4种改良剂对土壤-黑麦草系统中镉行为的影响

以黑麦草（Lolium perenne L.）作为修复植物,开展了石灰、磷灰石、木炭、猪粪4种改良剂对重金属Cd污染土壤的田间原位修复试验研究。结果表明：改良剂提高了土壤pH值并促进土壤Cd从生物可利用性高的形态向迟效态转化,降低对生物和环境的直接毒害作用,促进黑麦草的生长。以黑麦草生物量和Cd富集量的增加作为评价指标,4种改良剂修复Cd污染土壤效果依次为：石灰〉磷灰石〉木炭〉猪粪。石灰处理中黑麦草Cd富集量为13.11 mg,与其他处理均呈现显著差异。污染土壤重金属Cd的化学形态与黑麦草对Cd的吸收密切相关。黑麦草地上部分Cd质量分数,与土壤B-2态Cd呈极显著正相关关系,相关系数为0.730。黑麦草地下部分Cd质量分数,与B-2、B-3态Cd均呈极显著正相关关系,相关系数分别为0.756、0.786;黑麦草地上部分和地下部分Cd质量分数均与B-4态Cd呈极显著负相关关系,相关系数分别为0.757和0.708。     

模拟酸雨对磷基材料稳定化土壤Cu、Cd、Pb和P活性的影响

为了研究酸雨淋溶前后不同磷基材料对土壤重金属稳定化的影响,通过室内土柱淋溶实验,考察不同pH值酸雨淋溶前后磷酸二氢钾(PDP)和羟基磷灰石(HAP)稳定化重金属污染土壤pH值、重金属和P有效活性的变化。结果表明:PDP和HAP增加了土壤pH值和速效P含量,降低了土壤有效态Cu、Cd和Pb含量,促进了重金属由活性态向非活性态和潜在活性态转化,但pH=3.5的酸雨使PDP和HAP处理土壤pH值降低0.45和0.47,且酸雨淋溶降低了PDP处理速效P含量,提高了土壤有效态Cu和Cd含量;酸雨淋溶使HAP处理土壤总Cu含量和CK处理总Cd含量分别降低14.5%～15.9%和20.4%～26.5%,但增加了HAP和PDP处理离子交换态Cu和Pb含量;PDP和HAP处理显著增加了土壤总P、树脂P、HCl结合态P和残渣态P含量,但酸雨淋溶降低了PDP处理总P和树脂P含量,显著增加了HAP和PDP处理土壤稳定态P含量(P0.05)。模拟酸雨作用下HAP较PDP处理对Pb和Cd具有更好的稳定化效果和更低的P释放风险,具有更好的应用潜力。     

改良剂对铜镉污染土壤的修复效果及健康风险评估

为了解磷灰石、石灰、木炭对贵溪冶炼厂周边重金属污染土壤的修复效果,通过化学浸出等方法研究了修复后第1年(2010年)和第4年(2013年)土壤中Cu和Cd的可浸出性、有效态(CaCl_2)和生物可给性。结果表明,添加磷灰石、石灰和木炭显著增加了土壤p H值,降低土壤交换性酸和交换性铝含量。改良剂的添加降低了土壤中Cu和Cd的可浸出性和有效态,且磷灰石和石灰处理效果优于木炭,但随着时间推移处理效果减弱。磷灰石和石灰处理1 a后土壤的Cu生物可给性较对照分别降低28.6%和23.1%,Cd生物可给性分别降低21.7%和22.8%,第4年Cu和Cd的生物可给性均有上升趋势。另外,改良剂处理后Cu和Cd的风险系数(QH)均小于1,儿童的风险系数均大于成人。总体上,磷灰石处理在降低Cu和Cd可浸出性、有效态和生物可给性方面具有更好的效果。     

