超声波活化风化煤腐植酸对小白菜吸收Pb、Cd和土壤酶活性影响

采用土培盆栽试验研究不同超声波活化风化煤腐植酸添加量0,10,20,40,60g/kg(以风化煤计)对小白菜吸收重金属铅、镉和土壤酶活性的影响。结果表明:在加风化煤量40g/kg条件下,有效降低了土壤中铅、镉的可移动性,使小白菜中铅、镉含量明显降低;在加风化煤量20～40g/kg条件下,明显降低了土壤中铅、镉的生物毒性,提高了土壤酶(过氧化氢酶、脲酶、蔗糖酶)活性。故施适量的超声波活化风化煤(20～40g/kg)可有效减轻土壤中重金属铅、镉单一污染对小白菜的毒害,从而为铅、镉单一污染的小白菜区域增施腐植酸肥提供理论依据。     

活化剂联合柳树对重金属Cd污染土壤的修复效果研究

为有效提高植物提取污染土壤重金属的效率,以绿色安全的有机物料为活化剂代替存在安全隐患、不可降解的螯合剂及表面活性剂,探究不同活化剂对土壤重金属镉的活化效果及对植物镉积累的影响。通过室内培养试验与盆栽试验的方法,研究了紫云英、黄腐酸钾和柠檬酸3种活化剂在0.3%施用量下对污染土壤中镉的生物有效性、赋存形态的影响及活化剂强化柳树对镉的积累。结果表明:(1)添加活化剂会改变土壤的pH。培养结束时,黄腐酸钾处理对土壤pH的降低效果优于紫云英处理,显著低于对照0.50个单位(p<0.05),而酸性较强柠檬酸处理的土壤pH显著高于对照0.26个单位(p<0.05);添加活化剂均可提高土壤有机质含量。培养结束时,黄腐酸钾处理对土壤有机质含量提升效果优于其他2种活化剂,显著高于对照2.97 g/kg(p<0.05)。(2)添加活化剂均可提高土壤有效态镉含量,但不同活化剂的活化效果不同。培养20天时,紫云英与黄腐酸钾处理的土壤有效Cd含量均达到最高,优于柠檬酸处理,分别高于对照0.38 mg/kg(p<0.05),0.17 mg/kg。培养10~30天时,柠檬酸处理的土壤有效Cd含量逐渐增加,至30天时,柠檬酸处理对土壤有效Cd含量提升效果优于其他活化剂,显著高于对照处理0.39 mg/kg(p<0.05)。(3)添加活化剂影响了土壤镉形态分布,培养10~30天,3种活化剂可活化土壤残渣态Cd,提高酸可提取态Cd所占百分比。(4)3种活化剂处理对柳树的株高、生物量无显著影响,但均提高了根系的形态参数,其中柠檬酸处理的根系长度、表面积、根系体积均显著高于对照,分别提高了75.54%,80.05%,82.93%(p<0.05)。活化剂中黄腐酸钾处理明显提高了柳树叶片、枝条、根系镉含量,分别高于对照133.44%(p<0.05),75.21%,264.64%(p<0.05),并大大提高了柳树对土壤镉的富集与净化。以有机物料为活化剂,可有效提高土壤重金属生物有效性,提高植物对土壤镉的吸收,具有良好的应用前景。     

