污泥土地利用中重金属铜在土壤中的迁移行为

研究通过模拟土柱淋溶实验来研究污泥土地利用中重金属铜在土壤中的迁移行为。结果表明污泥土地利用会明显增加土壤中铜的总量,但大部分集中在40 cm以上的土壤中。通过BCR连续提取法发现,经淋溶后耕作层（0 cm~30 cm）土壤中的铜仍然以残渣态为主（占50%以上）,但能被植物利用的酸溶/可交换态和可还原态铜有了明显的增加。与去离子水相比,模拟酸雨（pH=4.5）会使土壤中铜的淋溶强度增加,并更能促使其向下迁移。     

珠三角农用地土壤重金属污染治理修复研究实践与展望

利用改性膨润土材料稳定钝化修复重金属污染土壤技术对珠三角典型农用地土壤重金属Cd,Pb污染修复进行了研究与应用探讨。在对选择的典型污染工作区进行污染现状详细调查与评价的基础上,以钙基膨润土为基础材料,研制了18种改性膨润土修复材料,通过吸附解吸重金属实验筛选出7种吸附能力较强的改性材料;并通过盆栽模拟修复试验和污染场地示范修复试验,最终筛选出对Cd,Pb污染土壤有较好修复能力的修复材料,即巯基化改性膨润土及钠化胡敏酸改性膨润土。     

改性黏土矿物修复重金属污染底泥的稳定化试验研究

为控制河流污染底泥中重金属的迁移和生物有效性,将膨润土、硅藻土和海泡石分别进行改性得到有机膨润土、Mn-硅藻土和酸改性海泡石,按照10%的比例添加至污染河流底泥中,进行稳定化实验。结果表明:在2种浸提剂作用下,有机膨润土和酸改性海泡石对Cu、Pb、Cr的释放皆具有抑制效果,Mn-硅藻土对Pb和Cr的释放皆具有一定控制作用。重金属形态分布结果显示,3种稳定化剂对Pb具有良好的修复效果,分别使其稳定态增加92.85%、75.62%、71.02%,提升了Pb的稳定性;有机膨润土和酸改性海泡石使弱酸提取态Cu降低了39.05%和10.35%,Mn-硅藻土和酸改性海泡石则对含Cr底泥具有一定修复作用,使其不稳定态降低了22.25%和35.71%,二者的生物有效性均得到控制。     

Fe-Al改性硅藻土与CaO配施改良Cd污染土壤

以人工模拟Cd污染土壤为研究对象,以Fe-Al改性硅藻土和CaO为原料制备组配改良剂,通过土壤培养试验研究了Fe-Al改性硅藻土与CaO不同配比对组配改良剂改良Cd污染土壤效果的影响.结果表明,向Cd污染土壤施加Fe-Al改性硅藻土与CaO以不同配比所制得组配改良剂对土壤Cd形态、pH值、CEC值、OM值、含水率、有效氮、速效磷、有效钾均产生了积极的影响.当Fe-Al改性硅藻土与CaO的配比为1：6时,土壤可交换态Cd含量较空白对照降低了74.67%,较单一施加Fe-Al改性硅藻土和CaO分别降低了64.63%和7.87%,与对照相比,土壤pH值提升了0.45,土壤CEC提升了69.78%,土壤有效氮、速效磷分别提升了28.57%、70.85%.Fe-Al改性硅藻土与CaO配施能有效控制土壤Cd污染,同时还可有效改善土壤耕作性能.     

