几种含磷材料对紫色土铅稳定条件优化及磷淋失环境风险评价
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摘要
以西南地区广泛分布的紫色土-灰棕紫泥为对象,探讨了磷酸二氢钾(MPP)、过磷酸钙(SSP)、钙镁磷肥(CMP)和磷矿粉(PR)4种含磷材料,在不同剂量下对不同程度Pb污染土壤的稳定化效果,并对其长期稳定性和P淋失的环境风险进行了研究。结果表明4种含磷材料对土壤Pb均具有显著稳定化效果。在P:Pb(摩尔比)为1时,稳定效率相对大小顺序:MPP>SSPěCMP>PR。当Pb污染浓度<600 mg·kg~(-1)时,4种稳定剂均能实现土壤Pb的稳定化。当Pb浓度ě1 200 mg·kg~(-1)时,MPP依然保持高效的稳定化能力,但是PR对土壤稳定化不能满足浸出标准。固定Pb污染浓度为1 200 mg·kg~(-1),含磷材料稳定化Pb的效果受其剂量的影响。MPP在P:Pb为1时稳定化处理3 d即可达到浸出标准,SSP和CMP在P:Pb为1.5和2时稳定化处理30 d可达到浸出标准,PR在P:Pb为4时稳定化处理60 d基本达到浸出标准,增加稳定剂剂量能够显著提高对紫色土Pb的稳定速率。施用系列含磷材料稳定剂后,除SSP外均使土壤pH升高,且随着稳定时间的延长,土壤中可交换态(Exc-Pb)逐渐降低,残渣态(Res-Pb)所占比例逐渐升高。满足Pb浸出标准的处理在稳定化9个月内土壤中Pb浸出浓度始终维持在极低水平,并且土壤有效P也一直保持在土壤P淋失临界值以内,说明合理剂量和类型的含磷材料能满足持续稳定化和环境风险控制要求。
The effects of four phosphorus-containing materials(monopotassium phosphate, MPP; calcium superphosphate, SSP; calcium-magnesia phosphate, CMP; ground phosphate rock, PR) at different dosages on the stabilization of Pb-contaminated soil were studied, taking gray-purple soil, a widely distributed soil in southwest China, as the object, and its long-term stability and P leaching risk were investigated. The results showed that all four kinds of phosphorus-containing materials had significant stabilizing ability on Pb-polluted soil. Under the condition of P:Pb = 1:1(molar ratio), their stable efficiencies followed an order of MPP > SSP ě CMP > PR.When soil Pb concentration was less than 600 mg·kg~(-1), all stabilizing agents could match the requirement of soil Pb stabilization. When the concentration of Pb was over 1 200 mg·kg~(-1), MPP still maintained high stabilization efficiency, while PR could not meet the leaching standard. At a fixed Pb pollution level of 1 200 mg·kg~(-1), the stabilizing efficiency increased with increase of the dosage of the stabilizing agent. MPP treatment with a P and Pb ratio of 1:1 could realize the leaching standard after 3 days stabilization, while a higher dosage of P:Pb ratios of1.5 and 2 and a longer stabilization time of 30 days were needed for SSP and CMP, respectively. Moreover, a highest dosage of P:Pb ratios of 4 and a longest stabilizing time of 60 days was needed for PR. The soil pH all increased after stabilization except for SSP. The proportion of exchangeable Pb(Exc-Pb) gradually decreased and the residual Pb(Res-Pb) remarkably increased during the stabilizing process, and those of the Pb bound by carbonates(Carb-Pb)and ferromanganese oxides(Fe Mn O?-Pb) showed no obvious changes. All the four stabilizers at optimized conditions can meet the requirements of continuous stabilization and low risk for P leaching. After 9 months of stabilization, the Pb leaching concentration form stabilized soils remained at an extremely low level(far lower than leaching standard),and the available P in soil also remained within the P leaching threshold.
