铜、砷单一及复合污染对黑藻的毒性效应

通过室内模拟试验,研究了铜(Cu)、五价砷〔As(Ⅴ)〕单一及复合污染对黑藻〔Hydrilla verticillata (L.f.) Royle〕生长、富集Cu和As的能力以及对超氧化物歧化酶(SOD)活性的影响.毒性测试结果表明,Cu和As(Ⅴ)对黑藻的4 d-EC₅₀分别为2和12 μmol/L,单一Cu对黑藻的毒性远高于As(Ⅴ). 复合污染试验结果表明,对于5 μmol/L As(Ⅴ)处理组,低浓度Cu〔c(Cu)<2 μmol/L〕的加入,促进了植物生长,降低了植物体内的As总量〔w(As)〕,同时降低了植物体中占主要部分的三价砷的含量(w〔As(Ⅲ)〕). 对于Cu处理组,As(Ⅴ)的加入同样抑制了黑藻对Cu的富集,SOD活性也高于单一Cu处理,可见在低浓度Cu处理下,Cu和As(Ⅴ)之间存在拮抗作用;而高浓度Cu〔c(Cu)≥2 μmol/L〕的加入,虽然植物对Cu和As(Ⅴ)的富集与单一Cu和As(Ⅴ)处理相比均显著降低,但植物生长受到抑制,SOD活性与单一处理相比也显著降低(P<0.05),因此高浓度Cu处理下,二者对黑藻毒性起协同作用. 总之,黑藻具有应用于处理低浓度Cu和As(Ⅴ)单一及复合污染水体的潜力.      

耐酸砷还原菌Bacillus sp.strain P3-23的分离鉴定及其对高砷土壤砷释放影响

砷还原微生物在原生高砷地下水形成中起关键作用,研究其对不同环境因素改变的响应以及对砷迁移与转化的影响是十分必要的。从石门土壤中分离得到一株耐酸砷还原菌,研究其形态和生理生化特征,通过分子生物学和微生物学手段对其进行系统分类和生理生化特性鉴定,并使用微生物学方法在不同温度、pH值和电子供体条件下进行培养,探究其对环境因素波动的适应能力,检测菌株对高砷土壤砷释放的影响。实验结果表明:该耐酸砷还原菌为芽孢杆菌属(Bacillus)成员,故命名为Bacillus sp.strain P3-23(以下简称P3-23);菌株P3-23最适宜的生长温度为30℃,在pH值为3.5~7.5范围内均可生长且具有砷还原能力,能够利用乳酸钠、丙酮酸钠、柠檬酸钠、酵母味素、丙三醇、葡萄糖、蔗糖为电子供体;菌株P3-23能够在72 h内完全还原2.0 mM As(Ⅴ)且菌液浓度呈上升趋势,具有强耐砷能力,40.0 mM砷存在条件下仍能生长;菌株P3-23促进土壤中砷释放能力较强,砷形态分析显示释放的可溶性砷中As³⁺占比达83.3%以上。菌株P3-23的分离不仅丰富了人们对砷还原微生物的认识,也说明砷还原微生物对不同环境因素胁迫具有相应的应答机制,预示着其可能存在于极端环境中。对不同环境中砷还原微生物进行研究,在完善砷的生物地球化学循环模式的同时有助于砷污染机制及砷修复生物手段的探索。     

纳米二氧化钛增强五价砷对丰年虾的慢性毒性作用

为探究长期暴露下人工纳米材料与其他污染物的联合慢性毒性效应,考察了纳米二氧化钛(titanium dioxide nanoparticles,nano-TiO₂)与五价砷〔arsenate,As(Ⅴ)〕单独或联合暴露对丰年虾(Artemia salina)的慢性毒性效应,观察其存活率、体长、肠道形态及超微结构变化,同时测定了丰年虾对As的累积以及As在丰年虾亚细胞组分中的分布情况. 结果表明:①28 d低剂量As(Ⅴ)暴露导致丰年虾存活率降低, 肠道形态及肠道超微结构损伤,且nano-TiO₂与As(Ⅴ)联合暴露组的毒性效应增强. ②与As(Ⅴ)单独暴露组相比,nano-TiO₂存在条件下丰年虾在暴露前期(第7和14天)对As的摄入及排泄均增加;而暴露后期(第21和28天),nano-TiO₂促进丰年虾排泄As的效应减弱,导致联合暴露组中丰年虾体内As的累积显著增加(P < 0.05). ③与As(Ⅴ)单独暴露组相比,联合暴露组中As在生物解毒组分——热稳定蛋白(heat-stable protein,HSP)组分中的占比下降. 在暴露的第14、21和28天时,联合暴露组中As在HSP组分中的占比较As(Ⅴ)单独暴露组分别显著降低了39.83%±9.54%、43.27%±5.29%和50.91%±7.60%(P均小于0.05). 研究显示,nano-TiO₂可能会抑制丰年虾对As的解毒作用,从而导致As毒性上升.      

