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1、Proposal of a simple screening method for a rapidpreliminary evaluation of “heavy metals”mobility in soils of contaminated sitesValentina Pinto & Francesca Chiusolo & Carlo CremisiniReceived: 23 June 2009 / Accepted: 22 February 2010# Springer-Verlag 2010AbstractPurpose Risks associated to “

2、heavy metals” (HM) soi contamination depend not only on their total content but, mostly, on their mobility. Many extraction procedures have been developed to evaluate HM mobility in contaminated soils, but they are generally time consuming (especially the sequential extraction procedures (SEPs) and

3、consequently applicable on a limited number of samples. For this reason, a simple screening method, applicable even “in field”, has been proposed in order to obtain a rapid evaluation of HM mobility in polluted soils, mainly focused on the fraction associated to Fe and Mn oxide/hydroxides。对土壤中的重金属的污

4、染的迁移性的初步快速的简单的筛选测定方法的建议(摘要) (对“重金属”在土壤中的污染风险联系不只局限于他们的总重量,通常来说,和他的迁移转化有关。在污染的土壤中很多萃取方法被又来评价重金属的迁移转化,但他们随着时间的而变特别是连续抽样,因此适用于有限数量的样本。由于这个原因,已提出建议,以获得一个快速的适用工作现场",甚至一个简单的筛选方法来重金属在土壤中的污染迁移转化,主要侧重于相关联的铁和锰的氢氧化物的分数。)Materials and methods A buffer solution of trisodium citrate and hydroxylamine hydroch

5、loride was used as extractant for a single-step leaching test. The choice of this buffered solution was strictly related to the possibility of directly determining, via titration with dithizone (DZ), the content of Zn, Cu, Pb and Cd, which are among the mostrepresentative contaminants in highly mine

6、ralised soils. Moreover, the extraction solution is similar, aside from for the pH value, which is the one used in the BCR SEP second step. The analysis of bivalents ions through DZ titration was exploited in order to further simplify and quicken the whole procedure. The proposed method generically

7、measures, in few minutes, the concentration of total extractable “heavy metals” expressed as molL1 without distinguishing between elements。我们是用的材料和方法 A 缓冲溶液的钠枸橼酸和羟胺盐酸作为萃取剂一步浸出试验。此缓冲的解决方案的选择是密切相关的直接测定可能性,滴定法双硫腙( DZ),锌、 铜、 铅镉的内容通过,当中污染的不准确性是污染物中土壤中很高的矿化原因。此外,在 BCR 体感诱发电位的第二步中,使用类似提取解决方案时要出去PH值,从而进一步简化

8、和加速整个过程被利用二价离子通过DZ滴定分析Results and discussion The proposed screening method has been developed and applied on soil samples collected from rural, urban and mining areas, representing different situation of soil contamination. Results were compared with data obtained from the BCR procedure . Conclusion

9、s The screening method demonstrated to be a reliable tool for a rapid evaluation of metals mobility. Therefore, it could be very useful, even “in field”, both to guide the sampling activity on site and to monitor the efficacy of the subsequent remediation action。 对于收集来自农村、 城市和采矿地区代表土壤污染的不同情况的土壤样品结果及

10、建议的筛选方法探讨已开发和应用。然后结果是与从 BCR 过程中获得的数据进行比较。结论证明:筛选方法是一个可靠评价金属转移快慢的工具。因此,在工作现场它可能是非常有用",甚至两个站点上指导采样活动和留意后续修复操作的效果。Keywords Dithizone . Extraction procedures . In-field test . 双硫腙关键字。 抽取过程。 在现场试验Metals mobility . Screening method 金属流动性。 筛选方法1 IntroductionThe environmental impact of soil contaminati

11、on by toxicologically relevant metals depends not only on the total concentration but mostly on the form in which metals occur, their mobility and, consequently, bioavailability (Alloway 2005). Risks become relevant in the following 土壤中对有毒金属污染的不仅取决于他的总浓度,通常还和金属的反应,流动性,生物作用有关风险成为有关,以下所示:cases:& m

12、edium/high levels of concentration and high mobility,but also& very high levels of concentration and moderate mobility The knowledge of trace elements mobility in contaminated soils is becoming an important requisite for any further environmental evaluation: In Europe, many countries have alread

13、y adopted laws used to regulate land contamination and considering pollutant bioavailability risks (Carlon 2007) and even the Soil Thematic Strategy, concerted by the European Commission in view of a future Soil Framework Directive, underlines the need of “improvement and harmonisation of the concep