The effects of four phosphorus-containing materials(monopotassium phosphate, MPP; calcium superphosphate, SSP; calcium-magnesia phosphate, CMP; ground phosphate rock, PR) at different dosages on the stabilization of Pb-contaminated soil were studied, taking gray-purple soil, a widely distributed soil in southwest China, as the object, and its long-term stability and P leaching risk were investigated. The results showed that all four kinds of phosphorus-containing materials had significant stabilizing ability on Pb-polluted soil. Under the condition of P:Pb = 1:1(molar ratio), their stable efficiencies followed an order of MPP > SSP ě CMP > PR.When soil Pb concentration was less than 600 mg·kg~(-1), all stabilizing agents could match the requirement of soil Pb stabilization. When the concentration of Pb was over 1 200 mg·kg~(-1), MPP still maintained high stabilization efficiency, while PR could not meet the leaching standard. At a fixed Pb pollution level of 1 200 mg·kg~(-1), the stabilizing efficiency increased with increase of the dosage of the stabilizing agent. MPP treatment with a P and Pb ratio of 1:1 could realize the leaching standard after 3 days stabilization, while a higher dosage of P:Pb ratios of1.5 and 2 and a longer stabilization time of 30 days were needed for SSP and CMP, respectively. Moreover, a highest dosage of P:Pb ratios of 4 and a longest stabilizing time of 60 days was needed for PR. The soil pH all increased after stabilization except for SSP. The proportion of exchangeable Pb(Exc-Pb) gradually decreased and the residual Pb(Res-Pb) remarkably increased during the stabilizing process, and those of the Pb bound by carbonates(Carb-Pb)and ferromanganese oxides(Fe Mn O?-Pb) showed no obvious changes. All the four stabilizers at optimized conditions can meet the requirements of continuous stabilization and low risk for P leaching. After 9 months of stabilization, the Pb leaching concentration form stabilized soils remained at an extremely low level(far lower than leaching standard),and the available P in soil also remained within the P leaching threshold.
引文
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[15]付煜恒,张惠灵,王宇,等.磷酸盐对铅镉复合污染土壤的钝化修复研究[J].环境工程,2017,35(9):176-180.
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[22]王碧玲,谢正苗,孙叶芳,等.磷肥对铅锌矿污染土壤中铅毒的修复作用[J].环境科学学报,2005,25(9):1189-1194.
[23]曹心德,魏晓欣,代革联,等.土壤重金属复合污染及其化学钝化修复技术研究进展[J].环境工程学报,2011,5(7):1441-1453.
[24]吴新民,潘根兴.影响城市土壤重金属污染因子的关联度分析[J].土壤学报,2003,40(6):921-928.
[25]LANG F,KAUPENJOHANN M.Effect of dissolved organic matter on the precipitation and mobility of the lead compound chloropyromorphite in solution[J].European Journal of Soil Science,2003,54(1):139-148.
[26]DAVENPORT J R,PERYEA F J.Phosphate fertilizers influence leaching of lead and arsenic in a soil contaminated with lead arsenate[J].Water,Air&Soil Pollution,1991,57-58(1):101-110.
[27]SHARPLEY A N,MCDOWELL R W,WELD J L,et al.Assessing site vulnerability to phosphorus loss in an agricultural watershed[J].Journal of Environmental Quality,2001,30(6):2026-2027.DOI:10.2134/jeq2001.2026.
[2]宋波,曾炜铨,陆素芬,等.含磷材料在铅污染土壤修复中的应用[J].环境工程学报,2015,9(12):5649-5658.
[3]程新伟.土壤铅污染研究进展[J].地下水,2011,33(1):65-68.
[4]环境保护部,国土资源部.全国土壤污染状况调查公报[J].中国环保产业,2014,36(5):10-11.
[5]魏秀国,何江华,陈俊坚,等.广州市蔬菜地土壤重金属污染状况调查及评价[J].生态环境学报,2002,11(3):252-254.
[6]王金达,王艳,任慧敏,等.沈阳市城乡结合部土壤-作物系统铅含量水平及其影响因素分析[J].农业环境科学学报,2005,24(2):261-265.