添加螯合剂诱导－栽培红叶菾菜（Beta vulgaris var. cicla L.）修复铅和镉污染土壤效果的研究

以雄安新区安新县重金属污染农田土壤为供试土壤,以Cd超积累植物红叶菾菜（Beta vulgaris var. cicla L.）为供试植物,设置不同浓度EDTA和柠檬酸（0,2.5,5,7.5,10 mmol kg?1）处理进行盆栽试验,探究螯合诱导－红叶菾菜修复Cd、Pb污染土壤的可行性。结果表明:（1）与对照相比,添加EDTA螯合剂使红叶菾菜生长及生物量均受到抑制,一定浓度柠檬酸处理能显著促进植物生长,5 mmol kg?1柠檬酸处理对植物株高、茎粗及生物量与对照相比的上升比例分别为4.52%、44.07%和50%;（2）添加EDTA螯合剂后土壤中Cd、Pb有效态含量相比对照分别提高了108.61% ~ 235.39%、67.98% ~ 224.16%,柠檬酸处理后土壤Cd、Pb有效态含量最大提高了180.07%、186.01%,EDTA对土壤重金属的活化效率显著高于柠檬酸;（3）通过对红叶菾菜地上部Cd、Pb含量及富集系数比较发现,EDTA更能促进红叶菾菜对Pb的吸收,柠檬酸更能促进红叶菾菜对Cd的吸收;（4）螯合剂处理后土壤中铵态氮、有效磷、速效钾含量显著增加。就本文试验条件、供试材料而言,螯合诱导－红叶菾菜修复铅镉复合污染土壤是可行的。     

四种典型重金属污染对土壤吸附磷的影响

以空白土壤和人工制备的不同浓度铜、砷、镉和铅污染土壤为对象,研究了在不同pH值、温度和柠檬酸浓度条件下重金属污染对土壤吸附磷的影响,并对其进行了相关过程的等温和吸附动力学的机理分析。研究结果表明,空白土壤和As污染土壤吸附磷的等温吸附过程符合Temkin方程,Cu、Pb、Cd污染土壤吸附磷的等温吸附过程符合Freundlich方程,空白土壤和重金属污染土壤吸附磷的动力学过程均符合Elovich方程;重金属污染对土壤吸附磷有一定的抑制作用,抑制程度与污染物浓度呈现显著的正相关,且随外在环境因子的改变而不同。当重金属元素铜、铅、砷、镉的含量分别为200、80、25、0.8 mg kg^-1时:pH值为5时,重金属对土壤吸附磷抑制作用最小,土壤吸附磷量分别降低了30.18%、13.54%、30.74%、37.23%,其抑制作用程度为:Cd> As> Cu> Pb;土壤吸附磷量与温度呈现显著的正相关,温度变化为25~45℃时,土壤对磷的吸附量分别增大了17.14%~28.83%、6.72%~16.05%、8.68%~9.13%、10.30%~23.45%,同一条件下重金属对土壤吸附磷抑制作用程度为Cu> Cd> As> Pb;重金属污染土壤吸附磷量与柠檬酸浓度成负相关,柠檬酸浓度为50 mg L^-1时,土壤吸附磷量分别降低了19.87%、21.94%、23.18%、24.84%,相同柠檬酸浓度下其抑制作用程度为Cd> As> Pb> Cu。     

浙西石灰岩地区土壤和稻米镉含量研究

为理解石灰岩地区农田土壤重金属积累特点及污染风险,以浙西石灰岩地区为例,随机选择了153块重金属污染农田,点对点采集了土壤和水稻样品,分析了土壤和糙米中镉的含量及土壤性状,探讨了石灰岩地区污染农田土壤与稻米镉积累特点及其与土壤性状的关系。结果表明,土壤全镉随粘粒含量的增加而增加,随土壤pH的下降而下降;土壤有效镉占全镉的比例与土壤pH呈负相关,糙米中镉含量与土壤有效镉、水溶性镉呈显著正相关;糙米中镉含量与土壤pH、有机质含量及粘粒含量均呈现显著负相关,土壤pH是影响石灰岩地区农田糙米镉积累最为重要的因素。《土壤环境质量－农用地土壤污染风险管控标准（试行）》（GB 15618—2018）的污染风险筛选值并不适用于石灰岩地区高pH的土壤。当6.5 < pH ≤ 7.5时,土壤重金属镉含量与农产品中重金属镉超标结果并不一致,其风险筛选值（0.60 mg kg?1）偏低,实际的风险筛选值可能在0.80 mg kg?1以上。土壤水溶性镉较土壤全镉和有效镉能更好地评估石灰岩地区农作物重金属镉的污染风险。     