石灰、硅钙镁改良剂对不同土壤-水稻系统Cd吸收累积的影响

为研究改良剂(石灰、硅钙镁肥)对典型稻田土壤-水稻系统Cd吸收累积的影响,选取河沙泥(潮土母质发育)和紫泥田(紫色砂页岩母质发育)模拟制备成中度Cd污染土壤,施加不同用量的石灰和硅钙镁肥,进行水稻盆栽试验,分析土壤pH、土壤Cd形态以及水稻各部位Cd含量变化,探讨不同改良剂对不同土壤-水稻系统Cd吸收累积的影响.结果表明,施用石灰和硅钙镁肥能显著提高河沙泥土壤pH值,分别提高0.62—0.79个单位、0.35—0.46个单位,但对紫泥田pH值无显著影响.向河沙泥中施用石灰能降低其土壤酸提取态Cd含量,且在S3.0处理时降幅最大;而紫泥田施用硅钙镁肥能显著降低其酸提取态Cd.施用石灰和硅钙镁均能降低河沙泥水稻糙米Cd含量,分别降低23.5%—35.9%、9.5%—21.9%,且随着施用量的提高,糙米Cd含量降低幅度逐渐增大;施用硅钙镁肥能显著降低紫泥田糙米Cd含量,下降幅度为23.5%—34.1%.同种改良剂对水稻Cd吸收累积的影响因土壤类型不同而存在差异,向河沙泥中施用石灰和紫泥田中施用硅钙镁能最大程度抑制水稻对Cd的吸收累积,降低糙米Cd含量,提高稻米品质.     

磷灰石等改良剂对土壤-黑麦草系统中铜行为的影响

以黑麦草作为修复植物,开展了石灰、磷灰石、木炭、猪粪等4种改良剂对重金属Cu污染土壤的田间原位修复研究.结果表明,改良剂提高了土壤pH值并促进土壤Cu从可利用态向潜在可利用态和不可利用态转化,以降低对生物和环境的直接毒害作用,促进黑麦草的生长.以黑麦草生物量和Cu富集量作为评价指标,添加改良剂的4种处理修复Cu污染土壤...     

典型固废拆解区土壤Cd、Cu含量特征及其对农产品安全的影响

以浙东沿海某典型固废拆解区为研究区域,通过采集土壤、灌溉水、农作物以及大气干湿沉降样品进行分析测试,研究土壤Cd、Cu含量特征及其对农产品安全的影响.结果表明,研究区表层(0～20 cm)土壤已遭受较为严重的Cd、Cu污染,土壤Cd、Cu含量平均值分别为0.34和65.83 mg·kg-1.土壤中活性较高的水溶态、离子交换态和碳酸盐结合态Cd占Cd总量的比例达45.37%,说明其生物有效性和潜在危害性极大.大气干湿沉降、污水灌溉对土壤Cd、Cu的累积均有一定影响.农作物尤其是蔬菜Cd、Cu含量已有不同程度的累积甚至超标,食用的潜在危害性较大.相关分析表明,农作物Cd、Cu含量与土壤中Cd、Cu含量均呈显著正相关关系.     

广州郊区农业土壤重金属含量与土壤性质的关系

研究了广州郊区农业土壤性质和土壤中的重金属含量,并对2者的相关关系进行了分析。结果表明:广州郊区农业土壤中壤土占样品总数的70.5%,土壤pH值平均为5.93,土壤有机质平均含量为31 7g·kg-1,土壤阳离子交换量不高,且各区之间变幅较大;Cu、Pb、Zn、Ni、Cd、As和Hg有效态含量在3种土壤中顺序为菜园土>水稻土>赤红壤;土壤重金属和土壤理化性质间的关系复杂,如有效态Cu、Zn、Ni与土壤有机质含量呈极显著相关,Cd与土壤有机质含量和土壤粘粒含量呈极显著相关,As除与有机质含量和粘粒含量有关,与pH、阳离子交换量也有极显著相关关系。     

模拟酸雨下Cd、Cu、Zn复合污染对土壤微生物量碳和酶活性的影响

在实验室内，研究了模拟酸雨下Cd、Cu、Zn复合污染对供试土壤中微生物量碳和酶活性的影响．结果表明，污染土壤中微生物量碳和酶活性明显降低，脱氢酶活性几乎丧失，脲酶、酸性磷酸单脂酶、总磷酸酶和多酚氧化酶活性均明显降低到一较低水平．污染土壤中微生物量碳和酶活性随重金属量增加而进一步降低，有效性Cd、Cu、Zn含量与土壤微生物量碳和酶活性之间呈显著性负相关．     