Effect of ionic strength on adsorption of As（Ⅲ） and As（Ⅴ） on variable charge soils

The study was to investigate the adsorption behavior of arsenite (As(Ⅲ)) and arsenate (As(Ⅴ)) on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at different ionic strengths and pH with batch methods. Results indicated that the amount of As(Ⅲ) adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As(Ⅲ) was mainly adsorbed on soil positive charge sites through electrostatic attraction under the acidic condition. Moreover, intersects of As(Ⅴ) adsorption-pH curves at different ionic strengths (a characteristic pH) are obtained for both soils. It was noted that above this pH, the adsorption of As(Ⅴ) was increased with increasing ionic strength, whereas below it the reverse trend was true. Precisely the intersect pH was 3.6 for Haplic Acrisol and 4.5 for Rhodic Ferralsol, which was near the values of PZSE (soil point of zero salt effect) of these soils. The effects of ionic strength and pH on arsenate adsorption by these soils were interpreted by the adsorption model. The results of zeta potential suggested that the potential in adsorption plane becomes less negative with increasing ionic strength above soil PZSE and decreases with increasing ionic strength below soil PZSE. These results further supported the hypothesis of the adsorption model that the potential in the adsorption plane changes with ionic strength with an opposite trend to surface charge of the soils. Therefore, the change of the potential in the adsorption plane was mainly responsible for the change of arsenate adsorption induced by ionic strength on variable charge soils.     

Fe(II)、Fe(III)对砷与不同分子量腐植酸络合性能的影响

以腐植酸（HA）代表天然有机质,采用平衡透析和超滤的方法研究铁离子（Fe （II）、Fe （III））对不同分子量HA与砷离子（As （V）、As （III））络合作用的影响,并利用红外光谱（FT-IR）表征其络合特征.结果发现,Fe （II）和Fe （III）均能增强HA络合As能力,且对As （V）络合能力的增强作用大于As （III）;pH值显著影响HA络合As能力;溶解性有机碳（DOC）浓度由5mg/L增大到200mg/L,As络合百分比随之增加,此时HA-Fe （III）络合As （III）百分比最大,为24.55%;初始As浓度由10μg/L增加1000μg/L,As络合百分比随之降低,其中HA-Fe （III）络合As （III）百分比最低,为3.11%.相同环境条件下,分子量>100kDa络合As百分比最大,其中HA-Fe （II）络合As （III）的百分比最高为26.43%;分子量小于10kDa的HA络合As百分比明显高于其他分子量的HA.Fe的增强作用主要源于Fe与羧基形成桥梁再与As络合形成三元络合物.     

Phylogenetic analysis and arsenate reduction effect of the arsenic-reducing bacteria enriched from contaminated soils at an abandoned smelter site

Microbial reduction of As(V)(i.e.,arsenate)plays an important role in arsenic(As)mobilization in aqueous environment.In this study,we investigated As(V)reduction characteristics of the bacteria enriched from the arsenic-contaminated soil at an abandoned smelter site.It was found that As(V)was completely reduced to As(III)(i.e.,arsenite)in 21 h.After 3-d incubation,a yellow solid was precipitated and the concentration of As(III)decreased sharply.After 150 h incubation,ca.65%of soluble arsenic was removed fro...     

不同pH条件下As还原对砷释放的影响实验研究

通过考察不同pH条件下Fe(Ⅲ)-A(sⅤ)体系和Fe(Ⅲ)-As(Ⅲ)体系各Fe形态、As形态、以及体系ORP的变化,考察不同pH条件下As还原对砷释放的影响。实验结果表明:在pH为3⁵左右范围内,Fe(Ⅲ)-A(sⅤ)体系和Fe(Ⅲ)-A(sⅢ)体系中的Fe(Ⅲ)均发生部分絮凝沉淀,在水样pH为65左右范围内,Fe(Ⅲ)-A(sⅤ)体系和Fe(Ⅲ)-A(sⅢ)体系中的Fe(Ⅲ)均发生部分絮凝沉淀,在水样pH为6¹0范围内,Fe(Ⅲ)-As(Ⅲ)体系中Fe(Ⅲ)的絮凝沉淀较Fe(Ⅲ)-As(Ⅴ)体系明显。Fe(Ⅲ)-As(Ⅴ)体系与Fe(Ⅲ)-A(sⅢ)体系中As总随pH的变化趋势基本一致,但是Fe(Ⅲ)-A(sⅢ)体系As总的浓度水平要比Fe(Ⅲ)-A(sⅤ)体系的浓度水平要高。结果表明:同等pH环境条件下,如果A(sⅤ)被还原成A(sⅢ),则Fe(Ⅲ)-As体系中就会出现As的释放,且不同pH条件下对应的As总的差值即可反映出当A(sⅤ)还原成A(sⅢ)时Fe(Ⅲ)-As体系中所释放的砷的量。     

