土壤-植物系统中的汞污染与农产品安全生产

对农产品的汞污染及其安全生产问题作了综述，内容包括：汞在土壤．植物系统中的循环，汞污染对农产品安全生产的威胁与对策措施，例如，可利用植物生物技术选育低积累汞的作物基因型、采取植物修复及相应的农艺措施，以进行有效的农产品安全生产与调控，减小环境中过量的汞对土壤．植物系统和食物链造成的危害，最终保障人体的健康。     

镉污染土壤的植物修复

Cd在土壤中有稳定、积累和不易消除的特点,且可通过食物链富集使人体产生慢性中毒。我国农村镉污染尤其严重。植物修复技术是优秀的土壤镉污染治理技术,近两年来成为研究热点。本文阐述了土壤镉污染植物修复技术的机理、具体做法和技术进展。     

成都市土壤-植物系统铅污染状况初步研究

为研究成都市土壤-植物系统铅污染状况，分析了成都市五种蔬菜及其根系土的铅含量。结果表明，土壤铅含量变化范围61．0～115．0mg/kg，均值为77．3mg/kg，所有样品含量均超过成都市土壤环境背景值，以城东和城南污染最为严重；蔬菜中铅含量以莴笋叶最高，萝卜最低，叶菜类高于瓜果类；蔬菜污染严重区与土壤污染区差别明显，说明土壤铅和植物铅污染源不同。     

褪色光度法测定食品中痕量铜(Ⅱ)

铜在自然界中分布很广，是人体及动植物必需的微量元素之一，对机体的新陈代谢有重要的调节作用，但过量摄入铜也会产生危害。过量铜对水生生物的危害较大，其毒性与形态有关，游离铜离子的毒性比络合态的铜大得多，因此研究铜的分析方法一直受到人们关注。目前，环境、食物、植物、药物中痕量铜的测定常用原子吸收光谱法和萃取光度法。     

特选榨菜对铀污染土壤的修复评价

本文通过两种不同的加铀方式,加入不同种类及浓度的螯合剂,以及土壤改良剂(有机肥、微生物肥料、腐殖酸、尿素)的方法,研究了不同因素对特选榨菜修复铀污染土壤的影响。结果表明:在pH=5时把UO_2(NO_3)_2·6H_2O溶液喷洒入土壤,使土壤中铀污染浓度为100 mg·kg~(-1)时,特选榨菜地上部铀富集的浓度最大可以达到1103.42 mg·kg~(-1),根部为1909.49 mg·kg~(-1),去除率为7.81%;上述含铀土壤放置2年后制备成模拟铀污染的土壤,进而栽种特选榨菜进行修复,在100 mg·kg~(-1)铀污染浓度下,植物上部铀富集浓度最大为295.83 mg·kg~(-1),根部为268.42 mg·kg~(-1),年去除率为2.52%。用Tessier五步连续提取法测定两次修复土壤中铀的形态,发现模拟铀污染土壤比铀喷洒于土壤中有效态的铀(交换态和碳酸盐结合态)要低52.7%;加入柠檬酸、苹果酸等螯合剂以及有机肥、微生物肥料、腐殖酸、尿素等土壤改良剂,在模拟铀污染土壤修复时发现有机肥会降低植物上部对铀的富集;而柠檬酸和微生物肥会增强植物上部对铀的富集。     

土壤的植物修复与超积累植物研究

被污染土壤的植物修复将是未来更好与更廉价的修复技术,所以近年来对植物修复与超积累植物的研究兴趣日益增加。本文简要介绍了近期的发展趋势。目前研究的重点包括根际土壤微环境中的复杂反应与吸收过程,金属从土壤向植物根以及从植物根向叶的传输过程,金属在超积累植物中的定位与螯合作用等等。这是分析化学与环境科学及植物科学交叉研究的新领域,充满挑战。     

生物修复放射性污染土壤的研究进展

核能的利用给人类带来了福利也带来了灾难。部分土壤被放射性物质污染,放射性物质通过食物链进入人体,威胁人类健康。目前各国科研工作者正在积极寻找可行的办法解决土壤的放射性污染问题,并发展起来许多方法来修复放射性污染的土壤。本文就放射性污染土壤的来源、危害、处理等进行综述,并重点介绍了生物修复放射性污染土壤的研究进展。     