长期不同施肥对红壤Cu和Cd含量及活化率的影响

对始于1990年的红壤旱地施肥长期定位试验的6个处理包括对照(不施肥,CK)、施氮(N)、氮磷(NP)、氮磷钾(NPK)、氮磷钾+有机肥(NPKM)和有机肥(M)的历年耕层土壤重金属Cu和Cd全量和有效态含量进行分析,以阐睨长期不同施肥条件下红壤Cu、Cd含量及活化率变化特征.结果表明,16 a连续不施肥或施用化肥(N/NP/NPK)条件下土壤Cu、Cd全量和有效态含量基本保持不变;Cu活化率随施肥时间变化不显著,但Cd的活化率在施肥后期(1996-2006)呈明显上升趋势,在施氮处理上高达95.7%;不施肥和配施化肥下Cd的活化率与土壤pH值呈极显著负相关.化肥配施有机肥(NPKM)和单施有机肥处理(M)的土壤中Cu、Cd全量和有效态含量及其活化率随时间均呈显著上升趋势;土壤Cd含量从1990年的0.12 mg·kg-1 上升为2006年的1.31～1.48 mg·kg-1,平均年上升0.08～0.09 mg·kg-1;土壤有效态Cd含量2006年达到0.53～0.58 mg·kg-1,为1990年的18.0～19.9倍;Cd活化率与土壤有机质含量呈显著正相关.长期施用有机肥红壤Cu、Cd含量超标严重,土壤Cu和Cd全量之间达极显著相关(r=0.887**,n=30),其来源具有一致性,有机肥为环境带来的风险应予以重视.     

改性污泥对矿区铜、镉污染土壤的修复

城市污泥的重金属含量超标是限制其资源化利用的主要瓶颈,论文采用石灰＋硫粉＋生物淋滤的方法去除重金属,制备改性污泥,探讨其对矿区Cu、Cd污染农田土壤的修复效果,以期实现以废治污的目标。供试水稻土采自江西某矿区附近农田,土壤Cu和Cd的TCLP（Toxicity characteristic leaching procedure）浸出量分别为40.34 mg·kg-1和660.1μg·kg-1,其中Cu的质量分数超过国际标准值15 mg·kg-1。通过室内土培的方法,将改性污泥分别按土重的0%、1%、3%、5%和10%施入供试土壤培养30 d后,分析土壤Cu和Cd的活性、形态变化以及土壤蛋白酶和脲酶活性等指标评价改性污泥对污染土壤的修复效果及作用机理。结果表明,改性污泥对土壤Cu产生显著的钝化作用,且各施用量对Cu的有效态含量表现出显著差异。当改性污泥的用量为土重的5%时,Cu的有效态含量降至12.03 mg·kg-1,低于国际标准。改性污泥对土壤Cd的钝化效果相对较弱。当改性污泥的用量为1%时,土壤Cd的活性反而有所增加。当改性污泥的用量为5%时,Cd的活性显著降低,土壤Cd的浸出量降至539.6μg·kg-1。土壤重金属形态分析的结果表明,土壤Cu主要以碳酸盐结合态、有机结合态和残渣态存在。改性污泥用量增加,可交换态Cu含量下降,当改良剂用量为土重的5%时,可交换态Cu由8.10%降至4.10%。相反,有机结合态Cu含量由26.45%增加至32.34%。土壤的可交换态Cd含量由36.80%降至30.69%。说明施用改性污泥,土壤可交换态Cu、Cd向有机结合态发生转化。土壤蛋白酶和脲酶的活性变化能较好地指示修复效果,且土壤脲酶的指示效果优于蛋白酶。     

