金昌市郊农田土壤Cu,Zn,Ni形态分布特征与生物有效性评价

通过野外调查和室内测试分析,研究了金昌市郊农田土壤重金属Cu,Zn和Ni的形态特征,并以麦粒中重金属含量为重点进行了Cu,Zn和Ni的生物有效性评价.结果表明,研究区域土壤重金属Cu和Ni污染严重;Cu的主要存在形态为有机结合态,Zn的主要存在形态为残渣态,而Ni的主要存在形态为潜在可利用态;三种元素的生物有效性大小顺序为NiZnCu.对麦粒中重金属健康风险进行评价反映出麦粒中Ni含量对人体健康风险较大,而Cu和Zn对人体健康风险较小.逐步回归分析结果表明,农田土壤中Cu可交换态和碳酸盐结合态对麦粒中Cu含量贡献最大,而对麦粒吸收Zn和Ni贡献最大的形态分别为Zn的碳酸盐结合态和Ni的可交换态、碳酸盐结合态、铁锰氧化态和有机结合态.土壤重金属Cu,Zn和Ni各形态分配系数较总量和各形态含量更适合表征本研究区域土壤重金属的生物有效性.     

硅酸盐、腐殖酸对Cr污染土壤中小白菜生理及吸铬量的影响

针对在铬污染区土壤中的叶菜类吸铬量是果菜类2~3倍,以及硅酸盐或腐植酸在重金属污染土壤上的最佳施用量研究较少的问题,为保障蔬菜的品质安全,文章通过土壤盆栽试验,研究硅酸盐、腐殖酸不同用量对Cr污染土壤中小白菜(Brassica Chinensis)生理指标和吸铬量的影响.结果表明,施低质量分数的硅酸盐(1.0 g·kg-1)效果最佳,既能提高受Cr污染小白菜的生物量、叶绿素相对含量,又能减轻Cr毒害对抗氧化酶系统中SOD酶活性的抑制,缓解小白菜受到的过氧化胁迫,有效降低小白菜吸铬量;高质量分数硅酸盐(2.0 g·kg-1)对生长产生抑制.腐殖酸在设计的3个质量分数水平上均不能有效降低小白菜吸铬量,对生长的促进作用也不明显.     

某铀矿区农田土壤重金属生物有效性分析

为探究某铀矿区附近农田土壤的重金属生物有效性,以该铀矿采矿区、冶炼厂和尾矿坝附近农田土壤为研究对象,分析土壤理化性质并采用经改良后的BCR四步提取法对土壤重金属Pb、Cd、Cr、Cu和U生物有效性进行评估。结果表明:研究区农田土壤偏酸性;不同区位农田土壤有机质含量由大到小依次为尾矿坝、冶炼厂和采矿区;重金属赋存形态主要为残渣态;重金属元素Pb、Cd、Cr和Cu生物有效态含量分别占其总含量的27%～42%,放射性核素U生物有效态含量为U总含量的43%～45%;不同区位农作物对重金属Cr、Cd、Cu和Pb富集系数由大到小依次为采矿区、冶炼厂和尾矿坝;各区位农作物对U的富集效果均最强。综上,研究区农田土壤重金属生物有效性受pH值、有机质含量及重金属生物有效态含量等因素的综合影响,重金属生物有效性越强,其引起的生态风险越大;不同区位农田土壤中重金属Cr、Cd、Cu和Pb生物有效性由大到小依次为采矿区、冶炼厂和尾矿坝;不同区位农田土壤重金属中U的生物有效性均最强;由于受提炼铀矿石的影响,冶炼厂相较于其他研究区域具有更强的U生物有效性;虽然尾矿坝农田农作物对重金属元素的富集效果较差,但考虑到该区位土壤重金属含量较大,其带来的生态风险仍值得关注。研究结果可为今后该矿区重金属污染的科学生物防治提供重要理论依据。     

