Metal toxicity in a sediment-dwelling polychaete: Threshold body concentrations or overwhelming accumulation rates?

We followed the net accumulation of As, Cu and Zn in the deposit-feeding polychaete Arenicola marina exposed in the laboratory to natural metal-contaminated sediments, one exposure leading to mass mortality between day 10 and 20, and the other not causing lethality over a period of 60 days of exposure. The worms showed lower total accumulated metal concentrations just before mortality occurred (<20 days) at the lethal exposure, than after 30 days of exposure to sediments not causing mortality. Moreover rates of accumulation of As, Cu and Zn were significantly higher in the lethal exposure than in the sublethal exposure. Our results show that it is not possible to link mortality to a critical total body concentration, and we add to a growing body of literature indicating that metal toxicity occurs when organisms cannot cope with overwhelming influx and subsequent accumulation rates.     

攀西蔬菜基地蔬菜砷、汞污染安全性评价

系统研究了攀西地区主要蔬菜基地的瓜类、茄果类、根菜类、叶菜类、豆类等五类蔬菜中砷、汞污染及其累积情况。结果表明,这五类蔬菜砷、汞含量都未超过相应产品限量标准,超标率为0％,污染程度都为安全,污染水平为清洁。各蔬菜对As的吸附能力为叶菜类〉根菜类〉豆类〉瓜类=茄果类;各蔬菜对Hg的吸附能力为叶莱类〉瓜类〉茄果类〉根菜类〉豆类。以叶菜类对As,Hg的富积能力最强,综合污染指数明显高于其他蔬菜。     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

纳米Fe3O4覆盖对沉积物-水界面砷释放的影响

为揭示纳米四氧化三铁（nFe₃O₄）覆盖对沉积物溶解态砷（As）和有效态As的钝化效果,在开展室内培养试验的基础上,利用微界面分析技术、高分辨率平衡式间隙水采集技术（HR-peeper）和薄膜扩散梯度技术（DGT）,探究nFe₃O₄覆盖下沉积物氧化还原环境、铁锰含量等因素对As的作用机制.结果表明：在nFe₃O₄覆盖下沉积物pH值较对照组逐渐增大,Eh先减小后增大;nFe₃O₄可以有效去除沉积物溶解态As,最大有效去除率为22%;nFe₃O₄覆盖使得有效态As的平均值降低了2.30mg/L;溶解态As与溶解态Fe （II）、溶解态As与溶解态Mn、有效态As与有效态Fe （II）、有效态As与有效态Mn均存在显著正相关关系（P<0.001）;nFe₃O₄的覆盖可以促进铁铝低结晶状无定形水合氧化态As含量的增加.     

施硅对水稻铁膜砷固定和体内砷转运的影响

水稻铁膜对砷(As)的固定及其体内As的转运深刻影响着糙米中As的累积.施硅(Si)能够抑制水稻对As的累积,然而,施Si如何调控铁膜对As的固定和水稻各部位的As向糙米的转运,相关机制目前尚未十分清楚.以As超标土壤中的水稻铁膜为研究对象,通过开展不同Si处理水平的土壤盆栽试验,研究施Si对水稻根表铁膜固定As和各组织器官中As向糙米转运的影响及作用机制.结果表明,Si2(0.66 g·kg^-1)处理显著提高了水稻根系CAT(1.81倍)、SOD(7.98倍)和POD(1.25倍)酶活性,增加了铁膜中的DCB-Fe含量(44.35%),提高了铁膜的表面粗糙度(108.91%),导致铁膜的DCB-As含量明显升高(88.32%);而且,Si2处理显著增加了水稻根中As的累积率,降低了根和叶对As的转运能力,最终导致糙米中As含量的显著降低(53.12%).施Si增强水稻根表铁膜对As固定的原因可归结于Si促进铁膜的形成和增大铁膜的表面粗糙度,而施Si抑制根和叶中As向糙米的转运则可能与Si竞争水稻体内As的转运蛋白,促进As-巯基络合物形成以及增强As液泡区隔化等...     

锰氧化物负载施氏矿物去除酸性矿山废水中As(III)的性能及机理

施氏矿物是天然的砷吸附剂,但其存在酸性条件下对As(III)吸附性能较弱且无法对As(III)氧化降毒的缺陷. 采用液相沉淀法成功制备出锰氧化物负载施氏矿物(MnO_x@Sch),研究锰负载量、初始pH值和共存离子对MnO_x@Sch去除As(III)的影响,并采用吸附动力学结合XPS、FTIR及TEM等表征探究该过程的机理. 结果表明:在初始pH=3、投加量为0.5 g·L^-1、As(III)初始浓度为1 mg·L^-1的条件下,As(III)与MnO_x@Sch反应后的剩余浓度仅为2.42~3.38 μg·L^-1.MnO_x@Sch去除As(III)受初始pH影响较小,H₂PO₄^-共存时As(III)去除存在明显的抑制作用. MnO_x@Sch 去除As(III)的过程符合准二级动力学方程和颗粒内扩散方程. 液相化学组分和固相产物表征分析显示MnO_x@Sch对As(III)的去除机理可概括为As(III)氧化、静电吸附和络合配位及配体交换. 研究结果可为施氏矿物及其改性材料应用于酸性矿山废水砷污染治理提供理论依据.     

