缓释微胶囊EDTA强化玉米提取土壤中铅铜的效应研究

将EDTA转化成具有缓释性能的微胶囊EDTA（Cap-EDTA）作为螯合剂,采用大宝山矿区周边重金属复合污染农田土壤进行重金属连续批浸提及盆栽试验,比较研究Cap-EDTA和未微胶囊化EDTA（Ncap-EDTA）对土壤铅铜活化的动态变化及其对玉米吸收提取铅铜的影响。结果表明：Cap-EDTA处理土壤溶液中初始增溶的铅铜质量分数显著低于Ncap-EDTA处理,且使土壤溶液中的铅铜质量分数长时间持续保持在适度范围内。添加Cap-EDTA的处理显著提高玉米吸收提取铅铜的效率,如实施3 mmol·kg-1的Cap-EDTA使玉米地上部Pb的积累高达1.26 mg·pot-1,是对照处理的1.9倍,是等量Ncap-EDTA处理的1.4倍。因此,在进行污染土壤植物修复的EDTA调控时,采用微胶囊化EDTA,能降低因直接实施EDTA而带来的污染地下水风险,且显著提高玉米修复效率。     

包膜控释和常用氮肥氮素淋溶特征及其对土水质量的影响

大量施用氮素化肥所引起的氮素损失和环境污染正日益受到重视。通过土柱模拟氮素养分的淋洗试验,探讨包膜控释氮肥和常用氮肥的氮素淋失特点及其对土壤和地下水质量的影响。研究结果表明,不同氮肥施入土壤后氮素的淋失率有着显著的差异,其中硝酸钾中氮素淋失率最高,其次为尿素,硫酸铵和碳铵的氮素淋失量明显较小。然而控释氮肥因其控制释放的特点,在氮素释放的高峰期,其模拟淋失量较高,但如果在田间条件下此释放高峰期与作物吸肥高峰期相吻合,则会显著地降低其淋失率。除尿素外,被淋失的氮素均以硝态氮为主,尿素则以酰胺分子态被淋溶。大量速效化肥的施入会形成土壤中的肥料"微域点",引起交换性Ca2+、Mg2+离子的淋失,从长远来看可引起土壤结构的破坏,而施用控释肥则很少形成这种"微域点",有利于土壤结构和肥力的维持。不同氮肥处理淋洗后对土壤pH值和有效氮含量变化的影响差异较大,其中以控释肥对土壤pH值变化的影响较小。大多数氮肥处理在淋洗后,土壤中各层速效氮含量较淋洗前有所降低,然而两种控释氮肥处理的土壤表层却能持续保持较高的有效氮含量。     

大宝山排土场植物稳定修复对模拟酸雨重金属淋溶的响应

以广东省韶关市大宝山排土场多金属重度污染土壤为研究对象,通过模拟酸雨淋溶实验,探究淋溶对植物稳定修复(土壤改良+种植红麻/苎麻)后土壤重金属迁移的影响.结果表明,在土柱上层(0-10 cm)土壤中施加0.4%石灰+0.2%有机肥,能显著提高淋出液pH值,并大幅度降低0-10 cm土壤中的重金属有效态含量;种植红麻和苎麻处理后,淋出液pH值较空白组显著提高,淋溶液淋失量相较于空白处理分别减少了32.5%和12.4%,淋出液中铅、锌、铜、镉重金属含量分别降低了65.2%和71.3%、81.6%和78.5%、79.4%和71.7%以及86.7%和85.3%;且种植红麻、苎麻后,土柱下层(21-30 cm)的土壤铅、锌、铜、镉重金属有效态含量相较于空白处理分别降低了16.3%和22.9%、30.5%和17.9%、18.8%和32.5%以及38.1%和29.7%.因此,种植红麻、苎麻不仅能显著降低径流淋溶失量,而且降低了淋出液中重金属含量,减轻了淋出液对地下水造成的污染;在模拟酸性降雨条件下,种植红麻、苎麻并施用改良剂处理重金属污染土壤的模式在植物稳定修复方面具有较好的应用潜力.(图7表6参42)     