钛改性锰矿的除砷效果及机理研究

天然锰矿是一种廉价、易得的除砷矿物材料,为了进一步提高天然锰矿的除砷效果和吸附容量,采用TiCl4对广西桂林天然锰矿进行改性,并对其改性的条件进行优化。实验结果表明最佳的改性条件为:TiCl4浓度为10 mg/L,浸泡时间为18 h,pH=3.05,振荡吸附时间为1 h。与天然锰矿的去除效率(82.95%和77.93%)相比,改性锰矿对As(Ⅲ)和As(Ⅴ)去除率分别可达94.87%和99.31%,相应的饱和吸附量分别为3.48 mg/g和3.27 mg/g,较天然锰矿各自提高了1.25 mg/g和1.21 mg/g。改性锰矿对As(Ⅲ)的吸附符合Freundlich等温吸附模型,对As(Ⅴ)的吸附更符合Langmuir等温吸附模型。     

Effect of external and internal phosphate status on arsenic toxicity and accumulation in rice seedlings

Phosphorus (P) deficiency is thought to exacerbate the arsenic (As) phytotoxicity in paddy rice. The experiments were conducted to investigate the e ects of external phosphate supply on As accumulation in rice and its toxicity under phosphate deficiency conditions. Rice seedlings pretreated with a phosphorus deficient nutrient solution (–P) for 14 d accumulated more As than those pretreated with a normal phosphorus supply nutrient solution (+P). Rice protreated with –P showed As toxicity symptoms after being exposed to 50 mol/L arsenate for 4 h, while +P rice did not show any toxicity symptoms. Arsenic toxicity symptoms can be alleviated by increasing external P concentrations. The arsenate uptake rate and accumulation corresponded with the As toxicity in rice plants. Arsenic concentrations in rice roots decreased with increasing external phosphate concentrations. The lowest As accumulation and the highest P accumulation were found when the external P concentration reached 100 mol/L. In short, P deficiency increased the sensitivity of rice to arsenate and increasing of external phosphate supply could alleviate As toxicity.     

高砷地下水中砷的形态检测

地下水中砷污染严重影响着人类的健康,砷的生态毒理效应主要取决于其存在形态。文章用阴离子交换柱对内蒙古杭锦后旗高砷地下水在现场进行分离,在室内用原子荧光光度计进行检测。总砷浓度范围为80~1172μg/L,其中A(sⅢ)浓度百分含量为75.37%~92.39%,A(sⅤ)和颗粒态砷浓度百分含量分别为0.56%~13.87%、5.87%~20.65%。形态分析结果表明,该地区主要是还原环境,且颗粒态砷占有一定的比例,这对于进一步研究砷的去除和砷的地球化学行为有一定的指导意义。     

A(sⅢ)和A(sⅤ)对小球藻(Chlorella sp).的生长影响研究

砷是广泛存在于自然界中最常见的毒性污染物,包括土壤,沉积物,水体,大气层,甚至生物体,毒性极强。环境中砷的污染严重威胁人类的健康,已被视为一个全球性的公共卫生问题。为了研究砷对小球藻的生长影响,文章通过实验室培养方式,选取了6个不同浓度的As(Ⅲ()0.5、1.0、2.0、5.0、10.0、20.0 mg/L)和As(Ⅴ()1.0、5.0、10.0、20.0、50.0、100.0 mg/L)的培养处理,以在680 nm下小球藻的吸光度(OD680)作为衡量因子,对小球藻Chlorella sp(.100 ai)在不同浓度砷离子的培养液中的细胞密度进行了试验,整个实验共进行了7 d。结果表明,As(Ⅲ)和As(Ⅴ)浓度分别在10.0 mg/L和20.0 mg/L以上时抑制100 ai细胞生长,导致其密度下降。用概率统计方法计算得到A(sⅢ)对100 ai的96 h半数有效抑制浓度EC50值为25.79 mg/L。参照藻类生长抑制评价标准,A(sⅢ)对100 ai的毒性比A(sⅤ)大。     

药用植物三七对土壤中砷的累积特征及其健康风险

三七[Panax notoginseng(Burk.)F.H.Chen]是我国传统珍贵草本药用植物.通过野外调查和室内分析相结合的方法,研究了云南文山三七种植区土壤砷污染现状,揭示了三七对土壤中砷的吸收转运规律并分析其健康威胁.结果表明,所调查的三七种植区土壤砷含量范围为6.9～242.0 mg·kg-1,其中,48%...     