广州市蔬菜地土壤重金属污染状况调查及评价

探讨了广州市蔬菜地土壤重金属污染状况，测定了95份土壤样品中铅、镉、铬、砷、汞的含量水平。土壤中铅、镉、铬、砷、汞的含量分别在6.44-153.10mg/kg、0－0.682mg/kg、5.82-101.60mg/kg、0.04-45.36mg/kg、0.01-0.32mg/kg之间。就污染的普遍性而言，铅污染最为普遍，其次是砷污染；就污染的程度而言，镉污染最严重，其次为砷、汞。对比今昔污染变化，广州市土壤污染治理已了得显著成效，但仍需努力。土壤中镉、砷、汞三种元素的变异系数。特别是镉的变异系数较大，这可能预示着点源性污染的存在。     

田块尺度污染农田土壤铅、镉和砷含量的空间变异及其对土地利用的启示

为了探明铅冶炼污染区田块尺度下农田土壤重金属含量的空间变异及其对污染农田土壤安全利用的意义,在某冶炼厂附近一面积为4800 m2的农田用网格法采集120个0~20 cm土样,测定样品镉、铅和砷含量。研究表明,研究区土壤中存在砷、镉和铅的积累。从平均污染指数来看,以镉的积累程度最大,铅次之、砷最小。土壤全镉含量的变化范围为1.10~3.84 mg kg^-1,镉含量处于1.10~2.27 mg kg^-1之间的样品占97.50%。从重金属空间分布上看,镉和铅含量的空间分布有较高的一致性,均是研究区北部和南部含量较高,中间区域含量较低。相关分析表明,土壤镉和铅含量之间存在显著正相关(P <0.01)。根据土壤铅含量计算稳定铅时所用普通过磷酸钙的用量范围为0.312~0.419 kg m^-2,平均值为0.367 kg m^-2。根据其他研究者得到的土壤全镉含量与小麦籽粒镉含量的相关方程计算,不同方程得到的小麦籽粒镉含量结果有很大差异,较可信的小麦籽粒镉含量变化范围为0.095~0.814 mg kg^-1。采样区中部为小麦籽粒镉含量较低且铅稳定剂需要量较低区域。以上结果表明,研究区田块尺度下土壤镉含量存在较大的空间变异,且土壤镉含量的空间变异导致小麦籽粒镉含量可能存在较大的空间变异。     

有机酸淋洗对土壤Cd纵向迁移及有效性的影响

针对保定市污灌区土壤重金属污染现状,采用土柱模拟淋洗试验,以自然Cd污染土壤为对象,研究了EDTA、柠檬酸、草酸3种淋洗剂对污染土壤中镉纵向迁移的影响,以及有效态镉在表层污染土壤中(0-20cm)的变化规律。结果表明:淋洗后表层污染土壤中Cd含量均随着有机酸添加量的增加而降低,随着EDTA添加量增加各处理较对照分别降低了4.72%,8.96%,19.38%,30.46%;不同柠檬酸添加量处理较对照分别降低了0.42%,1.14%,16.9%,27.9%;不同草酸处理较对照分别降低了4.23%,5.70%,14.01%,17.75%。随着有机酸添加量的增加,底层全镉(20-50cm)迁移深度增加,最大迁移深度可达到40cm,含量随着深度的增加而减少,3种有机酸对污染土壤镉迁移能力顺序为EDTA>柠檬酸>草酸。除低柠檬酸添加量处理下(<75kg/667m2)表层污染土壤有效镉含量较对照略有降低外,土壤有效态镉的含量均随着各有机酸添加量的增加而增加,且两者之间呈显著的线性正相关。     