The effect of humic substances on Cu migration in the soil profile

Humic substances (HS) are widely used for diverse purposes. The effect of HS on the metal’s status in contaminated soils is contradictory. The aim of this work was to investigate the Cu migration in soils treated with HS. A model field experiment with the addition of Cu (1.243?mg?Cu/kg) and HS Extra® (potassium humate) was performed. The Cu addition resulted in acidification (by 0.7 pH) after 3 months. The major part of the added Cu remained in the upper 7-cm-thick soil layer; 4% reached the lower soil layer, while only 0.1% were removed beyond the profile. The addition of HS mitigated soil acidification increased the content of Cu bound to solid-phase organic substances and abruptly reduced the Cu activity in the soil liquid phase. Simultaneously, the HS addition increased the water-soluble organic substances (WSOS) by four times, including those in the hydrophilic and hydrophobic fractions, resulting in a twofold increase in the content of soluble Cu. Copper complexes with hydrophilic WSOS mainly reached lysimeters, and hydrophobic organic substances were absorbed by the soil. The HS addition to a slightly acidic soil can accelerate the migration of Cu to adjacent environments.     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

Cu、抗生素协同污染对土壤微生物活性的影响

随着畜禽养殖业的规模化发展,重金属和抗生素在土壤环境中协同污染的几率不断升高。为分析和评价重金属、抗生素协同污染对土壤微生物生态系统的影响,以Cu、磺胺甲基嘧啶为添加毒物,其中,Cu的添加质量分数为0、100、500mg·kg-1;磺胺甲基嘧啶的添加质量分数为0、5、25、50、100mg·kg-1,采用室内培养试验的方法研究分析了cu、磺胺甲基嘧啶协同污染对土壤微生物微生物基础呼吸、微生物量碳、微生物量氮、硝化势、尿酶以及脱氢酶等土壤微生物指标的影响。结果表明,与磺胺甲基嘧啶单独污染处理相比,在Cu的质量分数为100mg·kg。协同污染污染下土壤微生物呼吸,土壤微生物量碳、氮以及土壤尿酶等指标的活性均明显增加;即表明它们对Cu与磺胺甲基嘧啶的协同污染表现出不同程度的交互抗性;在cu的协同污染质量分数为500mg·kg-1,Cu与磺胺甲基嘧啶对土壤各微生物指标则基本表现为协同抑制作用;在不同剂量Cu的协同污染处理下,当磺胺甲基嘧啶处理质量分数≥10mg·kg-1时,各土壤微生物指标的活性随着其处理质量分数的增加而显著降低,表现出很好的剂量依赖效应。因此,低剂量的Cu．磺胺甲基嘧啶协同污染可能会诱导土壤微生物对二者产生交互抗性;而高剂量协同污染则对土壤微生物生态功能产生较为严重的协同抑制作用。     

Heavy-metal fractionation and distribution in soil profiles short-term-irrigated with sewage wastewater

Six soil profiles irrigated and non-irrigated with sewage wastewater were investigated for soil pH, electrical conductivity (EC), organic matter (OM), and CaCO₃. The distributions and chemical fractions of Cu, Zn, Cd, and Pb, and their lability were also studied. The results indicated that pH, EC, OM, and CaCO₃, as well as metal fractionation in soil profiles were affected by wastewater irrigation, especially in the surface layer. The surface layer (0-15 cm) irrigated with wastewater exhibited a 0.6 unit decrease in soil pH, a 40.6% decrease in CaCO₃, and a 200% increase in EC as compared with that of the non-irrigated soil. The soil OM increased from 0.04% to 0.35% in the surface layer. The irrigation of soil with wastewater resulted in transformation of metals from the carbonate fraction (CARB) towards the exchangeable (EXCH), Fe-Mn oxide (ERO), and organic (OM) fraction for Zn, towards the EXCH, the OM, and residual fraction for Cu, and towards the exchangeable (EXCH) fraction for Cd. It was concluded that the use of sewage wastewater led to salt accumulation and an increase in the readily labile fraction of Zn, Cu, and Cd in the surface layer. Therefore, this reason may limit the use of wastewater under arid and semi-arid conditions.     

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.     