[7]蔡苇,何正浩,刘红瑛.黄石市郊主要蔬菜地土壤重金属污染状况分析[J].湖北理工学院学报,2006,22(3):69-72.
[8]胡文,王海燕,查同刚,等.北京市凉水河污灌区土壤重金属累积和形态分析[J].生态环境学报,2008,17(4):1491-1497.
[9]郑袁明,陈同斌,陈煌,等.北京市不同土地利用方式下土壤铅的积累[J].地理学报,2005,60(5):791-797.DOI:10.11821/xb200505010.
[10]李小平,刘洁,夏舒楠,等.我国城市土壤铅与儿童血铅空间分布格局[J].土壤通报,2015,46(1):226-232.
[11]徐礼生,吴龙华,高贵珍,等.重金属污染土壤的植物修复及其机理研究进展[J].地球与环境,2010,38(3):372-377.
[12]TANG X Y,ZHU Y G,CHEN S B,et al.Assessment of the effectiveness of different phosphorus fertilizers to remediate Pb-contaminated soil using in vitro test[J].Environment International,2004,30(4):531-537.DOI:10.1016/j.envint.2003.10.008.
[13]王碧玲.含磷物质修复铅锌矿污染土壤的机理和技术[D].杭州:浙江大学,2008.
[14]姜冠杰.磷矿粉及其活化产物对土壤铅的钝化与机理[D].武汉:华中农业大学,2011.
[15]付煜恒,张惠灵,王宇,等.磷酸盐对铅镉复合污染土壤的钝化修复研究[J].环境工程,2017,35(9):176-180.
[16]EPA U S.Toxicity characteristics leaching procedure:Method 1311[S].Environmental Protection Agency,Washington,DC,1992.
[17]TESSIER A,CAMPBELL P G C,BISSON M.Sequential extraction procedure for the speciation of particulate trace metals[J].Analytical Chemistry,1979,51(7):844-851.DOI:10.1021/ac50043a017.
[18]李学平,石孝均,刘萍,等.紫色土磷素流失的环境风险评估-土壤磷的“临界值”[J].土壤通报,2011,42(5):1153-1158.
[19]KAPLAN D I,KNOX A S.Enhanced contaminant desorption induced by phosphate mineral additions to sediment[J].Environmental Science&Technology,2004,38(11):3153-3160.DOI:10.1021/es035112f.
[20]THEODORATOS P,PAPASSIOPI N,XENIDIS A.Evaluation of monobasic calcium phosphate for the immobilization of heavy metals in contaminated soils from Lavrion[J].Journal of Hazardous Materials,2002,94(2):135-146.DOI:10.1016/S0304-3894(02)00061-4.
[21]CAO X,MA L Q,RHUE D R,et al.Mechanisms of lead,copper,and zinc retention by phosphate rock[J].Environmental Pollution,2004,131(3):435-444.DOI:10.1016/j.envpol.2004.03.003.
[22]王碧玲,谢正苗,孙叶芳,等.磷肥对铅锌矿污染土壤中铅毒的修复作用[J].环境科学学报,2005,25(9):1189-1194.
[23]曹心德,魏晓欣,代革联,等.土壤重金属复合污染及其化学钝化修复技术研究进展[J].环境工程学报,2011,5(7):1441-1453.
[24]吴新民,潘根兴.影响城市土壤重金属污染因子的关联度分析[J].土壤学报,2003,40(6):921-928.
[25]LANG F,KAUPENJOHANN M.Effect of dissolved organic matter on the precipitation and mobility of the lead compound chloropyromorphite in solution[J].European Journal of Soil Science,2003,54(1):139-148.
[26]DAVENPORT J R,PERYEA F J.Phosphate fertilizers influence leaching of lead and arsenic in a soil contaminated with lead arsenate[J].Water,Air&Soil Pollution,1991,57-58(1):101-110.
[27]SHARPLEY A N,MCDOWELL R W,WELD J L,et al.Assessing site vulnerability to phosphorus loss in an agricultural watershed[J].Journal of Environmental Quality,2001,30(6):2026-2027.DOI:10.2134/jeq2001.2026.