14、ts and the modeling of the transfers of contaminants from and within the soil and of the subsequent risks” (Van-Camp et al. 2004). 中等浓度或高浓度对应的流动性而且高浓度对应的流动性研究受污染的土壤中痕量元素迁移的知识成为了将来评价环境的要条件。在欧洲,许多国家已经采取将土壤污染和污染物的生物风险纳入到国家法律中甚至一些欧洲国家机构考虑到对于将来STS的观点;重视改善环境保持和谐环境的理念和重塑污染物在土壤中的迁移和土壤中和的后续的风险成为了土壤策略主题。In th

15、e last decades, many single and sequential extraction procedures (SEPs) have been developed and proposed as standard methods for the study of metals mobility (Bacon and Davidson 2008; Cappuyns and Swennen 2008; Rao et al. 2008; Pacifico et al. 2007). The most extensively used SEPs are the one develo

16、ped by Tessier et al. (1979) and the revised BCR standardised three-step sequential extraction procedure (Rauret et al. 2000), but they are time consuming and, in general, applicable on a limited number of samples selected among a larger set.。在近几十年间,很多单独和连续提取过程已经发展成为作为研究金属流动性的标准方法。中被Tessier et al发现的

17、SEPs最广泛的是和经修订的 BCR 标准化三步连续提取工艺是最为被广泛利用的。但是他的缺点主要是它受时间的限制和对样品有选择性。Therefore, considering that contaminated sites to be studied are often quite wide and heterogeneous with the consequential need of a large number of samples to be analysed, there is urgency of rapid and simple screening tools for a rel

18、iable identification of the most significant sampling points, in terms of metal mobility, that can be successively characterised through standard leaching test or SEPs (Fig. 1) (Brunori et al. 2005; Pacifico et al. 2007). In fact, screening methods have some of the following characteristics: They te

19、nd to have a qualitative rather than quantitative emphasis; they normally involve little or no sample treatment; they are rapid, and the response is used for immediate decision-making, and the result obtained generally requires confirmation by a conventional alternative (Valcàrcel et al. 1999;

20、Munoz-Olivas 2004). The proposal of a simple in-field screening method is based on the foregoing considerations, and in this work, a single-step leaching test has been developed and studied in order to obtain a rapid evaluation of metals mobility in polluted soils, mainly focused on the fraction ass

21、ociated to Fe and Mn oxide/hydroxides more dependent on the pH and oxidizing variation in the soil environment (Alloway 2005) and, qualitatively and quantitatively, more representative of the risks related to HM mobility. The proposed method is less complex and more specific, in terms of soil fracti

22、on analysed, than other existing in-field screening systems such as the rapid test proposed by Jozic et al. (2009), which, moreover, involves reagents that create safety problems when used for in-field analysis。 因此,考虑到待研究污染的场地往往相当广泛和大量连续的样品的分析,人们迫切的需要一种快速和简单的筛选工具来确定重要的取样点的一个可靠的指标。就金属流动性而言,这可以通过SEPs或

23、试验先后特点浸出。实际上,有以下特征筛选方法:它们的重点往往是定性分析而不是定量:他们通常涉及很少或没有样品的处理;它们快速反应和快速的反应结果,结果通常需要确认有常规的替代。基于上述的考虑建议一种简单的板块筛选方法。为了获得在污染土壤中金属流动性的快速评价,所以在这的工作单步执行浸出试验,主要侧重于相关联的Fe和Mn氧化物或氢氧化物的分数在土壤中和土壤环境的PH值及氧化性的多样和金属流动性的风险来决定是定性还是定量。比其他如被Jozic et al 提出的起初快速检测涉及创建安全问题时用于板块中分析的试剂现有的字段筛选系统,他提出的方法是不太复杂和更具体的土壤分数分析。In the pres

24、ent study, a buffer solution of trisodium citrate and hydroxylamine hydrochloride at pH9.3 was used as extractant for a single-step leaching test. The choice of this buffered solution was strictly related to the possibility of directly determining, via titration with dithizone (DZ), the content of Z

25、n, Cu, Pb and Cd, which are among the most representative contaminants in highly mineralised soils. Moreover, the extraction solution is similar, aside from the pH value, which is the one used in the BCR SEP second step. The analysis of bivalents ions through DZ titration was exploited in order to f

26、urther simplify and quicken the whole procedure。 最近研究,钠的柠檬酸和羟胺盐酸的缓冲溶液在ph=9.3时作为萃取剂用于单步执行浸出试验。此缓冲的解决方案的选择是密切相关的直接决定它的可能性,通过用双硫腙来滴定Zn,CuP,b,Cd,其中高矿化重金属污染的土壤最具有代表。此外,提取解决方案是于pH 值在其中使用 SEP BCR的第二部类似。从而通过通过 DZ 滴定分析二价离子进一步简化和快速整个过程。Diphenylthiocarbazone, or DZ, is an organic compound widely used, especial