光度法测定食品中微量铜

铜是人体必需的微量元素，存在于血浆铜蓝蛋白、超氧化物歧化酶、细胞色素C氧化酶等。含铜酶在新陈代谢过程中表现出多种多样的生化功能。如运送氧气、O2^-的歧化、Fe^2＋的氧化、包括细胞色素C在内的有机底物氧化、单氧合作用以及电子传递，但摄入过量的铜盐将导致严重的健康问题。近年由于农业上大量使用含铜杀虫剂和除霉剂，加上工业“三废”的污染，使许多食品中铜含量超标。     

乙醚萃取-高分辨率连续光源石墨炉原子吸收光谱法测定金矿石中铊的含量

正铊是一种有毒重金属,铊及其化合物在水体、土壤和植物中的增加,通过食物链进入人体,会给人体带来极大的健康隐患。在自然界中,铊属于分散元素,是亲硫元素,也具有亲石性,主要存在于金、铜、铅、砷、锌和铁等的硫化矿物中。因此,在金矿石的开采及选矿过程中,会对环境造成污染。建立准确可靠的金矿石中铊的测定方法,可对金矿石开发工艺指标控制,资源评价及选冶工艺排放提供可靠的     

土壤铜污染的微生物及酶学指标研究

通过室内培养试验,研究了土壤铜污染对土壤微生物基础呼吸及土壤脲酶、脱氢酶、酸性磷酸酶的影响。结果表明,土壤微生物基础呼吸在低水平铜（≤100mg／kg）添加下呈现出先上升后下降的趋势,而随着土壤铜添加水平的进一步提高（〉100mg／kg）,微生物基础呼吸作用迅速增强;土壤脲酶则随着铜含量的增加呈现出不断下降趋势,土壤磷酸酶活性则在低水平下上升而随着添加水平的进一步提高迅速降低。可见,这两种酶对土壤铜毒害反应灵敏,可作为土壤铜污染评价的指标;而土壤脱氢酶则对铜含量的变化没有表现出明显的统计规律性,不适宜作为土壤铜污染评价的酶学指标。     

土壤重金属生物有效性的评价方法

土壤重金属污染已成为人们广泛关注的全球性的环境问题之一。重金属生物有效性已成为污染生态学研究的前沿。对国内外土壤重金属生物有效性评价方法的研究进展作了简要综述，并对今后的研究作了展望。     

Transfer of technetium in the soil-rice plant system

In order to assess the behavior of Tc in flooded soil-plant systems, laboratory experiments have been done using^95mTc as a tracer. Two common soil types in Japan, Andosol and Gray lowland soils, were used. Soil-plant transfer factors of Tc in rice grain were very low, i.e. 5×10^–5 for Andosol and 6×10^–4 for Gray lowland soil. It was found that the Tc concentrations in rice plants were influenced by those in soil solutions. Concentrations of^95mTc in both soil solutions decreased rapidly in the early period of cultivation. It was observed that redox-potential (Eh) also decreased markedly following flooding. A relationship was found between the decrease of the^95mTc concentrations in soil solutions and the drop of Eh in the soils. The Tc (VII) added to soil was transformed to insoluble Tc (IV) under the reduced conditions existing in flooded soil.     

Copper(II) influence on flumequine retention in soils: macroscopic and molecular investigations

The coadsorption of flumequine (fluoroquinolone antibiotic) and copper(II) on a alkaline soil sample (collected from the Champagne-Ardenne region, France) was studied at macroscopic and molecular scales by means of batch experiments and X-ray absorption spectroscopy. The retained antibiotic amount onto the soil surface increases (from 2- to >20-fold) with the copper concentration due to the formation of a Cu(II)-flumequine ternary surface complex, which leads to the accumulation of flumequine into soils. Flumequine can be classified at environmentally relevant pH values as a slow-mobile compound in soils and a very slow-mobile compound in the presence of copper, even at relatively low concentrations.     