硅钙镁肥对不同母质稻田土壤水稻Cd吸收累积的影响及其差异研究

为研究硅钙镁肥(GF)对不同母质稻田土壤水稻Cd吸收累积的影响及其差异,选取黄泥田(板页岩母质发育水稻土)和麻砂泥(花岗岩母质发育水稻土)进行水稻盆栽试验,分析各生育时期土壤pH值与CEC变化、土壤溶液中Cd浓度、水稻各部位(根、茎、叶、谷壳和糙米) Cd含量及水稻全株总累积量、水稻根表铁膜Cd、Fe含量与总累积量.结果表明:稻田土壤施用GF显著降低了土壤溶液Cd浓度;施用GF显著提升了土壤pH和CEC;施用GF降低了水稻根、茎、叶、谷壳与糙米中的Cd含量,显著降低水稻全株Cd累积量.稻田土壤施用GF促进了水稻根表铁膜的形成,增加了各生育时期DCB-Fe、降低了DCB-Cd含量,抑制了Cd由根部向上迁移;稻田土壤施用GF,黄泥田与麻砂泥水稻糙米Cd含量降低至0.11 mg/kg和0.15 mg/kg,均低于国家标准.相关性分析表明,土壤pH与土壤溶液Cd浓度、水稻糙米Cd含量呈显著(P0.05)或极显著负相关(P0.01),水稻根表铁膜Fe累积量与DCB-Cd、根与糙米Cd含量呈极显著负相关(P0.01); GF使叶对糙米Cd再转运贡献率降低5.88%(黄泥田)和12.80%(麻砂泥).稻田土壤施用GF可有效阻控水稻对Cd的吸收累积,且麻砂泥效果优于黄泥田.     

稻壳炭施用对太湖滨岸灰潮土氮磷淋失及土壤性质的影响

探究稻壳炭施用对太湖滨岸灰潮土养分淋失的抑制效应,以及对灰潮土性质的改良作用,为太湖滨岸植被带恢复提供理论依据。通过16周的土柱淋溶试验,研究了不同施用率(0%,1%,2%和5%)稻壳炭与肥料(NH_4NO_3和KH_2PO_4)混施后,对太湖滨岸灰潮土氮磷淋失以及土壤性质的影响。结果表明,随着稻壳炭施用量的增加,灰潮土土柱渗滤液中铵态氮累积淋失量减少11.7%—26.6%,硝态氮累积淋失量减少32.4%—67.3%。然而,当稻壳炭施用率为2%和5%时,土柱渗滤液中磷酸盐累积淋失量分别显著增加了32.1%和54.2%。稻壳炭施用16周后,灰潮土土壤总氮含量显著增加,土壤有效磷含量在2%和5%施用率下显著增加。同时,添加稻壳炭使土壤铵态氮含量显著减少,而土壤硝态氮含量显著增加,这表明稻壳炭添加增强了滨岸灰潮土土壤硝化作用。灰潮土土壤微生物生物量碳在2%和5%的稻壳炭施用率下分别显著增加了22.4%和36.8%,土壤微生物生物量氮在5%的稻壳炭施用率下显著增加了48.4%。随着稻壳炭施用量的增加,灰潮土土壤容重减小,而pH值、土壤总孔隙度以及土壤持水能力增加。因此,施用稻壳炭减少了太湖滨岸灰潮土土壤氮素的淋失,但当施用率为2%—5%时,增加了土壤磷素淋失的风险;添加稻壳炭使土壤总氮,有效磷以及土壤微生物生物量增加,这将有利于太湖滨岸植被带的恢复。     

动物粪便堆肥的养分淋溶特征模拟研究

通过室内土柱模拟实验,研究了自然条件下土壤施用不同量的动物粪便堆肥对氮、磷和钾的淋失的影响,结果表明:氮、磷和钾的淋出量都与堆肥用量呈正相关关系,总氮的淋出主要集中在土壤下层,随着施肥量的增加,淋出液总氮浓度最高达到300mg·l-1,可能对地下水造成污染,总磷主要聚集在土壤的上层,最高达到8.5mg·l-1,磷向下迁移较为缓慢,随淋溶次数的变化不显著.土柱上层渗滤液中钾的含量远大于下层,各施肥量处理都在前三次淋溶中随淋溶次数的增加而有一定程度减小,随后趋于稳定.     