27、ly in the past, for the colorimetric determination of various heavy metals (Sandell 1959). DZ dissolves in most organic solvents to a greater or less extent and exists in two tautomeric forms: 二苯基硫卡巴腙或双硫腙对各种重金属含量的比色测定是一种使用广泛的一种有机化合物。DZ 在某种程度上是机溶剂中的溶解与存在于两个异构体窗体When a solution of DZ in an immiscible

28、organic liquid is shaken with an aqueous solution of a reacting heavy metal, an internal complex dithizonate is formed, which is soluble in the organic solvent and to which it imparts a colour depending upon the metal involved. Many heavy metals can be extracted as dithizonates, but the extraction e

29、fficiency and selectivity depend on the nature of the metal and on the pH of aqueous solution. Considering that DZ is a dibasic acid: 对DZ 的不相容的液体中解决方案时,是将金属与混合充分震荡,于是就形成了一个内部复杂的DZ,于是就可溶在溶液中,溶液的颜色一般和金属有关。很多金属可以和DZ产生沉淀而被分离出来,但沉淀的程度取决于金属本身的性质和溶液的PH值。其中DZ是一种二元酸。H2DZ<=> Ht t HDZ_HDZ<=> Ht t D

30、Z2_since the secondary ionisation constant of DZ is estimated to be less than 1015, at pH9, most of the excess of DZ will be present in the aqueous phase (w) as HDZ and will form, with metal ions, a primary metal dithizonate soluble in the immiscible organic solvent (o):由于在ph=9时第二电离常数小于10-15是一个很小的数,

31、溶液中主要以HDZ一价存在和金属反应生成沉淀。M+(W) +2HDZ_<=>MeHDZT2 e0TIn the past, the colorimetric determination of Zn, Cu, Cd and Pb with DZ in chloroform (CHCl3) at pH9.3 was extensively used in our laboratory for in-field preconcentration of metals and preliminary analysis of fresh waters (Brondi et al. 1986).

32、 Anyway, the use of toxic CHCl3 has discouraged this procedure, and at the beginning of our work, different experimental conditions have been evaluated in order to obtain a rapid and relatively non-toxic method for heavy metals determination through DZ titration。在以前在 pH9.3 CHCl3的三氯甲烷用比色法测量,我们的实验室中广泛

33、用于板块中富集金属及淡水的初步分析。无论如何,通过重金属测定方法我们不提倡用有毒CHCl3,我们工作的开始,所以在不同试验条件得一快速和相对不含毒性 的方法是DZ滴定 。 Initially, in order to avoid a solvent-extraction step and, in particular, the use of toxic CHCl3, many studies have been carried out on DZ dissolution in homogeneous phase: a method using inexpensive anionic micel

34、lar systems, such as sodium dodecyl sulphate, has recently been applied for spectrophotometric determination of trace level mercury (Khan et al. 2005), but our trials revealed that it could not be used for titration with visual appreciation of the colour change.。起初,为了避免萃取溶剂-步骤地,特别是有毒的 CHCl3,我们使用一种廉价

35、阴离子的胶束系统方法,使用非极性DZ 来滴定分离:,如钠十二烷基硫酸,最近已经应用的分光光度法测定痕量级别汞汗 (et al.,2005)但我们的试验显示可见颜色变化的不能用它来进行滴定。For this reason, successively, the DZ dissolution and behaviour in relatively non-toxic organic solvents such as ethyl acetate, hexane, ciclohexane, toluene and a mixture of toluene/ciclohexane have been in

36、vestigated. Anyway, only DZ in toluene showed to be a valid alternative of DZ in CHCl3 and, at pH 9.3, it can be used for a selective, sensitive, rapid and simple titrimetric determination of Zn, Cd, Cu and Pb: The proposed method generically measures, in few minutes, the concentration of total HM e

37、xpressed as mol L1 without distinguishing between elements: 1 mL of dithizone 2 nmol of M+ (Zn, Cd, Cu and Pb)。因如此,一系列的用DZ 滴定分离用到相比较无毒性如乙酸乙酯、 己烷、环己烷、 甲苯和苯的混合有机溶剂中的行为进行了调查,但是,在ph值=9.3 是溶剂是CHCl3甲苯的DZ中的较其它显示,它有更高的选择性的、 敏感的、 快速的、 简易性来滴定法测定锌、镉、铜、铅。通常建议的,在几分钟的时间,以 mol L1为单位, 元素之间总浓度没有区别的: 1 毫升的双硫腙 2 nmol