辽河干流坝间耕地土壤重金属污染特征研究

通过对辽河干流坝间10个断面耕地土壤0~5 cm、5~15 cm、15~30 cm沉积层重金属铜、镉、锌、铅含量测定,评价了该区土壤重金属污染程度,并采用地质累积指数法评价单一重金属污染状况与潜在生态危害指数,综合评价重金属生态危害程度。研究结果表明,该区土壤铜、铅、锌与镉含量均值分别为32.42 mg?kg~(-1)、38.23 mg?kg~(-1)、47.35 mg?kg~(-1)和1.625 mg?kg~(-1);铅、锌含量均值在达牛渡口最大,分别为55.54 mg?kg~(-1)和80.51 mg?kg~(-1);铜、镉含量均值在通江口处最大,分别为50.24 mg?kg~(-1)和3.103 mg?kg~(-1)。除镉外,铅、铜、锌含量各断面不同深度浓度均低于全国土壤环境质量Ⅱ级标准,镉含量均值是全国土壤环境质量Ⅱ级标准的1.70倍,最大值为3.402 mg?kg~(-1);辽河大桥上游干流镉含量是下游镉含量的6.47倍。镉的地质累积指数值在坝间均显污染,其中,辽河大桥以上各断面显强污染。通江口至毓宝台特大桥重金属潜在生态风险指数值最强。各断面镉对多种金属潜在生态风险指数值的贡献达78.77%~98.23%,贡献率与潜在生态危害指数(RI)呈正相关。多种重金属潜在生态风险指数值变化趋势与镉地质积累指数分布趋势相同,最大值出现于通江口断面。     

滇西陇川县耕地土壤环境质量分析评价

为揭示滇西地区土壤环境质量状况,以陇川县为例,参照《绿色食品产地环境技术条件》,对耕地土壤pH值、有机质、全氮、速效磷、速效钾营养元素含量及重金属元素铅、镉、汞、砷、铬、铜总量进行测定分析。采用标准对比法、单因子污染指数法和Nemero综合污染指数法,对其土壤环境质量进行了评价。结果表明,研究区土壤pH值介于3.49~7.45之间,均值为5.05,土壤偏酸;各营养元素平均值中有机质、全氮、速效磷含量为优良,速效钾含量为中等,有机质、全氮、速效磷、速效钾含量分别有64.17%、59.34%、75.33%、71.66%的耕地面积达到生产绿色食品土壤肥力要求,分别有35.83%、40.66%、24.67%、28.34%的面积土壤肥力不足;采用单因子污染指数法对土壤重金属评价,砷、铬、铜处于清洁状态;有20.27%、2.03%、4.73%的样本铅、镉、汞单因子污染指数大于1,所代表的面积受到铅、镉、汞轻度污染,镉有1.35%样本单因子污染指数大于2,所代表的面积受到镉中度污染;综合污染指数评价,4.79%样本达到轻度污染。     

螯合剂对大叶井口边草Pb、Cd、As吸收性影响研究

用室内土培试验方法,研究在采自田间的Pb、Cd、As、Zn和Cu复合污染土壤上种植大叶井口边草条件下,外源分别添加0、1.5、3、6、12 mmol/kg乙二胺二琥珀酸（EDDS）、氨三乙酸（NTA）和乙二胺四乙酸（EDTA）对大叶井口边草吸收Pb、Cd和As的影响。结果表明,3种螯合剂处理对大叶井口边草生物量没有显著影响,说明大叶井口边草对3种螯合剂耐性较强;6、12 mmol/kg EDTA处理能极显著提高土壤Pb有效态浓度,进而促进大叶井口边草对Pb的吸收。大叶井口边草地上部Pb吸收量最高达（47.4 ± 1.7）mg/kg,是对照的3.66倍。6、12 mmol/kg EDTA处理能极显著地提高土壤中Cd的有效性,但未促进大叶井口边草地上部对Cd吸收。6 mmol/kg EDDS和3 mmol/kg NTA显著提高了土壤中As有效态浓度,进而提高大叶井口边草地上部对As的吸收,大叶井口边草地上部吸收As最高达（276 ± 10） mg/kg。6 mmol/kg EDTA和6 mmol/kg EDDS处理下大叶井口边草提取的Pb、As量最大,分别为（317 ± 53） μg/盆和（873 ± 41）μg/盆,说明6 mmol/kg EDDS处理下大叶井口边草对复合污染土壤中As的修复具有较大的潜力。     

Effects of Chelating Compounds on Mobilization and Phytoextraction of Copper and Lead in Contaminated Soils