壳聚糖对污染土壤中吸附态Pb（Ⅱ）的解吸作用

土壤中重金属的吸附-解吸直接影响重金属在土壤及其生态环境中的形态转化、迁移和归趋.利用螯合剂促进普通植物富集吸收土壤中重金属是一种新的土壤组合修复技术, 向污染土壤中施用螯合剂可增加土壤溶液金属的浓度和活度,有利于金属到根部而被植物吸收.通过吸附等温实验研究了壳聚糖对污染土壤中铅的解吸作用.将壳聚糖提取液加入含Pb土壤中结果表明,壳聚糖螯合剂能提高土壤中吸附态铅的解吸效率,增加解吸溶液中Pb2 的浓度.壳聚糖对污染土壤中铅的解吸作用随着壳聚糖加入量的增大而增大,用浓度为0.4 g·L-1的90%脱乙酰度壳聚糖做提取液,提取液pH＝3,提取平衡时间10 h达到最高提取率32.4%,该吸附过程遵从Langmuir等温吸附方程; 土柱淋溶实验表明壳聚糖对污染土壤中Pb2 的提取率为27.4%.研究结果为铅在环境中的迁移转化和治理技术等方面的实际应用提供有价值的参考.     

EDTA、茶皂素及其混剂对土壤中Pb、Zn的解吸效果

以广东大宝山尾矿库区土壤为研究对象,通过振荡提取实验,研究了不同pH值下EDTA、茶皂素及其混剂对土壤中重金属铅和锌的解吸效果,结果表明:(1)EDTA对土壤中铅、锌的解吸率最高可分别达到54.19%、48.75%;茶皂素对土壤中铅、锌的解吸能力远弱于EDTA,尤其在pH值大于3的条件下,茶皂素对土壤中铅的解吸效果非常有限;(2)EDTA与茶皂素的混剂对土壤中铅的解吸高于锌,最高可分别达到73.98%、65.78%,这主要与土壤中铅、锌的形态分布有关;(3)在pH值在3—6范围内,铅的解吸率随pH值减小而增加,在pH值为4—6,锌的解吸率随pH值减小而增加.实验结果表明,茶皂素能强化EDTA对重金属的洗脱效率,并且在pH值2—7范围内,二者的协同作用受pH的影响较小.     

稻田土壤磷淋失潜力与磷积累的关系

了解稻田土壤磷积累对排水和渗漏液中磷浓度的影响,可为稻田磷素淋失预测提供依据.采用室内模拟方法,研究稻田土壤Olsen-P水平与土壤溶液中磷质量浓度之间的关系.结果表明,土壤溶液中磷质量浓度随土壤Olsen-P水平增加而增加,其中,黏土、壤黏土和壤土的Olsen-P超过临界值(分别为84、65和53 mg·kg-1)后,土壤溶液中磷质量浓度显著增加.土壤Olsen-P水平较低时,黏土、壤黏土和壤土的土壤磷素积累与排水和渗漏液中磷质量浓度之间的关系较为相近,这3类土壤溶液中磷质量浓度与土壤Olsen-P水平存在线性相关关系.而砂土溶液中无明显临界值,砂土溶液中磷质量浓度与土壤Olsen-P水平间也存在线性相关关系.相同Olsen-P水平时,砂质土壤磷淋失潜力明显高于其他土壤.     

金顶铅锌矿区铅锌氧化矿石中镉的风化淋滤实验

云南金顶铅锌矿是中国较为典型的高镉铅锌矿区之一。通过模拟常温条件下天然雨水的自然淋滤过程,对矿区两个典型的富镉氧化矿石样品进行了长时淋滤实验研究。初步结果表明:随着淋滤时间的延长,滤液中pH值(pH=7.2～8.5)和SO42-浓度无显著变化。滤液中Cl-离子浓度随时间呈显著增大趋势。溶解态镉和其它主要元素铅、锌、铜和锰质量浓度变化随时间呈降低趋势。铅锌氧化矿石易淋出而释放出镉等有害元素,滤出元素可以迅速发生沉淀或被沉淀物包裹,其能力表现为Zn>Pb>Cd。两个不同矿石镉的淋失量有所差别,矿石中菱锌矿质量分数是影响镉淋失的主要因素。矿区富镉岩石和矿物的自然风化对矿区流域水生态环境造成潜在危害。     