Fe-Al改性硅藻土的制备及其对土壤Cd污染固定化效果

为了提高硅藻土对土壤镉污染的原位固定化效果,采用羟基Fe-Al对硅藻土进行改性,通过土壤培养实验研究了Fe/Al摩尔比、OH/cation摩尔比、陈化时间、(Fe+Al)/硅藻土比、反应温度、老化时间对土壤镉污染固定化效果的影响,同时采用扫描电镜(SEM)和傅里叶红外光谱(FTIR)分析了改性前后硅藻土理化特征的变化.结果表明,改性硅藻土最佳制备工艺条件为Fe/Al摩尔比1∶8、OH/cation摩尔比2.0~2.2、陈化时间2 d、(Fe+Al)/硅藻土比10 mmol·g-1、反应温度60℃、老化时间2 d.改性硅藻土显著降低了土壤中可交换态镉的含量,硅藻土改性前后对交换态Cd含量的降低率由11.83%提升到39.52%.SEM与FTIR分析表明,通过改性增加了硅藻土的比表面积和Si—O—H基团,并且羟基铁铝被成功置入硅藻壳体内部,形成了有效柱体,增大了孔道间距,增强了硅藻土的表面活性.因此,羟基铁铝改性能有效地促进硅藻土对土壤镉的固定效果.提供的改性方法和实验结果,为硅藻土固定土壤重金属提供了新的技术手段和理论依据.     

磷肥对铅锌矿污染土壤中铅毒的修复作用

用连续提取法研究了不同磷肥对铅锌矿污染土壤中铅化学形态的影响、磷肥降低铅毒性的机理以及磷肥的有效使用条件.结果表明,3种磷肥都具有显著降低铅的各种非残渣形态含量的作用.磷肥用量在P/Pb摩尔比为7.0时已经足够修复土壤的铅毒,并且在该磷肥用量水平时,从非残渣形态铅总量的降低幅度上看,3种磷肥修复铅污染的效果顺序为：过磷酸钙（85%）、钙镁磷肥（83%）〉〉磷矿粉（16%）;把铅的形态与其生物有效性联系起来比较,3种磷肥修复铅污染效果顺序为：钙镁磷肥（94%）、过磷酸钙（92%）＞磷矿粉（61%）.磷肥具有原位修复铅污染土壤的潜能,其主要机理是通过磷肥中的磷与各种非残渣形态铅反应形成溶解度极小的磷（氯/羟基/氟）铅矿沉淀,从而降低铅的溶解性的结果,3种磷肥中以磷矿粉最为经济.     

典型山区燃煤型电厂周边土壤重金属形态特征及污染评价

为了揭示毕节金沙电厂周边土壤重金属（Hg、As、Cd、Cr、Cu、Pb和Zn）污染状况,在电厂周围采集了32个土壤表层样品,采用改进的BCR连续提取法进行形态分析,并以Hakanson潜在生态危害指数法、改性灰色聚类法及风险评估编码法（RAC）进行生态风险评估.结果表明：重金属含量变化具有一定的空间变异结构和空间分布特征,除了Cd和Cr的含量平均值低于贵州省土壤平均背景值外,其余重金属含量的平均值均大于该背景值.土壤中的大部分重金属主要以残渣态形式存在,而Cd主要以酸可提取态和可还原态存在,具有很强的环境危害.相关性分析结果显示,Hg与As、Cd表现为极显著相关,而Zn与其余重金属元素相关性都较弱.生态风险评价得出7种重金属的生态风险大小顺序为Cd > Hg > As > Cu > Pb > Zn > Cr,综合潜在生态风险指数（RI）平均值为129.72,处于中等生态风险.通过改性灰色聚类法对土壤重金属污染进行分析评价,表明电厂西面污染明显高于东面,且Hg和Cd为主要污染物;由风险评估编码法得出元素Cd有效态占18.17%,对环境构成中等风险等级,元素Cr和Zn对环境的危害处于低风险状态,元素Hg、Pb、As和Cu处于无风险状态.综合以上研究结果,金沙电厂土壤受到不同程度的重金属污染,应特别重视Hg和Cd这两种重金属污染的治理.     