Six chelating compounds: ethylenediamine-tetraacetic acid (EDTA), ethylenediamine-N, N'-disuccinic acid (EDDS), tartaric acid, citric acid, glycine and histidine, were tested as potential agents to mobilize copper (Cu) and lead (Pb) from two soils polluted with the emissions from copper smelters. Copper was mobilized with the following efficiency: EDTA > citric and tartaric acids > histidine > EDDS and glycine, while Pb extractability followed the order: EDTA > EDDS >> tartaric and citric acid >> glycine and histidine. With respect to these results, EDTA and EDDS were chosen for a pot experiment on chelate-induced phytoextraction of Cu and Pb by maize (Zea mays). Chelates were applied at the rates of 0.2, 0.5, and 1.0 mmol kg^?1, and this experiment was carried out at two different watering regimes. Both EDTA and EDDS caused significant increase of Cu uptake from soils, but its concentrations in biomass were far below those required for efficient soil remediation. Lead uptake was only slightly affected by chelate application. Losses of Cu from soil by leaching were much higher than those caused by plant uptake.     

Effect of Organic Matter and Salinity on Ethylenediaminetetraacetic Acid–Extractable and Solution Species of Cadmium and Lead in Three Agricultural Soils

Abstract

A study was conducted to investigate the chemical speciation of added cadmium (Cd) and lead (Pb) and their availability as influenced by fresh organic matter (OM) and sodium chloride (NaCl) in three agricultural soils. The soils were treated with 20 mg Cd/kg as cadmium nitrate [Cd(NO₃)₂ · 4H₂O], 150 mg Pb/kg as lead nitrate [Pb(NO₃)₂], 20 g/kg alfalfa powder, and 50 mmol/kg of NaCl and then incubated for 3 months at 60% water‐holding capacity (WHC) and constant temperature (25 °C). Subsamples were taken after 1, 3, 6, and 12 weeks of incubation, and electrical conductivity (EC), pH, dissolved organic carbon (DOC), and concentrations of cations and anions were determined in the 1:2.5 soil/water extract. Available Cd and Pb were determined in 0.05 M ethylenediaminetetraacetic acid (EDTA) extract. Concentrations of organic and inorganic species of Cd and Pb in soil solution were also predicted using Visual Minteq speciation program. The most prevalent species of dissolved Pb and Cd in the soils were Pb‐DOC and Cd²⁺ species, respectively. Salinity application increased the available and soluble Cd significantly in the acid and calcareous soils. It, however, had little effect on soluble Pb and no effect on available Pb. Organic‐matter application decreased availability of added Pb significantly in all soils. In contrast, it raised soluble Pb in all soils except for the acid one and approximated gradually to the added Pb with time. Impact of OM on available Cd was somewhat similar to that of Pb. Soluble Cd increased by OM application in the calcareous soil, whereas it decreased initially and then increased with time in the other soils.     

污灌区土壤团聚体重金属含量分布特征研究

  目的  研究污灌区农田土壤团聚体重金属负载和分布特征,为受污染耕地风险评估和安全利用提供科学指导。  方法  以河南省新乡县某污灌冬小麦种植农田土壤为研究对象,通过干筛法对不同土壤团聚体进行筛分,采用重金属分布因子和质量负载因子法,分析了不同粒径土壤团聚体中重金属Cr、Ni、Cu、Zn、Cd、Pb全量及有效态含量特征。  结果  研究区土壤pH值、有机质、阳离子交换量和电导率分别为7.38 ~ 9.07、11.04 ~ 42.99 g kg?1、5.80 ~ 14.81 cmol kg?1和124.77 ~ 394.70 μS cm?1。pH变异系数为3%,属于弱变异性,而有机质、阳离子交换量和电导率的变异系数分别达到17%、15%和24%,为低变异性。Cr在1 ~ 0.50 mm粒径土壤团聚体中含量最高,达到253.98 mg kg?1,而Ni、Cu、Zn、Cd和Pb含量在0.50 ~ 0.25 mm粒级团聚体最高,分别为22.49、6.59、18.99、1.12和22.88 mg kg?1。不同粒径团聚体中Cr、Ni、Zn和Pb分布因子均小于1,Cu分布因子仅在0.5 ~ 0.25 mm粒径的团聚体大于1,而Cd在不同粒径团聚体上的分布因子均大于1,不同粒径中重金属质量负载因子表现为5 ~ 2 mm > 8 ~ 5 mm > 2 ~ 1 mm > （ < 0.25 mm） > 1 ~ 0.50 mm > 0.50 ~ 0.25 mm。Cr、Zn有效态含量在< 0.25 mm粒径团聚体中含量最高,而Ni、Cu、Cd和Pb有效态含量在0.50 ~ 0.25 mm粒径团聚体中含量最高,团聚体各粒级重金属全量与有效态含量显著正相关（P < 0.05）。  结论  小粒径团聚体重金属总量和有效态含量较高,且两者呈显著正相关关系,而大粒径团聚体负载因子较高;所有重金属中Cd分布因子最高。     