秸秆生物炭修复电镀厂污染土壤的效果和作用机理初探

以某电镀厂污染场地重污染区域土壤为研究对象,利用秸秆生物炭对污染土壤进行稳定化试验,研究不同生物炭添加量(0、10、30、50、70和100 g.kg-1)条件下土壤中重金属全量和形态变化。结果表明,秸秆生物炭能够改变污染土壤中重金属的形态分布,对该污染土壤有明显的稳定化作用。其中对铬的作用效果最明显,随生物炭添加量的增加,残渣态铬含量明显上升,100 g.kg-1生物炭添加量处理残渣态铬含量较对照(1 098.75 mg.kg-1)增幅最大,增加59.51 mg.kg-1;对铜和镍的稳定化效果受添加量的影响,当生物炭添加量分别在70和30g.kg-1以上时,对铜和镍有一定稳定化作用;对该污染土壤中锌则无明显稳定化作用。当生物炭添加量为50 g.kg-1时,4种重金属残渣态总量较对照(1 745 mg.kg-1)明显增加,为1 805.95 mg.kg-1,添加量也较为合理。     

熟污泥改良土壤中Cd的形态分布特征和生物有效性

通过苜蓿盆栽实验和Tessier五步提取法,研究了不同比例的堆肥污泥施入黄土后,土壤中Cd的形态分布和生物有效性及重金属在施污土壤-苜蓿中的迁移转化规律。结果表明：不同比例的污泥施入黄土后,随着污泥施入量的增加,土壤中Cd的主要赋存形态由对照组的不可利用态(残渣态)向潜在有效态(铁锰氧化态)转化,污泥的施入提高了重金属Cd的生物有效性;苜蓿的种植对施污根际土中Cd的活性产生了钝化作用,使施污黄土根际土壤中潜在有效态Cd主要向不可利用态的Cd转化;苜蓿各器官对Cd均有富集和转移能力,苜蓿各部位重金属Cd含量的分布规律为：根部>茎叶部;线性回归分析结果表明：碳酸盐结合态Cd是苜蓿茎叶部和根部吸收Cd的主要贡献形态;因此在实际生产时须严格控制污泥的施用量,以避免Cd在苜蓿体内富集危害动物和人体健康。     

不同钝化剂对土壤环境中重金属有效性和微生物群落的影响

以云南省澜沧拉祜族自治县铅矿区农田污染土壤为研究对象,采用土培实验的方法,研究生物炭、腐殖土和海泡石单施及配施条件下,土壤Pb、Zn和Cd有效态含量、重金属形态分布及微生物群落的变化.结果表明,腐殖土和生物炭改良剂均能有效地降低生物有效态Pb、Zn和Cd的含量,低剂量海泡石的添加修复效果不明显.其中,腐殖土的施入使土壤...     

施用改良剂对岩溶地区矿山污染农田土壤中锌生物有效性的影响

以玉米（ZeamaysL．）为研究对象,采用盆栽试验,观测在重金属锌污染的土壤（总锌含量为1412．1mg·kg0）上施用不同改良剂（石灰、石灰＋泥炭、石灰＋胡敏酸钠、石灰＋泥炭＋硅肥、石灰＋胡敏酸钠＋硅肥,分别简称S、SN、SH、SNG、SHG）对土壤锌形态、生物有效性及其在作物中富集的影响。结果表明,施用各种改良剂均显著提高土壤pH值,显著降低土壤弱酸可溶态锌和可还原态锌含量,提高可氧化态锌和残渣态锌含量;提高玉米生物量和产量,增产效果为SHG〉SNG〉SH〉SN〉S。施人改良剂可显著降低锌在玉米不同部位的吸收和转运,植株根、茎、叶、籽粒锌富集明显下降,以SHG、SNG的效果最明昂．S的效果最小。     

水稻不同生育期土壤砷形态分布特征及其生物有效性研究

采用田间原位试验和Tessier连续提取方法,在水稻（Oryza sativa L.）不同生育期研究了重金属复合污染高、中、低3个水平下的土壤砷的形态分布特征及其生物有效性。结果表明：在水稻不同生育期中,土壤各种形态的砷质量分数均表现为高污染水平土壤〉中等污染水平土壤〉低污染水平土壤;土壤中砷在水稻整个生育期均以残留态为主,占90%以上,交换态砷所占比例最低,不到0.5%;不同形态砷之间大都显著正相关,但是两种有效性较高的砷形态（交换态和碳酸盐结合态）与有机态砷之间的相关性较差;土壤砷的生物有效性表现为高污染水平土壤〉中等污染水平土壤〉低污染水平土壤,且随着水稻生育期的延长,土壤砷的生物有效性逐渐升高。     