模拟降水对碱性盐化土壤中镉的淋滤及形态变化的影响

采用人工模拟方式,试验研究了不同pH值的降水对碱性盐化土壤中镉的连续淋滤效果,分析了淋洗后土壤中镉的形态变化特征。结果表明,在不同pH值降水对土壤中镉的淋滤过程中,12h内基本上达到高峰,12h后镉的淋滤量较低,随着时间的延续镉的淋洗量基本保持不变;降水有利于土壤中的镉释放,且pH值越低,镉的释放量越高。土壤盐化对降水淋洗镉的效果有一定影响,氯化物的存在,有利于镉的淋滤,淋滤量增加值在18%～94%之间,随着淋洗液pH值的增加,镉的淋滤量增加幅度减少;与对照组土壤样品相比,淋洗液pH降低利于增大硫酸盐型盐化土壤中镉的淋滤量,当pH值为中性时,镉的淋滤量减少;苏打型盐化土壤镉的淋洗效果与硫酸盐型土壤相似。模拟降水淋洗后,土壤中镉的形态发生明显变化,与淋洗前相比,土壤中镉的可交换态、碳酸盐结合态、有机结合态的质量分数降低,随着淋洗液酸性的增加,降低幅度增大;镉的铁锰氧化态相对质量分数在淋洗后有所增加。     

Toxic elements leaching in different soils affected by the spill from the aznalcollar pyrite mine (Sevilla,Spain)

A study has been made of the leaching of Cd, Zn, Pb, Cu, Tl and As in three representative soils of the zone affected by the spill from a pyrite mine in Aznalcollar (Sevilla, Spain) employing packed soil columns. According to the breakthrough and cumulative leaching curves, the relative mobilities of the different toxic elements in the columns are as follows: Tl > Cd > Zn > As > Cu > Pb. The results also show that the soils themselves have a good capacity for immobilizing the soluble fraction of the elements from the spilled mud, this capacity varying as follows: clayey soil with a high carbonate content > clayey soil with a moderate carbonate content > sandy‐clay loam soil with a low carbonate content. The results obtained in the work are a valuable contribution to the necessary assessment of the impact of the toxic spill on underground waters.     

模拟酸雨对南方红壤镉释放的影响

采用室内模拟酸雨淋溶土柱的方法,研究了酸雨对2种红壤镉释放的影响。结果表明,酸雨加速了红壤中镉的释放。在pH4.5的酸雨作用下,镉的平均释放水平是对照的1.6～1.7倍,在pH3.5的酸雨作用下,镉的平均释放水平是对照的2.0～6.5倍。经过相当于9150～10650mm降水量的淋溶后,pH4.5的酸雨使红壤镉的累积释放量提高63.0%～80.0%,pH3.5的酸雨使其提高102.7%～630.6%。红壤镉的释放与铝、铁的释放具有极显著或显著相关性。酸雨对镉释放的影响可增加水体中镉的负荷,从而加重镉对人类的直接或潜在危害。     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO?) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0-5% powdered eggshell waste and curing the soil (1,246 mg Pb kg?1 soil and 17 mg Cd kg?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl?), 1 M CaCl?, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH?COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO? and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO? and eggshell waste, regardless of extractant. Using CaCl? extraction, the lowest Cd concentration was achieved upon both CaCO? and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH?COOH or EDTA in soils treated with CaCO? and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO? for the immobilization of heavy metals in soils.     

有机酸对根际土壤中铅形态及其生物毒性的影响

采用根袋盆栽试验和连续浸提方法研究外源柠檬酸、EDTA对根际土壤中Pb形态转化及其生物毒性的影响。结果表明，有机酸能明显活化根际土壤中的Pb，高浓度(3mmol／L)比低浓度(0．5mmol／L)的柠檬酸对Pb的活化能力强；EDTA在低浓度(0．5mmol／L)时对Pb的活化能力就很强。柠檬酸、EDTA能增强土壤Pb的毒性，提高小麦根部对Pb的吸收，并促进Pb由根部向地上部转移。     

Natural and synthesised iron-rich amendments for As and Pb immobilisation in agricultural soil

The immobilisation of heavy metals in contaminated soils is a promising alternative to conventional remediation techniques. Very few studies have focused on the use of iron-rich nanomaterials and natural materials for the adsorption of toxic metals in soils. Synthesised iron-rich nanomaterials (Fe and Zr–Fe oxides) and natural iron-rich materials (natural red earth; NRE) were used to immobilise As and Pb in contaminated agricultural soil. Total concentrations of As and Pb in the initial soil (as control) were 170.76 and 1945.11 mg kg^?1, respectively. Amendments were applied into the soil at 1, 2.5 and 5% (w/w) in triplicate and incubated for 150 days. Except for the NRE-amended soil, soil pH decreased from 5.6 to 4.9 with increasing application rates of Fe and Zr–Fe oxides. With addition of Fe and Zr–Fe oxides at 5%, the ammonium acetate (NHO₄Ac)-extractable Pb was greatly decreased by 83 and 65% compared with NRE addition (43%). All subjected amendments also led to a decrease in NHO₄Ac-extractable As in the soils, indicating the high capacity of As immobilisation. Soil amended with NRE showed a lower ratio of cy19:0 to 18:1ω7c, indicating decreased microbial stress. The toxicity characteristic leaching procedure produced results similar to the NHO₄Ac extraction for As and Pb. The NRE addition is recommended for immobilising heavy metals and maintaining biological soil properties.     