贵州某锑冶炼厂周边农田土壤锑、砷污染与人体健康风险评估

本研究以贵州省独山县某锑冶炼厂周边农田土壤为研究对象,系统采集17个土壤样品,测定了土壤中Sb、As总含量,并采用生理提取试验(PBET)和简化生物可给性提取试验(SBET)两种体外胃肠模拟实验方法分析了土壤中Sb、As的生物可给态含量,基于土壤Sb、As总量和生物可给性(PBET和SBET)评估了研究区锑、砷污染土壤暴露引起的潜在人体健康风险。结果表明:研究区农田土壤锑、砷污染严重,土壤中Sb(55.63±75.59 mg/kg)和As(44.31±38.34 mg/kg)的平均含量均超过贵州省区域背景值和我国农用地土壤污染风险筛选值;土壤中SBET和PBET提取的生物可给态Sb和As含量和计算得到的生物可给性都较低,大多数样品的生物可给性低于40%。相对于元素总量,基于Sb和As生物可给性(PBET和SBET)的人体非致癌风险(HQ和HI)和致癌风险(CR)均显著降低,其中成人和儿童的非致癌风险值均降至安全值范围,但是As的致癌风险除了CR_SBET-成人降至安全水平,CR_PBET-成人、CR_SBET-儿童以及CR_PBET-儿童值仍处于1.0E-06~1.0E-04之间,表明As对当地成人和儿童的潜在致癌风险仍不容忽视,特别是儿童。     

无定形Fe (OH)3 和Fe3 O4 共沉淀态As的化学提取

无定形铁氧化物结合态砷的迁移性和生物可利用性易受环境变化影响.分别以1 mol·L-1盐酸和0.2 mol·L-1草酸铵缓冲溶液为提取剂,以新制备和室温老化(3个月、6个月)的共沉淀态Fe(OH)3-As和Fe3O4-As为提取对象,研究提取时间、液固比、Fe/As摩尔比和室温老化对As提取效率的影响.结果表明,1 mol·L-1盐酸提取Fe(OH)3-As、Fe3O4-As共沉淀时液固比应分别为50、200左右,0.2 mol·L-1草酸铵缓冲溶液提取Fe(OH)3-As、Fe3O4-As共沉淀时需保证加入的草酸根与固相中Fe的摩尔比分别为4、2.5;盐酸和草酸铵缓冲溶液提取时间2 h即可.样品Fe/As摩尔比和室温老化对Fe(OH)3-As共沉淀的溶解提取影响不大,但对Fe3O4-As共沉淀的提取影响比较大,Fe/As摩尔比越大,Fe3O4-As共沉淀越不易被提取;老化时间越长,其中共沉淀的As越不易被溶解提取.值得注意的是:盐酸和草酸铵缓冲溶液提取过程中如果有不溶固相存在,会发生As的再吸附,使无定形铁氧化物共沉淀态砷的测定不准确.     

pH、钙和磷对砷在水稻土中溶解度的影响及表面络合机制解析

为深入理解稻田土壤砷(As)的环境行为,以及不同环境因素对土壤溶液中As有效性的影响机制,通过吸附实验结合天然有机质-电荷分配(NOM-CD)模型分析了pH、 Ca²⁺和PO₄^3-对As在湖南株洲稻田土壤中溶解度和化学形态分布的影响,并揭示其影响机制.结果表明,土壤总As溶解度在pH 6.0左右最低,主要受Ca²⁺、 PO₄^3-、 As(Ⅲ)和As(Ⅴ)的静电作用及位点竞争作用控制;土壤溶液中Ca²⁺浓度的增加会促进As的吸附,降低土壤溶液中As的浓度,尤其在碱性条件下由于Ca²⁺的吸附增加了土壤氧化物表面正电荷,因而土壤溶液中As(Ⅴ)浓度随Ca²⁺浓度的升高明显降低;pH低于5.5时,添加PO₄^3-抑制了土壤As(Ⅴ)的还原,但pH高于5.5后,添加PO₄^3-促进了土壤As(Ⅴ)的还原,并由于PO