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。     

烟气脱硫石膏对滩涂围垦土壤重金属解吸及残留形态的影响

滩涂围垦土壤是重金属等难降解污染物的主要最终归宿场所之一,其重金属的解吸将影响重金属的迁移性、生物有效性和潜在毒性,研究重金属的解吸对土壤污染评价、修复及环境容量预测至关重要.研究了烟气脱硫石膏对广州市南沙滩涂围垦土壤重金属的解吸效果,并分析了烟气脱硫石膏对重金属形态的影响.在离心管中称取20.0 g过0.25mm筛土样,加入20 mL水和不同量的烟气脱硫石膏,在室温下于恒温振荡器振荡,风干研碎后用原子吸收分光光度法测定重金属全量,并用Tessier连续提取法研究了处理前后重金属形态变化.研究结果表明,随着脱硫石膏施用量的增加,经过振荡离心后的滩涂围垦土壤中重金属质量分数先急剧下降,之后变化趋于平缓.与原土相比各重金属最大解吸率分别为:Cd 30.38%,Cu17.73%,Ni 15.00%,Zn 14.19%,Pb 9.46%,Cr 8.89%.比较处理前后重金属的形态变化,发现各重金属的可交换态解吸率均达50%以上,并且重金属碳酸盐结合态质量分数也有减少.说明烟气脱硫石膏能降低土壤对重金属的吸附,经振荡离心后能降低土壤中重金属的毒性和生物可利用性.     

Long-term stability and risk assessment of copper and cadmium in a smelter-impacted soil treated by four amendments

In an effort to address public concerns of the long-term stability and ecological risk reduction of Cu and Cd in a farmland located at the Guixi, Jiangxi Province, China, containing ～ 800?mg?kg^?1 Cu and 0.8?mg?kg^?1 Cd soil, were treated in situ by attapulgite, apatite, montmorillonite and lime at the rate: 10, 10, 10 and 4?g?kg^?1 soil, respectively. Field experiment consisted of 2?×?3-m plots arranged in a randomised complete block design with each treatment. Soil and plant samples were collected in sixth years post-treatments and analysed for Cu and Cd bioaccessibility, chemical fraction and Cu, Cd concentration in plant tissue. The results indicated that the apatite and lime treatments significantly reduced bioaccessible and exchangeable fractions Cu and Cd in the soil at sixth years post the treatments. Cu and Cd concentration in plant tissue was positively related to the bioaccessibility of Cu and Cd. The treatment used 10?g apatite kg^?1 soil appeared to be most effective for overall risk reduction. The Cu and Cd stabilisation and risk reduction by the apatite treatments were accomplished by the induced transformation of labile Cu and Cu species to relatively insoluble forms. This study illustrated that in situ Cu and Cd stabilisation by apatite would be long-term and ecologically safe, which could safeguard human health and ecosystem from Cu and Cd contamination in mining areas.     

蔬菜土壤微生物种群数量与土壤重金属含量的关系

对呈贡县蔬菜土壤微生物种群数量和土壤重金属质量分数进行大田调查分析，结果表明，土壤微生物种群数量和微生物多样性指数变化较大，土壤微生物种群数量总体水平较高，但微生物多样性指数偏低，其中以细菌占较大的优势；土壤重金属对土壤微生物数量和微生物多样性均有一定的影响，其中土壤中Pb和Cu的质量分数与土壤微生物种群数量显著相关；土壤重金属综合污染指数与真菌／细菌个数比例、真菌／放线菌个数比例与微生物多样性指数均呈显著的指数相关。随着重金属综合污染指数的增加，微生物多样性指数呈指数式地迅速下降。     

土壤胶体表面吸附态铜的解吸动力学特征

供试土壤胶体吸附态Cu的解吸过程分为两个阶段,0~60min时间段为快速反应阶段,对应于静电吸附态Cu的解吸;60min以后为慢速反应阶段,对应于专性吸附态Cu的解吸.解吸遵循两点位一级反应方程;在3种介质下,两点位解吸速率常数及吸附量大小为k1＞k2,C2＞C1;各土壤胶体的解吸速率大小次序与表面电荷密度的大小相反.草酸、柠檬酸可以增加吸附态Cu的解吸;在NaNO3介质中,第二点位吸附态Cu量与总吸附量的比值(C2/C0)可作为专性吸附的特征值.