Schwermetallanreicherungen in Salzmarschen der südlichen Nordseeküste

Heavy metal accumulations in Salic Fluvisols of the southern North Sea coast The total contents of Cd, Pb, Cu and Zn (HNO₃ bomb digestion) and their EDTA extractable fractions in Salic Fluvisols were investigated. The mean total content of Cd was 0,09 mg/kg, of Pb 44,1 mg/kg, of Cu 11,4 mg/kg and of Zn 105,6 mg/kg. Mostly the highly developed soils showed higher contents than poorly developed ones. The EDTA extractable fractions were comparatively small: they were 59% (Cd), 44% (Pb), 15% (Cu) and 10% (Zn) of the total content. The heavy metal contents of the soils in Elisabeth-Außengroden were higher than of those in Jadebusen. The vertical heavy metal distribution showed a different sedimentation pattern over the last hundred years. Compared with the geological background values Cd was 2- to 3-fold enriched, Pb 7-fold, Cu 3- to 4-fold and Zn 3-fold in soils with high sedimentation rates. Even higher values are likely in soils with smaller sedimentation rates.     

3种有机酸对伴矿景天修复效率及土壤微生物数量的影响

伴矿景天(Sedumplumbizincicola)是一种Cd和Zn的超积累植物,常用于Cd污染土壤的植物修复。有机酸能够提高土壤重金属的有效性,促进植物对重金属的积累,对重金属污染土壤的植物修复效率具有强化作用,并对土壤微生物数量有重要影响。以河潮土和红黄泥为供试土壤,探讨了乙二胺四乙酸(EDTA)、柠檬酸、草酸对伴矿景天修复效率和土壤微生物数量的影响。结果表明,有机酸能显著提高土壤有效态Cd含量,柠檬酸处理的效果最好,河潮土和红黄泥中有效态Cd含量较单种伴矿景天分别增加72.73%,12.99%(P<0.05);伴矿景天地上部Cd含量在河潮土和红黄泥中以EDTA处理最高,在河潮土和红黄泥中分别比单种伴矿景天增加99.24%和33.32%;与单种伴矿景天相比,添加有机酸处理河潮土和红黄泥中伴矿景天修复效率显著提高。添加有机酸比单种伴矿景天显著增加土壤中微生物数量,其中柠檬酸处理河潮土中细菌和真菌数量分别增加34.38%和68.42%(P<0.05),草酸处理红黄泥中放线菌数量增加150.00%。研究结果可为重金属污染土壤的植物强化修复提供理论支撑。     

重金属污染土壤清洗导致几种营养元素流失的研究

通过HCl、柠檬酸、EDTA这3种提取剂对Pb、Cd、Cu、Zn污染土壤的漫提试验，研究了土壤清洗洗脱重金属的效果，并探讨了土壤清洗导致K、Ca、Mg、Fe、Mn这几种营养元素的流失和有效性的改变。试验结果表明，土壤清洗能有效地洗脱土壤中的Ph、Cd、Cu、Zn，伺时也造成了土壤中K、Ca、Mg、Fe、Mn的流失，降低了其中部分营养元素的有效性。EDTA对重金属的洗脱能力大于HCl和柠檬酸。HCl漫提造成的K、Ca、Mg的流失量大于柠檬酸和EDTA，柠檬酸浸提造成的Fe流失量大于HCl和EDTA，EDTA漫提造成的Mn流失量大于HCl和柠檬酸。HCl和柠檬酸浸提降低了土壤K、Ca、Mg的有效性EDTA浸提提高了土壤K的有效性。降低了土壤Ca的有效性。在高浓度时（50mmol／L），EDTA显著地降低了土壤Mg的有效性。HCl漫提导致土壤K的有效性下降比柠檬酸严重，高浓度的EDTA浸提导致土壤Ca的有效性下降比HCl和柠檬酸严重。HCl、柠檬酸、EDTA浸提都能提高土壤中Fe的有效性．且EDTA的效应大于其它2种萃取剂；在低浓度时，3种提取剂都能提高土壤中Mn的有效性，且以柠檬酸的作用最为明显，当提取剂浓度增加时，Mn的有效性有所回落。     

