矿过程中具有相似的地球化学特征;高镉含量与低锌镉比值叠合区主要位于已知铅锌矿床分布地段,向四周镉的富集程度有所降低;不同矿床的闪锌矿中,镉的富集系数及锌镉比值具明显阶梯性,除受控于闪锌矿的形成温度、颜色及类型外,还与矿区富银关系密切。该研究为了解广东省镉分布特征及镉矿地质评价工作提供了科学依据。     

冀东表层土壤中镉的环境地球化学基线

以土壤环境地球化学研究为主线,以冀东地区13 472 km2为研究区域,将土壤重金属污染元素镉的空间分布规律与环境地球化学机理研究相结合,建立区域土壤环境地球化学基线,选用合适的判别指标判识自然作用过程与人类活动过程对土壤环境的影响。通过对3 287个样品的镉含量的统计分析,结果表明,冀东地区表层土壤中镉的基线值为0.073 mg/kg,镉元素含量大于0.230 mg/kg的样品可能遭受人为污染的影响。地质累积指数分析结果显示,冀东地区49.0%的表层土壤未受镉污染,47.6%的表层土壤在无污染与中度污染之间,2.1%受中度污染,1.2%的表层土壤介于中度污染到强污染之间,只有1%受强污染。污染程度指数分析则显示,冀东地区94.5%的表层土壤未受到镉污染,98.8%的表层土壤污染程度小于2,总污染程度小于0,即总体未受到污染。