生物炭和熟石灰对土壤镉铅生物有效性和微生物活性的影响

以南京近郊某蔬菜基地土壤为研究对象,采用盆栽试验方法,研究熟石灰和生物炭两种钝化剂对镉铅复合污染土壤修复效果以及对土壤微生物活性的影响.结果表明,施加熟石灰和生物炭能够增加土壤pH和有机碳等养分含量,促进Cd、Pb由酸溶态向还原态和残渣态转化,降低Cd、Pb有效态含量.与对照处理相比,熟石灰和生物炭5.0%用量下,Cd有效态含量(DTPA、TCLP和CaCl_2等3种提取态)分别下降37.74%—41.46%和22.22%—31.71%,Pb有效态含量分别下降45.59%—52.82%和35.47%—41.94%.生物炭的施用提高了土壤微生物量碳氮和微生物群落功能多样性,促进微生物对碳源的利用能力,其中生物炭5.0%用量下土壤微生物活性最高.熟石灰和生物炭的添加显著降低小白菜可食部位和根部对Cd、Pb的富集,与对照处理相比,可食部位Cd、Pb含量分别下降7.14%—47.62%和45.93%—74.82%,但所有添加钝化剂处理小白菜可食部位含量均超出国家安全食用标准.     

植物对污灌区土壤锌形态的影响

通过大田试验研究种植5种植物(玉米、向日葵、大豆、高粱、菊花)对污灌区土壤锌形态的影响.结果表明,污灌区土壤中锌含量均未超过国家二级标准,且主要以残留态存在.土壤中各形态锌与种植前相比,除可交换态锌呈增加趋势,其余各形态锌均呈下降趋势.其中可交换态锌在向日葵土壤中增加最明显,达24.19%;碳酸盐结合态锌在玉米土壤中下降最明显,达47.68%;铁锰氧化物态锌和残留态锌在菊花土壤中下降最明显,分别达35.65%、27.46%;总锌和有机结合态锌在向日葵土壤中下降最明显,分别达15.68%、44.23%.土壤中可交换态锌含量与植物籽粒中锌含量显著相关(P<0.05),适于用作土壤锌污染的生物评价指标.土壤中锌的生物活性系数与种植前相比,在玉米、高粱和菊花土壤中呈降低趋势,其中在玉米土壤中降低最明显,达31.43%,在大豆和向日葵土壤中呈增加趋势.总之,向日葵籽粒中重金属锌含量超出食品中锌限量标准(GB13106-1991),不宜在污灌区种植;玉米、高粱、大豆等植物籽粒中重金属锌含量均未超出食品中锌限量卫生标准(GB13106-1991),可以在污灌农田长期种植.     

铬离子对藻类生长的影响

利用自然光照条件,在不同铬离子质量浓度下,对5种藻类的生长进行了实验研究.研究结果表明:5种藻类在不同的光波长下,其吸收光谱存在两个最强的吸收区: 420～440 nm的蓝紫光部分和660 nm 的红光部分;在不同铬离子质量浓度0～20.63 mg·L-1范围内,5种藻类生长受到不同程度的抑制,其耐受性也尽不相同,经过分析和比较后得出5种藻类对铬的耐受性大小顺序为:微囊藻(Microcystis)＞水华鱼腥藻(Anabaena flos-aquae)＞细长聚球藻(Synechococcus elongatus)＞斜生栅藻(Scenedesmus obliquus)＞蛋白核小球藻(Chlorella pyrenoidose).     

Carbon paste electrode modified with chromium thiopental for the potentiometric flow injection analysis of chromium (III)

A chemically modified carbon paste electrode for chromium (III) based on the formation of ion-association complex of chromium with 5-ethyl-6-oxo-5-pentan-2-yl-sulfanyl-pyrimidin-4-olate (thiopental, THP) as electroactive ion-exchanger (Cr-THP) was prepared and investigated. The electrode has a linear dynamic range of 1.7?×?10^?6–1.3?×?10^?2?mol?L^?1, with a Nernstian slope of 19.6?±?0.5?mV per decade and a detection limit of 9.0?×?10^?7?mol?L^?1. It has a fast response time of <15?s and can be used for at least 7 weeks without any considerable divergence in potential. The proposed sensor revealed good selectivity for Cr(III) over a wide variety of mono-, di-, and trivalent cations and could be used in the pH range of 2.3–6.5. The proposed electrode was used in batch measurements and in flow injection analysis. The Cr-CMCPE was successfully applied for the determination of Cr(III) in real samples (wastewater of hot dip galvanizing unit and alloys). The present electrode was also used as an indicator electrode in potentiometric titration of Cr(III). The results were highly satisfactory.     