Synthesis of 5-Iodo-1,4-disubstituted-1,2,3-triazoles Mediated by in Situ Generated Copper(I) Catalyst and Electrophilic Triiodide Ion

Mixing copper(II) perchlorate and sodium iodide solutions results in copper(I) species and the electrophilic triiodide ions, which collectively mediate the cycloaddition reaction of organic azide and terminal alkyne to afford 5-iodo-1,4-disubstituted-1,2,3-triazoles. One molar equivalent of an amine additive is required for achieving a full conversion. Excessive addition of the amine compromises the selectivity for 5-iodo-1,2,3-triazole by promoting the formation of 5-proto-1,2,3-triazole. Based on preliminary kinetic and structural evidence, a mechanistic model is formulated in which a 5-iodo-1,2,3-triazole is formed via iodination of a copper(I) triazolide intermediate by the electrophilic triiodide ions (and possibly triethyliodoammonium ions). The experimental evidence explains the higher reactivity of the in situ generated copper(I) species and triiodide ion in the formation of 5-iodo-1,2,3-triazoles than that of the pure forms of copper(I) iodide and iodine.     

The differential pulse anodic stripping voltammetry of copper and lead and their determination in EDTA extracts of soils with the mercury film glassy carbon electrode

The differential pulse anodic stripping voltammetry of copper and lead at the mercury film glassy carbon electrode is discussed. The mercury film prevents the occurrence of a monolayer stripping peak for copper. The influence of antimony and bismuth on the anodic stripping voltammetric behaviour of copper and lead is discussed. An interaction between copper and antimony distorts the copper stripping peak and gives rise to an intermediate peak. The method described is suitable for determining copper and lead simultaneously in EDTA extracts of soils.     

The effect of zeolites on copper uptake by plants growing in contaminated soils

Three-year pot experiments were carried out in a greenhouse with the aim of reducing the copper content in the 2nd link of the soil-plant-animal (man) trophic chain. For this purpose, synthetic zeolites of the 3A, 4A, 5A and 13X type were introduced into copper contaminated soils at levels of 1, 2 and 3% by weight in relation to the soil mass. Mono- and dicotyledonous plants were cultivated in mixtures of soils with the zeolites. The copper content in lettuce grown in the contaminated soil decreased in the presence of zeolites by 29–77%, in grass by 41–78%, in oats by 45–64% and in beets by 21–41%, as compared to the control.     

Changes in copper, lead and zinc concentrations in plants from paper mill sludge-treated soils

Effects of paper mill sludge addition on the availability of metals were studied on different soils both laboratory and naturally polluted; copper, lead and zinc concentrations were determined in Hordeum Distichum plants grown on the untreated and on sludge-treated soils. In some case a decrease of metal concentration is observed on sludge-treated soils; these results are consistent with the reduction of metal mobile forms in the soil, before plant growth. The decrease of metal availability in sludge-treated soils may be related with the pH value of the soil after sludge addition.     

Determination of tellurium in ores, concentrates and related materials by graphite-furnace atomic-absorption spectrometry after separations by iron collection and xanthate extraction

A method for determining approximately 0.01 mug/g or more of tellurium in ores, concentrates, rocks, soils and sediments is described. After sample decomposition and evaporation of the solution to incipient dryness, tellurium is separated from > 300 mug of copper by co-precipitation with hydrous ferric oxide from an ammoniacal medium and the precipitate is dissolved in 10M hydrochloric acid. Alternatively, for samples containing 300 mug of copper, the salts are dissolved in 10M hydrochloric acid. Tellurium in the resultant solutions is reduced to the quadrivalent state by heating and separated from iron, lead and various other elements by a single cyclohexane extraction of its xanthate complex from approximately 9.5M hydrochloric acid in the presence of thiosemicarbazide as a complexing agent for copper. After washing with 10M hydrochloric acid followed by water to remove residual iron, chloride and soluble salts, tellurium is stripped from the extract with 16M nitric acid and finally determined, in a 2% v/v nitric acid medium, by graphite-furnace atomic-absorption spectrometry at 214.3 nm in the presence of nickel as matrix modifier. Small amounts of gold and palladium, which are partly co-extracted as xanthates if the iron-collection step is omitted, do not interfere. Co-extraction of arsenic is avoided by volatilizing it as the bromide during the decomposition step. The method is directly applicable, without the co-precipitation step, to most rocks, soils and sediments.     