38、M (锌、镉、铜和 Pb) The proposed screening method has been applied on soil samples collected from rural, urban and mining areas and representing different situation of soil contamination. Results were compared with data obtained from the BCR procedure。应用了建议的筛选方法从农村、 城市和采矿地区收集和所代表的不同情况下的土壤污染的土壤样品上取样。然后从 BC

39、R 过程中获得的数据进行比较得出结果。2、Materials and methodsMaterials Sixty-nine percent HNO3, Aristar® (BDH), 40% HF Aristar® (BDH), 70% HClO4 RPE (FLUKA) and ultrapure water (18.2 Mcm1 at 25°C) obtained from a MilliQ Element System (Millipore, France) were used for 7 2samples and calibrating solution

40、 preparation and dilution. For leaching experiments, a buffer solution was prepared with 141g of trisodium citrate Na3C6H5O .2HO RPE (CARLO ERBA REAGENTI) and 19 g of hydroxylamm- monium hydrochloride NH2OH.HCl RPE (CARLO ERBA REAGENTI) dissolved in 1 L water and the pH adjusted to 9.3 with NH3 Aris

41、tar® (BDH). Acetic acid CH3COOH (J.T. BAKER), hydroxylammmonium hydrochloride NH2OH.HCl RPE (CARLO ERBA REAGENTI), 30% hydrogen peroxide H2O2 “suprapure”(Merck) and ammonium acetate CH3COONH4 (RUDI PONT) were prepared according to the BCR procedure (Rauret et al. 2000). For titration analysis 2

42、.105 M dithizone (1,5-diphenylthiocarbazone C13H12N4S (FLUKA) was prepared daily by dissolving the appropriate amount of the corresponding chemical in Toluene (J.T BAKER). Single element ICP-MS Aristar®, (BDH) standard solutions of 1,000 mgL1 in nitric acid were used for the preparation of cali

43、brating solutions. Rhodium ICP-MS standard solution Aristar® (BDH) was used as the internal standard to correct matrix interferences in ICP-MS analysis. Polypropylene Falcon Tubes (Blue Max) were used during sampling handling, and filter membranes (0.45µm Mil- lex®HV, Millipore®)

44、 and syringes BD Plastipack were used for leaching experiments. All labware used in the experiments was soaked in diluted nitric acid overnight and then rinsed with double deionised water. All the experiments were performed in triplicate,and the mean values were considered. A blank procedure was alw

45、ays evaluated.。 材料和方法;材料:69%的HNO3,Aristar ® BDH,40 高频 Aristar ® BDH、 70 HClO4 视网膜色素上皮 FLUKA 和纯水 182 Mcm1,从法国专家 MilliQ 元系统微孔,获得的 25 ° c 条件下将样品用和校准溶液制备及稀释。 浸出实验,缓冲溶液准备以 141 g 钠枸橼酸盐 Na3C6H5O.2HO 视网膜色素上皮卡罗和 19 g NH2OH.HCl 视网膜色素上皮卡罗 盐酸中的溶解 1 L 水中和 ph 值调整为 9.3 NH3 Aristar ® BDH。 醋酸 CH3

46、COOH J.T.贝克,hydroxylammmonium 盐酸 NH2OH.HCl 视网膜色素上皮卡罗 ERBA REAGENTI,30 过氧化氢 H2O2"suprapure"默克和铵醋酸 CH3COONH4 RUDI 蓬当时准备根据 BCR 过程 Rauret et al.,2000年。 滴定分析 2.105 M 双硫腙为 1,5-diphenylthiocarbazone C13H12N4S FLUKA 份由每天适当数额的甲苯 J.T 贝克在相应的化学溶解。 电感耦合等离子体质谱 Aristar ®,BDH 标准溶液中硝酸 1000 mgL1 的单个元素用

47、于校准解决方案的研制。 铑-等离子体质谱标准解决方案 Aristar ® BDH 用于内部标准作为更正电感耦合等离子体质谱分析中的矩阵干扰。 用聚丙烯猎鹰管蓝色最大 中采样处理与滤膜 0.45µm 密 lex ® 高压、 微孔 ® 和注射器屋宇署 Plastipack 用于浸出实验。 在实验中使用的所有 labware 泡稀硝酸在一夜之间,然后用双 deionised 水冲洗。 一式三份,进行的一切实验和被认为是平均的值。 一个空的过程始终计算。Instrumentation A microwave system (Milestone 1200 Mega