弱碱性矿粉对轻度Cu和Zn污染土壤的钝化修复试验研究

选用4种不同pH值的重金属污染土壤,通过室内模拟钝化试验,分别添加白云石、石灰石、硅灰石、磷矿粉4种矿粉,采用改进BCR法连续提取土壤中不同赋存形态的重金属,研究土壤中Cu和Zn赋存形态的变化,以获得不同矿粉对土壤中重金属的钝化特性。试验结果表明:白云石、石灰石、硅灰石、磷矿粉对土壤中Cu和Zn均有一定的钝化作用;多数情况下,白云石和石灰石对Cu污染的土壤钝化效果较好,在矿粉最高设计添加量2%(w/w)时,4种土壤中酸溶态Cu相对降低幅度为17.22%~50.49%,残渣态Cu相对升高幅度为3.24%~20.66%;石灰石和硅灰石对Zn污染的土壤钝化效果较好,在矿粉最高设计添加量2%(w/w)时,4种土壤中酸溶态Zn相对降低幅度为17.82%~28.48%,残渣态Zn相对升高幅度为5.98%~24.54%。     

改性纳米TiO2对砷污染土壤的稳定化试验

以黄壤、红壤、紫色土和黑土为供试土壤,研究改性纳米二氧化钛对土壤中砷的稳定化效果。采用溶胶-凝胶法制得活性炭负载纳米二氧化钛（ACT）和铁改性活性炭负载纳米二氧化钛（ACTI）,并将粒径为100 nm的纳米二氧化钛（T-100）和活性炭（AC）作为对照材料。将改性纳米二氧化钛按照不同质量比添加到供试土壤中,稳定化14 d后,采用生物有效性简化提取法（simple bioavailability extraction test,SBET）研究改性纳米二氧化钛对不同类型土壤中砷的稳定化效果。结果表明:4种供试土壤的固砷能力顺序为红壤>黑土>黄壤>紫色土。ACTI和ACT在4种类型土壤中对砷的稳定效果均优于对照材料T-100和AC,在2%的添加量下,4种土壤对砷的稳定化率均高于60%。因此,ACTI和ACT可用作修复砷污染土壤的稳定剂。     

膨润土的改性及其对废水中铬的吸附性能研究

探讨了膨润土的改性方法,系统地研究了活化钙基膨润土所需无机酸的浓度、活化时间及活化温度对膨润土活性的影响,确定出最佳改性条件;对改性机理进行了一定的探讨。然后做了用改性钙基膨润土吸附污水中的Cr（Ⅵ）的条件试验,证明了改性钙基膨润土对重金属离子Cr（Ⅵ）有比较强的吸附性能。     

钢渣和沸石去除猪场废水中的磷酸盐和氨氮

研究了猪场废水中磷酸盐和氨氮的去除,采用钢渣除磷酸盐,NaCl改性沸石除氨氮,考察了不同比例钢渣和沸石混合材料同时去除磷酸盐和氨氮的效果。结果表明:钢渣对猪场废水中磷酸盐去除效果明显,沸石对猪场废水中氨氮有很好的去除效果;混合材料中活化沸石和钢渣的比例为4:1时,氨氮和磷酸盐的去除率分别为75.87%和89.71%。猪场废水进行两级处理后,便可达到磷酸盐和氨氮的排放标准。     

Mineral materials as feasible amendments to stabilize heavy metals in polluted urban soils

Four minerals, agricultural limestone (AL), rock phosphate (RP), palygorskite (PG), and calcium magnesium phosphate (CMP), were evaluated by means of chemical fractions of heavy metals in soils and concentrations of heavy metals in leachates from columns to determine their ability to stabilize heavy metals in polluted urban soils. Two urban soils (calcareous soil and acidic soil) polluted with cadmium, copper, zinc and lead were selected and amended in the laboratory with the mineral materials) for 12 months. Results indicated that application of the mineral materials reduced exchangeable metals in the sequence of Pb, Cd > Cu > Zn. The reduction of exchangeable fraction of heavy metals in the soils amended with di erent mineral materials followed the sequence of CMP, PG > AL > RP. Reductions of heavy metals leached were based on comparison with cumulative totals of heavy metals eluted through 12 pore volumes from an untreated soil. The reductions of the metals eluted from the calcareous soil amended with the RP, AL, PG and CMP were 1.98%, 38.89%, 64.81% and 75.93% for Cd, 8.51%, 40.42%, 60.64% and 55.32% for Cu, 1.76%, 52.94%, 70.00% and 74.12% for Pb, and 28.42%, 52.74%, 64.38% and 49.66% for Zn. Those from the acidic soil amended with the CMP, PG, AL, and RP were 25.65%, 68.06%, 78.01% and 79.06% for Cd, 26.56%, 49.64%, 43.40% and 34.68% for Cu, 44.44%, 33.32%, 61.11% and 69.44% for Pb, and 18.46%, 43.77%, 41.98% and 40.68% for Zn. The CMP and PG treatments were superior to the AL and RP for stabilizing heavy metals in the polluted urban soils.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid (OA) on the immobilization of Pb(II) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(II) by KH₂PO₄, phosphate rock (PR), activated phosphate rock (APR) and synthetic hydroxyapatite (HAP) at different phosphate:Pb (P:Pb) molar ratios (0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or CaCl₂, Community Bureau of Reference (BCR) sequential extraction and toxicity characteristic leaching procedure (TCLP) methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after 120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was < 5 mg/L for the red soil at P:Pb molar ratio 4.0.Water-soluble Pb could not be detected and the TCLP-Pb was < 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APRwasmost effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pbmolar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