植物超富集砷机制研究的最新进展

砷污染是全球环境热点问题之一,土壤砷污染治理是一个急需解决的难题.随着不同砷超富集植物的发现,植物修复技术因其投资和维护成本低、不易造成二次污染等优点而成为国际学术界研究的热点和前沿领域.深入理解超富集植物体内砷代谢和富集机制是有效利用植物修复技术来治理砷污染土壤的关键.近年来,植物超富集砷机制的研究取得了很大进展.已有的研究结果证明,蜈蚣草(P.vittata)对砷的吸收和转运能力显著高于非超富集植物,转运到地上部的砷主要储存在羽叶细胞的液胞中;蜈蚣草具有很强的抗氧化胁迫能力和五价砷(As(Ⅴ))还原能力;菌根共生有利于蜈蚣草的生长和砷的富集.有关植物超富集砷机制的分子生物学研究也取得了可喜的进展.砷酸盐还原酶基因(PvACR2)和植络素合成酶基因(PvPCS1)都被克隆并表征,cTPI同源基因(PV4-8)也被证明具有将As(Ⅴ)还原成三价砷(As(Ⅲ))的功能.尽管植物超富集砷机制的研究取得了迅速进展,但至今学术界仍没有全面理解为什么这些蕨类植物具有超富集砷的功能,相关功能基因、酶和转运蛋白的研究有待进一步深入.     

中草药砷含量特征及其健康风险初步评价

通过野外采样和室内分析相结合的方法,对13种河北省主要地产中草药中砷的含量特征及其分布规律进行了研究,并对中草药中砷的人体健康风险进行了初步评价.13种地产草药分三类采集:中草药种植区的药材、以及相应市场销售的半成品和饮片.结果表明,以地下部入药的各种类中草药砷含量平均值在0.14～0.54 mg/kg之间,以地上部入药的中草药,祁菊花砷含量平均值为1.42 mg/kg,其它种类在0.09～0.27 mg/kg之间.根据《药用植物及制剂外经贸绿色行业标准》对总砷的限量(2.0 mg/kg),以地下部和地上部入药草药的超标率分别为3.27%(n=153)和9.09%(n=44),全部样品的总超标率为4.57%(n=197);直接采集的所有中草药样品砷含量范围在0.03～0.73 mg/kg,全部符合限量标准,而市场购买的半成品及饮片砷含量范围在0.05～7.05 mg/kg,其超标率为6.36%,来源于市场的草药砷含量显著高于种植区直接采集的中草药(p0.05);从13种草药隶属的科属分析,菊科草药砷含量范围较宽,在0.08～7.05 mg/kg,平均值为0.87 mg/kg,而其它6种科属砷含量的平均值范围在0.21～0.41 mg/kg,且各科75%的样品砷含量0.5 mg/kg,相比菊科样品,其药用安全性较高;通过服用半成品及饮片得到砷的日摄入量为0.90～19.7μg/d,其占每日允许摄入量ADI(allowable daily intake)的比值范围在0.70%～15.4%之间,其砷的健康风险显著大于服用采自种植区的原药(p0.05),说明草药饮片中砷对人体的健康风险不容忽视.     

Arsenic uptake and transport of Pteris vittata L. as influenced by phosphate and inorganic arsenic species under sand cu｜ture

In order to understand the similarity or difference of inorganic As species uptake and transport related to phosphorus in As-hyperaccumulator, uptake and transport of arsenate (As(Ⅴ)) and arsenite (As(Ⅲ)) were studied using Pteris vittata L. under sand culture. Higher concentrations of phosphate were found to inhibit accumulation of arsenate and arsenite in the fronds of P. vittata. The reduction in As accumulation was greater in old fronds than in young fronds, and relatively weak in root and rhizome. Moderate increases, from 0.05 to 0.3 mmol/L, in phosphate reduced uptake of As(Ⅲ) more than As(Ⅴ), while the reverse was observed at high concentrations of phosphate (≥ 1.0 mmol/L). Phosphate apparently reduced As transport and the proportion of As accumulated in fronds of P. vittata when As was supplied as As(Ⅴ). It may in part be due to competition between phosphorus and As(Ⅴ) during transport. In contrast, phosphate had a much smaller effect on As transport when the As was supplied as As(Ⅲ). Therefore, the results from present experiments indicates that a higher concentration of phosphate suppressed As accumulation and transport in P. vittata, especially in the fronds, when exposure to As(Ⅴ); but the suppression of phosphate to As transport in the root or rhizome may be insignificant when P. vittata when exposure to As(Ⅲ) under sand culture conditions. The finding will help to understand the interaction of P and As during their uptake process in P. vittata.     