Biochemical speciation in chromium genotoxicity

The biochemical speciation of chromium compounds in mammalian cells is discussed with respect to uptake, metabolism, DNA binding and damaging. Whereas soluble hexavalent chromium is taken up rapidly and accumulated intracellularly after its reduction, compounds of trivalent chromium penetrate biomembranes about three orders of magnitude slower. Cr(VI) after its uptake is metabolised by electron donating compounds via Cr(V) to Cr(III) compounds. Chromium from various Cr(III) compounds, but not chromate, binds to chromatin in isolated cell nuclei. The DNA‐protein crosslinks and DNA strand breaks observed in rat liver and kidney after chromate administration are also found in vitro, when Cr(III) compounds (but not chromate) interacts with isolated nuclei. In the Chinese Hamster cell HGPRT mutation assay, three out of four tested Cr(III) complexes were found to be mutagenic. In a direct DNA strand break assay with supercoiled bacteriophage PM 2 DNA, neither chromate nor the four Cr(III) compounds tested caused nicks. However, the combined action of chromate plus glutathione as well as the isolated complex of pentavalent chromium, Na₄Cr(glutathione)₄, did cause DNA breaks. Reactive oxygen species are inferred to be the ultimate DNA nicking agents in this assay. In conclusion there appear to be two mechanisms of chromate genotoxicity; one with direct DNA damage caused by Cr(V) species and one via DNA‐protein crosslinks formed with Cr(III), the final reduction state of chromate.     

Impact of rhizobacteria on growth and chromium accumulation in Scirpus lacustris L. grown under chromium supplementation

Four chromate tolerant rhizobacterial strains viz., RZB-01, RZB-02, RZB-03 and RZB-04 were isolated from rhizosphere of Scirpus lacustris collected from Cr-contaminated area. These strains characterized at morphological and biochemical levels. The most efficient chromate tolerant strain RZB-03 was inoculated to fresh plant of S. lacustris and grown in 2 microg ml(-1) and 5 microg ml(-1) of Cr+6 supplemented nutrient solution under controlled laboratory condition. The effects of rhizobacterial inoculation on growth and chromium accumulation in S. lacustris were evaluated. The inoculation of rhizobacteria increased biomass by 59 and 104%, while total chlorophyll content by 1.76 and 15.3% and protein content increased by 23 and 138% under 2 microg ml(-1) and 5 microg ml(-1) concentrations of Cr+6, respectively after 14 d as compared to non-inoculated plant. Similarly, the Cr accumulation also increased by 97 and 75% in shoot and 114 and 68% in root of inoculated plants as compared to non inoculated plants at 2 microg ml(-1) and 5 microg ml(-1) Cr+6 concentrations, respectively after 14 d. The chromate tolerant rhizobacteria which play an important role in chromium uptake and growth promotion in plant may be useful in development of microbes assisted phytoremediation system for decontamination of chromium polluted sites.     

大气降尘与土壤中重金属铬的形态分布规律

主要对成都理工大学校园内大气降尘和土壤中重金属铬的形态分布进行了分析比较,得出以下结论:重金属铬在大气降伞和土壤中的含量存在差别,大气降尘中铬的最明显大于土壤中的量,且基本上是土壤的两倍左右.且形态分布规律不同,大气降尘中铬含量的形态分布由大到小的次序是:残渣晶格态,铁锰氧化物结合态,有机结合态,碳酸盐结合态,可交换态;土壤中南大到小的次序是:残渣品格态,有机结合态,铁锰氧化物结合态,碳酸盐结合态,可交换态;铬在大气降尘中多存在于残渣晶格态(35.35%～59.82%)和铁锰氧化物结合态(25.97%～40.23%),且两者相差不大.而在土壤中多存在于残渣晶格态(37.22%～75.06%)和有机结合态(4.30%～12.98%),且主要以残渣品格态为主.形态分离方法采用Tessier五步连续提取法,重金属铬的测定方法采用国标方法(GB/T 5009.123-2003)示波极谱法.     