Phosphorus release from phosphate rock and iron phosphate by low-molecular-weight organic acids

Low-molecular-weight(LMW) organic acids widely exist in soils, particularly in the rhizosphere. A series of batch experiments were carded out to investigate the phosphorus release from rock phosphate and iron phosphate by low-molecular-weight organic acids.Results showed that citdc acid had the highest capacity to solubilize P from both rock and iron phosphate. P solubUization from rock phosphate and iron phosphate resulted in net proton consumption. P release from rock phosphate was positively correlated with the pκa values. P release from iron phosphate was positively correlated with Fe-organic acid stability constants except for aromatic acids, but was not correlated with pκa. Increase in the concentrations of organic acids enhanced P solubilization from both rock and iron phosphate almost linearly. Addition of phenolic compounds further increased the P release from iron phosphate. Initial solution pH had much more substantial effect on P release from rock phosphate than from iron phosphate.     

不同养分对磷酸盐固定的污染土壤中铜锌生物有效性的影响

采用盆栽试验,在磷酸盐固定铜、锌单一及复合的三级污染(Cu 200 mg·kg^-1、Zn 400 mg·kg^-1)红壤和水稻土中,种植黑麦草40　d,测定不加养分、加入KCl和NH₄Cl、K₂SO₄和(NH₄)₂SO₄后土壤中有效态铜锌含量、黑麦草生物量及其铜锌吸收量,以讨论养分对污染土壤中磷酸盐固定态铜锌的活化作用.结果表明,磷酸盐固定的铜单一、锌单一和铜锌复合污染红壤中,增加养分,有效态铜锌的含量都较未加入养分的增高,并且养分KCl和NH₄Cl的增高幅度大于K₂SO₄和(NH₄)₂SO₄,其中在磷酸盐固定的锌单一污染红壤中,有效态锌含量较未加入养分时增幅高达133.4%.虽然加入K₂SO₄和(NH₄)₂SO₄,促进了红壤中黑麦草植株的生长,最大增幅达22.2%,但同时也增加了植株21.5%～112.6%的铜锌吸收量.调节养分对水稻土中铜锌的生物有效性没有显著影响.施入氮钾等养分能够改变磷酸盐固定的污染红壤中铜锌的生物有效性,对固定的铜锌都有活化作用.因此,在重金属污染土壤的修复中要充分考虑施肥等养分条件对固定钝化的重金属活性的影响.     