Effects of arbuscular mycorrhizal fungi inoculation on arsenic accumulation by tobacco (Nicotiana tabacum L.)

A pot experiment was conducted to study the e ects of arbuscular mycorrhizal (AM) fungi (from contaminated or uncontaminated soils) on arsenic (As) uptake of tobacco (Nicotiana tabacum L.) in As-contaminated soil. Mycorrhizal colonization rate, dry weight, As and P uptake by plants, concentrations of water-extractable As and As fractions were determined. A low mycorrhizal colonization rate (< 25%) was detected. Our research indicated that AM fungi isolated from polluted soils were no more e ective than those from unpolluted soils when grown in symbiosis with tobacco. No significant di erences were observed in roots and stalks dry weights among all treatments. Leaves and total plant dry weights were much higher in Glomus versiforme treatment than that in control treatment. As contents in roots and stalks from mycorrhizal treatments were much lower than that from control treatment. Total plant As content exhibited the same trend. P concentrations in tobacco were not a ected by colonization, nor were stalks, leaves and total plant P contents. Roots P contents were remarkably lower in HN treatments than in other treatments. Meanwhile, decreased soil pH and lower water-extractable As concentrations and higher levels of As fraction bound to well-crystallized hydrous oxides of Fe and Al were found in mycorrhizal treatments than in controls. The protective e ect of mycorrhiza against plant As uptake may be associated with changes in As solubility mediated by changing soil pH. These results indicated that under As stress, proper mechanisms employed by AM fungi can protect tobacco against As uptake. Results confirmed that AM fungi can play an important role in food quality and safety.     

Removal of trace arsenic（V） and phosphate from water by a highly selective ligand exchange adsorbent

The ligand exchange adsorbent could be used to remove the toxic arsenic(V) and phosphate efficiently from water even in the presence of foreign anions and possible to apply in chemical industry.     

Changes in hair arsenic concentration in a population exposed to heavy pollution： Follow-up investigation in Chenzhou City, Hunan Province, Southern China

Follow-up investigation on hair arsenic concentration was conducted in an arsenic heavily polluted area of southern China in 2002 and 2006.The results showed that the geometric mean of hair arsenic concentration decreased from 2.95 mg/kg in 2002 to 1.78 mg/kg in 2006,when the percentage of the population with levels over 1 mg/kg only decreased from 93.4% in 2002 to 80.5% in 2006.Over this four-year period,the population with high arsenic concentrations decreased significantly while there was no obvious chan...     

砷超富集植物蜈蚣草中磷和钙的亚细胞分布及其与耐砷毒的关系

为了在研究砷超富集植物蜈蚣草中磷和钙的亚细胞分布,并探讨其与蜈蚣草耐砷毒的关系进行了试验研究.结果表明,蜈蚣草吸收的磷主要分布在胞质组分中(平均占各部位总磷含量的44%以上),吸收的钙主要分布在细胞壁组分中(平均占各部位总钙含量的48%以上).与低钙(0.03和2.5 mmol·L-1)处理相比,高钙(5.0 mmol·L-1)处理时,根部的胞质组分和叶柄的细胞器组分中磷含量较高.各器官的亚细胞组分中钙含量随着介质中添加钙浓度的提高而增加.介质钙浓度过高会抑制蜈蚣草的生长.在加砷处理下,根部和叶柄细胞壁组分的磷含量有所减少,但地上部细胞器组分的磷含量及其含磷总量占植株含磷总量的相对比例、根部细胞壁组分的钙含量增加.蜈蚣草自主调节磷和钙的亚细胞水平分布可能是其耐砷毒的机制之一.     

Biogeochemical reductive release of soil embedded arsenate around a crater area (Guandu) in northern Taiwan using X-ray absorption near-edge spectroscopy

This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan,using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry.Total arsenic (As) concentrations in the soil were more than 200 mg/kg.Over four months of laboratory experiments,less than 0.8% As was released into solution after reduction experiments.The 71% to 83% As was chemically reduced into arsenite (As(III)) and partially weathering into the soluble phase.The kinetic dissolution and re-precipitation of As,Fe,Pb and sulfate in this area of paddy soils merits further study.