对比生物体系以及合成体系中单核铜氧物种对碳氢键和氧氢键活化的理论研究展望

由于具有较好的催化性能,含过渡金属的酶一直备受研究者的关注.其中,铜作为生物体中含量仅次于铁和锌的过渡金属,在新陈代谢过程中发挥着重要作用.铜酶广泛存在于自然界中,该类生物大分子涉及电子转移、氧化还原、氧气的运输与活化等生物化学过程.多种铜酶在氧气活化方面表现出引人注目的性质,例如:颗粒状甲烷单加氧酶(pMMO)、多糖单加氧酶(LPMO)、双铜单加氧酶肽基甘氨酸α-羟基化酶(PHM)和多巴胺β-单加氧酶(DβM),它们均可活化氧气,并生成相应的铜-氧活性物种.铜酶或铜配合物活化氧气可生成多种铜-氧活性物种,包括Cu(II)-O₂^?,Cu(II)-OOH(R),Cu(II)-O^?及Cu(III)-OH等.这些活性物种通常具有不同强度的攫氢能力,可能是铜酶C-H/O-H活化的活性氧物种.近几十年来,为了深入揭示铜酶的催化活性和反应机理,阐明关键铜-氧中间体的结构和性质,研究人员合成了众多含铜配合物体系,并模拟探索了铜-氧活性物种的反应活性尤其是对底物C-H/O-H键活化能力.本文聚焦于含有单铜活性位点的酶及其配合物体系.结合密度泛函理论计算,深入比较了铜酶及配合物体系中铜-氧活性物种反应活性,总结得到以下普遍规律:(1)MN15泛函可准确描述单核铜氧配合物的热动力学性质,对各类铜氧物种催化的C-H/O-H键活化计算中,得到的热动力学性质都能与实验结果很好地吻合;(2)Cu(II)-O₂^?在生物体系和人工合成体系中表现出一致的反应活性:它对O-H键活化表现出高反应活性,但对C-H键反应活性较差,因此不太可能是铜酶中C-H活化的活性中间体;(3)Cu(II)-OOH没有活化C-H键的能力,但其近端氧原子上的自由基特性使其能够攫取中等强度O-H键上的氢原子,另外该物种还可以与另一分子Cu(I)偶联形成双铜物种.因此,在生物体系和合成体系中Cu(II)-OOH均可作为氧气活化路径上的关键中间体,但并不能作为C-H键活化的氧化剂;(4)Cu(II)-O^?对C-H键活化具有高反应活性,因此该类物种可能在单铜单加氧酶的C-H键活化中起关键作用;(5)尽管许多实验证明Cu(III)-OH对C-H键的活化有较高的反应活性,但是在单加氧酶中,生成这一物种在热力学上是非常不利的,因此不太可能是单加氧酶中的活性物种.综上,本文的观点可以为生物体系及合成体系中的铜氧物种的反应活性提供新的视角与思考.     

Utilization of optimized BCR three-step sequential and dilute HCl single extraction procedures for soil-plant metal transfer predictions in contaminated lands

The prediction of soil metal phytoavailability using the chemical extractions is a conventional approach routinely used in soil testing. The adequacy of such soil tests for this purpose is commonly assessed through a comparison of extraction results with metal contents in relevant plants. In this work, the fractions of selected risk metals (Al, As, Cd, Cu, Fe, Mn, Ni, Pb, Zn) that can be taken up by various plants were obtained by optimized BCR (Community Bureau of Reference) three-step sequential extraction procedure (SEP) and by single 0.5 mol L(-1) HCl extraction. These procedures were validated using five soil and sediment reference materials (SRM 2710, SRM 2711, CRM 483, CRM 701, SRM RTH 912) and applied to significantly different acidified soils for the fractionation of studied metals. The new indicative values of Al, Cd, Cu, Fe, Mn, P, Pb and Zn fractional concentrations for these reference materials were obtained by the dilute HCl single extraction. The influence of various soil genesis, content of essential elements (Ca, Mg, K, P) and different anthropogenic sources of acidification on extraction yields of individual risk metal fractions was investigated. The concentrations of studied elements were determined by atomic spectrometry methods (flame, graphite furnace and hydride generation atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry). It can be concluded that the data of extraction yields from first BCR SEP acid extractable step and soil-plant transfer coefficients can be applied to the prediction of qualitative mobility of selected risk metals in different soil systems.