磷矿粉和腐熟水稻秸秆对土壤铅污染的钝化

通过室内培养试验研究了磷矿粉和草酸活化磷矿粉与腐熟水稻秸秆配施及不同水分处理对土壤基本性质和铅形态变化的影响.结果表明,施用3种钝化材料都能提高土壤p H值、有效磷、交换性钙、阳离子交换量,其中活化磷矿粉效果最佳;与保持70%田间持水量相比,淹水处理增加p H、提高交换性钙效果更好,但有效磷较低.施用3种钝化材料能使可交换态铅减少,促进其向生物难利用态转变,活化磷矿粉对铅的钝化效果优于未活化的磷矿粉,两者最高分别可使交换态与对照相比降低40.3%和24.2%,且钝化效果与施用量呈正相关;腐熟水稻秸秆能增加土壤有机结合态铅;淹水处理可促使交换态铅向铁锰氧化物和残渣态转化.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid (OA) on the immobilization of Pb(II) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(II) by KH₂PO₄, phosphate rock (PR), activated phosphate rock (APR) and synthetic hydroxyapatite (HAP) at different phosphate:Pb (P:Pb) molar ratios (0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or CaCl₂, Community Bureau of Reference (BCR) sequential extraction and toxicity characteristic leaching procedure (TCLP) methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after 120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was <5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was <5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

负载磷酸盐生物质炭材料对重金属复合污染土壤的稳定化机制研究

为探讨负载磷酸盐生物质炭材料对重金属复合污染土壤中共存重金属的稳定化效果和迁移转化特征,以玉米秸秆和小麦秸秆为原材料,负载磷酸盐后在600 °C下无氧热解制备两种生物质炭材料,并将其用于重金属复合污染土壤中进行稳定化批处理试验. 结果表明:负载磷酸盐的玉米秸秆和小麦秸秆生物质炭材料可通过增加土壤中无定形铁、铝氧化物的含量而促进其对Cd的吸附,且负载磷酸盐后玉米秸秆生物质炭材料对土壤中无定形氧化物含量的增幅和游离态氧化物含量的降幅高于小麦秸秆生物质炭;同时,两种生物质炭材料均显著提高了土壤铁的活化度,进而有效控制了土壤重金属的生物有效性. 添加不同比例(如5%、10%和15%)的负载磷酸盐生物质炭均可降低土壤中Pb、Cd、Zn和Cu的迁移风险,并促进Pb的酸可提取态、铁锰结合态向有机结合态和残渣态转化,以及Cd、Zn和Cu的酸可提取态向残渣态转化. 两种负载磷酸盐生物质炭材料均可有效降低重金属的浸出浓度,10%及以上的添加量均可使Pb的浸出浓度降低98%以上. 15%的负载磷酸盐玉米秸秆生物质炭可使Cd和Zn的浸出浓度分别降低89%和47%,而15%的负载磷酸盐小麦秸秆生物质炭可使Cu的浸出浓度降低56%. 研究显示,施用10%~15%的负载磷酸盐生物质炭材料可显著降低重金属复合污染土壤中Pb和Cd的潜在环境风险,对矿区重金属污染土壤的安全利用具有参考和指导意义.      

磷肥对铅锌矿渣污染土壤中重金属的活性影响试验研究

本文通过实验室盆栽模拟试验,研究了磷肥对铅锌矿渣污染土壤中Zn、Cd、Pb、Cu等重金属的活性影响作用。结果表明:在铅锌矿渣污染土壤中施加不同比例的磷肥配比,对土壤中重金属活性影响很大,随着配比的逐渐升高,土壤中有效态重金属(Zn、Cd和Cu)含量呈现出升高-降低-升高的趋势,但Pb呈现出相反的变化趋势。     

烧结脱硫灰制备胶凝材料强度影响因素研究

通过正交及单因素试验方法研究了烧结烟气半干法脱硫灰复掺矿渣、钢渣,辅之外加剂,制备生态胶凝材料的可行性。结果表明采用分别预磨钢渣、矿渣及水泥熟料再与经低温煅烧的改性脱硫灰混磨制备的复合生态胶凝材料,具有良好的安定性、水化性能和力学性能;初凝时间、终凝时间合格。正交试验确定了一定比例和掺量的矿渣和钢渣复掺15%改性脱硫灰、15%水泥熟料和0.5%激发剂时胶凝材料的各项性能较好,通过单因素试验对方案进行了优化,用SEM对两组配方的水泥净浆体进行晶形微观分析,验证了不同水化产物在不同龄期对水泥体的强度影响。