Effects of carbon nanotube and biochar on bioavailability of Pb,Cu and Sb in multi-metal contaminated soil

This study examined the effects of carbon nanotube and biochar on the bioavailability of Pb, Cu and Sb in the shooting range soils for developing low-cost remediation technology. Commercially available multi-walled carbon nanotube (MWCNT) and biochar pyrolyzed from soybean stover at 300 °C (BC) at 0.5, 1 and 2.5% (w w^?1) were used to remediate the contaminated soil in an incubation experiment. Both DTPA (bioavailable) and TCLP (leaching) extraction procedures were used to compare the metal/loid availability and leaching by the amendments in soil. The addition of BC was more effective in immobilizing mobile Pb and Cu in the soil than that in MWCNT. The BC reduced the concentrations of Pb and Cu in the soil by 17.6 and 16.2%, respectively. However, both MWCNTs and BC increased Sb bioavailability by 1.4-fold and 1.6-fold, respectively, in DTPA extraction, compared to the control. The toxicity characteristic leaching procedure (TCLP) test showed that the leachability of Pb in the soil amended with 2.5% MWCNT was 1.3-fold higher than that the unamended soil, whereas the BC at 2.5% decreased the TCLP-extractable Pb by 19.2%. Precipitation and adsorption via electrostatic and π–π electron donor–acceptor interactions were postulated to be involved in the interactions of Pb and Cu with surfaces of the BC in the amended soils, whereas ion exchange mechanisms might be involved in the immobilization of Cu in the MWCNT-amended soils. The application of BC derived from soybean stover can be a low-cost technology for simultaneously immobilizing bioavailable Pb and Cu in the shooting range soils; however, neither of amendments was effective in Sb immobilization.     

中国典型土壤中铅的生物可给性的影响因素分析与健康风险评估

土壤铅污染及其危害备受关注.作为评估其对人体健康风险的科学指标之一,土壤铅的生物可给性的影响因素仍不甚明确.采集中国5种典型土壤(红壤、褐土、黑土、棕壤和黄壤),根据国标中一类建设用地的管制值制备成800 mg·kg-1的铅污染土壤样品,利用先进的基于生理学的体外试验方法(改进的PBET模型)研究经口部摄入的土壤铅的生...     

铅锌矿区农田土壤重金属有效态空间分布及其影响因子分析

利用地统计学方法,研究了广西岩溶地区某铅锌矿区农田土壤中Cd、Zn、Pb、Cu四种重金属有效态含量的空间分布特征及其影响因子.结果表明:研究区域不同程度地受到Cd、Zn、Pb、Cu的污染,且水田污染较旱地严重;与广西土壤背景值相比,污染程度最严重的是Cd,在水田和旱地中超标率均为100%,平均超标倍数分别为312.94和33.67;其次是Zn,在水田和早地中超标率分别为100%和34%,平均超标倍数分别为38.34和2.11;污染最轻的为Cu,超标率仅为7%.空间分析表明,有效态Cd、Zn、Pb、Cu的块金系数分别为2.7%、0.2%、6.5%、0.13%,体现了强烈的空间自相关性,且四种重金属空间分布特征相似,在离原铅锌选矿厂较近的西北偏西面有效态Cd、Zn、Pb、Cu含量最高,沿着西北偏西至东南偏东的灌溉渠流向,有效态Cd、Zn、Pb、Cu的含量呈递减趋势,东部旱地有效态Cd、Zn、Pb、Cu含量相对较低.土壤有效态Cd、Zn、Pb、Cu在污染区的空间分布与土壤基本理化性质关系密切,有效态Cd、Zn、Pb、Cu与pH、阳离子交换量、粘粒都呈极显著负相关,与有机质含量则呈极显著正相关.