Mikrosondenuntersuchungen an unterschiedlich stark mit Schwermetallen belasteten Böden. 2. Gehalte an Schwermetallen und anderen Elementen in Huminstoffaggregationen,Streustoffen und Holzkohlepartikeln

Electron microprobe studies on soil samples with varying heavy metal contamination. 2. Contents of heavy metals and other elements in aggregations of humic substances, litter residues and charcoal particles EMA point analysis show that the organic matter constituents of heavy metal contaminated soils are highly enriched with heavy metals. The maximal trace element accumulation were for Cu up to 13,000 mg/kg, for Zn up to 48,000 mg/kg, for Cd up to 2,100 mg/kg and for Pb up to 193,000 mg/kg. The affinity for the accumulation of the different heavy metals in aggregations of humic substances can be described by the sequence Cu > Pb ? Cd > Zn ? Ni > Co. In very strongly acidified humic top soil horizons the Pb and Cd accumulation in the organic matter constituents is in competition with the accumulation in Fe and Mn oxides. The heavy metal contents (especially of Cu) of the organic matter are often correlated with the content of organically bound calcium. The EMA results also show that high heavy metal amounts occur in combination with Ca-accumulations in the epidermis and the outer bark parenchym of decayed roots. EMA point analysis of the interior of fungus sclerotias show that sclerotias can contain high amounts of heavy metals, in particular lead (up to 49,700 mg Pb/kg). From statistical results of EMA point analysis follows that lead and other heavy metals attached to humic substances are not only bound as metal organic complexes but also as organic metal phosphate complexes. Also charcoal particles of polluted soils contain high amounts of heay metals. The accumulation affinity is quite similar to that of humic substances.     

Mixed chelators of EDTA,GLDA, and citric acid as washing agent effectively remove Cd,Zn, Pb,and Cu from soils

Purpose

Soil washing with chelators is a viable treatment alternative for remediating multi-contaminated soils. The aim of this study was to investigate the removal efficiencies of Cd, Zn, Pb, and Cu in alkaline and acid multi-metal-contaminated soils by washing with the mixed chelators (MC).

Materials and methods

The batch experiments were carried out to evaluate the removal efficiencies of heavy metals in contaminated soils by the MC with different molar ratios of EDTA, GLDA, and citric acid, and evaluated the washing factors, including contact time, pH, MC concentration, and single and multiple washings at the same MC dose, on the removal efficiencies.

Results and discussion

Results showed that the removal efficiencies for Cd, Zn, Pb, and Cu by the MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) were as much as those of the only EDTA washing from both soil at the same application dose of total chelators; moreover, the application dose of EDTA decreased by 80%. For the alkaline-contaminated soil, the removal efficiencies of Cd, Zn, Pb, and Cu decreased with the increasing of the solution pH, which was opposite to acid-contaminated soil. This was attributed to that the metal-ligand complex could be obviously re-adsorbed on the soil surface sites, particularly in low pH values. The removal efficiencies of Cd, Zn, Pb, and Cu depended on MC concentration. A higher MC concentration led to a more effective removal of Cd, Zn, Pb, and Cu in alkaline-contaminated soil; however, their changes were slightly increased in acid-contaminated soil. At the same dose of MC, single washing with higher MC concentration might be favorable to remove heavy metals, moreover, with much less wastewater generation.

Conclusions

The MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) may be a useful, environmentally friendly, and cost-effective chelators to remediate heavily multi-metal-contaminated soil.