In-situ monitoring of chromium cytotoxicity in sugarcane

The potential of in-situ monitoring of cytotoxic effects of chromium through root-tip assay was studied in a sugarcane cultivar CoLk 8102 (Saccharum spp. hybrid). Sugarcane setts supplied with graded concentrations of chromium (VI), exhibited a reduction of 85.92 and 95.10 % in mean root length at 40 and 80 ppm Cr dosages along with 61.25 and 82.50% reduction in mean root number/node respectively. Mitotic index of root tip cells of treated setts declined and the frequency of aberrant mitotic phases increased pari passu to the increasing chromium concentration. To compare and quantify the effect of graded chromium dosages on frequency of chromosome aberrations vis-à-vis inhibition of mitotic activity, a 'Decretion factor' (D.F.) has been used for the first time. The value of DF increased with the increase in the chromium dosages. The increase in chromosome aberration frequency was low at low chromium dosages (1 or 2 ppm), but the high Cr dosages (40 and 80 ppm), induced sharp reduction in mitotic efficiency of root system along with anomalies in the process of cell division and induced chromosome aberrations in sugarcane root meristem, which in turn affected the over all plant growth.     

Comparative effects of trivalent and hexavalent chromium on spermatogenesis of the mouse

It has been repeatedly stressed that the biological effectiveness of chromium depends entirely on its oxidation state. The present work compares the histological effects of ingested trivalent and hexavalent chromium compounds on the mouse testes. The results showed comparable data of food consumption and gain in body weight. Both compounds produced ambiguous levels of degeneration in the outmost cellular layers of a number of seminiferous tubules, reduced the number of spermatogonia per tubule and the sperm count, and caused significant increases in the percentage of morphologically abnormal sperms. Generally, all these effects were more pronounced in animals which ingested the hexavalent chromium.     

Bioavailability and metabolism of hexavalent chromium compounds †

Intratracheal instillation of ⁵¹CrCl₃ in anaesthetized rabbits resulted in partial absorption. In blood, the absorbed material was entirely confined to the plasma compartment. Only trace amounts were deposited in liver and kidney. By contrast, after similar application of Na, ⁵¹CrO₄ the bulk of blood radioactivity was present in red blood cells (RBC). Substantial deposition occurred in liver and kidneys. It is concluded that Cr(VI) may enter the body unreduced via the lung and is partially deposited in cells over a prolonged period of time.

Since chromium was accumulated in liver after administration of Cr(VI) we investigated the intracellular disposition of Cr(VI) in the isolated perfused liver. No significant sex differences in chromium distribution were observed. At the end of the experiments (1 h), 60% of the applied dose (312μg Cr/liver) was located in the cytosol, whilst 14% was in the mitochondria, 9% in the microsomal pellet and 2% was associated with the nuclei. Gel chromatography of the cytosolic compartment showed that the overwhelming part of chromium was eluted in fractions with an apparent molecular weight of 6,000 dalton. These fractions exhibited absorption maxima at 410nm and 548nm. It is concluded, that cytosolic reduction might be the main intracellular redox pathway for chromates. This view was confirmed by monitoring the reaction of Cr(VI) with GSH in vitro. GSH reduced Cr(VI) without further cofactors under formation of GSH‐chromium complexes, which possibly represent major intermediates in the metabolism of Cr(VI).     

Coordination chemistry and the carcinogenicity and mutagenicity of chromium(VI)

Chromate is a known carcinogen, it is only in recent years that the molecular mechanisms by which this toxicity may be expressed have been investigated. The toxicity of chromate may be mediated by the reaction of chromium(VI) with glutathione (GSH) to generate relatively stable chromium(V) complexes and other more reactive intermediates. The conditions favouring the formation of such complexes have been studied. Reactive intermediates generated during the reduction of chromate by GSH include thionyl radicals and at least two relatively stable chromium(V) species (g -1.996 and g -.986). Mixtures of chromium(VI) and glutathione and a chromium(V) complex of glutathione, which we have isolated from the reaction (g = 1.996), are capable of causing strand breaks in bacteriophage PM2 DNA. In contrast a chromium(III) complex of GSSG, one of the final products of the reaction between GSH and chromium(VI), does not damage DNA in closed circle assays. These observations support the suggestion that reactive intermediates generated during the reduction of chromium(VI) provide one route by which the genotoxicity of chromate may be expressed.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min^?1 when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min^?1 were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.