48、, Italy) was used for sample digestion. All the measurements of trace elements concentrations were made using a Perkin Elmer ICP-MS Elan 6100 equipped with a cross-flow nebuliser and a Perkin Elmer ICP-OES 2000 DV equipped with Scott-type spray chamber.。 使用配备横流 nebuliser 的珀金埃尔默电感耦合等离子体质谱大 6100 和斯科特I

49、CP OES 2000 DV型喷水室配备的珀金埃尔默来测量所有微量元素浓度的所有测量都了,从而用仪器仪表微波系统里程碑来消解。Sample description and preparation The proposed screen- ing method has been developed and applied on soil samples collected from rural, urban and mining areas, representing different situation of contamination: LIS samples were collected

50、 in a rural area 200 km South-East from Rome (Italy); CAR 36 and PIN31 urban samples were collected in traffic areas of Rome, and BL0102 sample was collected from horizons of selected soil profiles in the Baccu Locci stream catchment near Muravera (Southeastern Sardinia Italy), characterised by sulp

51、hide deposit exploited since ancient times, while EP3 and P5C19 samples came from an abandoned Sb mine in an area with abundant sulphide mineralization resulting from hydrothermal activities (Manciano- Tuscany). Soil samples were air-dried at 40°C and sieved at 2 mm before their use in the expe

52、riments.样品说明和建议的屏幕方法已开发和应用于从农村、 城市和采矿领域代表不同的污染情况收集的土壤样品的制备:LIS 样本是从罗马农村地区东南 200公里收集来的;在收集了CAR 36及 PIN31样本在罗马的交通区收集,并BL0102 示例所选的土壤剖面中是在附近 Muravera Baccu Locci 的视野流流域收集来的以自古以来的硫化物矿床特征的土壤,而EP3 和 P5C19 的的样品是来自一个被遗弃的锑矿山地区丰富硫化矿热液活动而引致的。 土壤样品在 40 ° C会风干,而且在试验之前应筛选出直径2mm之内。 Determination of total cont

53、ent The elemental composition of the soil samples was determined by analyzing several samples after digestion in microwave system with HNO3, HClO4 and HF (as determined by Brunori et al. 2005). This analytical procedure was considered reliable, having been widely experienced in the past in the netwo

54、rk of several intercomparison exercises on the same types of matrices for other trace elements. The analytical performance of the laboratory was evaluated by analysing 10 different aliquots of till 1 (soil) certified reference material (CRM) to ensure adequate quality assurance. Results of HM total

55、content in the studied soils are reported in Table 1.总浓度的测定:土壤样品的元素组成的测定时通过分析一些被以HNO3、 HClO4 和HF高频微波系统处理后的出来的。此分析过程被认为是可靠的而过去被广泛的应用在通过网络用相同方法追踪其他内在有某一定联系的元素。该实验室的性能分析是对10份不同组分的试样进行分析直到有一份CRM可以确保质量保证的土壤。表1是HM研究土壤中的总含量的报告结果。EP3Mine24 ± 1664 ± 304.0 ± 0.31,010 ± 9BL0102Mine30 ±

56、 1142 ± 101.0 ± 0.1152 ± 2P5C19Mine146 ± 111,560 ± 648.0 ± 0.2404 ± 5LIS 1Rural32 ± 156 ± 20.39 ± 0.02162 ± 2LIS 2Rural31 ± 154 ± 20.42 ± 0.01145 ± 1CAR 36Urban139 ± 151,026 ± 400.35 ± 0.10301 ± 6PIN 31Urb

57、an58 ± 3400 ± 500.41 ± 0.09291 ± 4Sequential extraction The BCR three-step sequential procedure (Rauret et al. 2000) was applied to different soils. The residues from step 3 were treated by the procedure used for determination of the total trace element content of the soil sample

58、s. The analytical performance of the laboratory in the sequential extraction procedure was evaluated by analysing BCR 701 (lake sediment) CRM. 连续提取的 BCR 三步序贯过程.被应用于不同的土壤。 第 3 步中的剩下来的被用来土壤样品总微量元素含量的测定。 通过分析 BCR 701 湖泊沉积物 CRM 评估顺序提取过程中实验室的分析性能。 The results obtained on CRMs (till 1 and BCR 701) always

59、substantially overlap the certified values.在CRM获得的结果重现性很大所以认证了它的价值 Leaching test For the kinetic studies, a single-step leaching test was performed: 0.5 g sample (soil) was used with 30-mL buffer solution. The tests were performed in triplicate. Polyethylene tubes containing samples and extractant were stirred using an end-over-end shaker at a speed of 30 rpm for a given time, different for each tube. At the end of the chosen mixing t

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