CN102205345A - 苯并(a)芘污染土壤的异位修复方法 - Google Patents
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Abstract
一种苯并(a)芘污染土壤的异位修复方法，具体修复步骤为：（1）土壤颗粒准备：首先将污染土壤风干，碾碎到粒径约2mm；（2）调节土壤酸碱度：用稀盐酸调节土壤pH到4.5~5.5；（3）调节土壤水分：第一次调节土壤水分到40±5%田间持水量，搅拌混匀并平铺成8~10cm厚的土层，然后均匀加水使土壤水分到达60±5%田间持水量；（4）土壤培养：放置40±2℃下避光恒温、恒湿、透气培养，持续时间为30~40天，不同污染土壤中苯并(a)芘的去除率可达37~99%。
Description
技术领域
本发明属于污染土壤修复技术领域，尤其涉及苯并(a)芘污染土壤的快速生物修复方法。
背景技术
多环芳烃是我国环境中的重要持久性有机污染物之一，尤其是苯并(a)芘的毒性通常占总多环芳烃毒性当量的50%以上。土壤介质作为多环芳烃的重要库和汇，可通过食物链传递及放大作用，对生态和人体健康造成严重的潜在危害。因此，土壤中苯并(a)芘的快速去除一直是多环芳烃污染土壤修复研究的重点和难点。
发明内容
解决的技术问题：本发明的目的是提供一种基于土壤pH、水分与温度综合调控的苯并(a)芘污染土壤异位修复方法。
技术方案：一种苯并(a)芘污染土壤的异位修复方法，采用恒温恒湿的环境调控措施，具体修复方法为：（1）土壤颗粒准备：首先将污染土壤风干，碾碎到粒径约2 mm；（2）调节土壤酸碱度：用稀盐酸调节土壤pH到4.5~5.5；（3）调节土壤水分：第一次调节土壤水分到40±5%田间持水量，搅拌混匀并平铺成8~10 cm厚的土层，然后均匀加水使土壤水分到达60±5%田间持水量；（4）土壤培养：放置40±2℃下避光恒温、恒湿、透气培养，持续时间为30~40天，在不同污染土壤中苯并(a)芘的去除率可达37~99%。
有益效果：土壤水分和温度是控制土壤微生物生长的重要环境因子。水分影响土壤的通气状况和氧化还原电位，影响苯并(a)芘的生物有效性和土壤微生物活性。微生物主要在好氧条件下对苯并(a)芘进行氧化开环降解，水分条件既要能满足微生物生长对水的要求，有要能满足土壤有足够的空隙，维持较高的氧化还原电位，有利苯并(a)芘的降解。土壤温度影响酶促反应的速度，在一定的范围内，提高温度，通常会提高酶的活性，及其酶促反应的速率。研究结果表明在土壤水分为田间持水量的60±5%左右，40±2℃培养28天，三种污染土壤（加气站，钢铁厂和焦化厂污染）中苯并(a)芘的去除率分别为99%，37.8%和66.5%。通过温度和水分的综合调控，对苯并(a)芘污染土壤具有较好的修复效果。
附图说明
图1. 不同水分条件下土壤中苯并(a)芘含量变化；
图2. 不同温度条件下土壤中苯并(a)芘含量变化；
具体实施方式
以下结合实例对本发明作进一步的描述：
实施例1：
1.1 供试土壤
供试土壤采自长江三角洲某典型多环芳烃污染农田土壤。土壤样品风干，拣出杂质，过10目筛后备用。土壤基本理化性质为有机质含量23.4 g/kg，全氮1.44 g/kg，全磷0.86 g/kg，全钾12.3 g/kg，阳离子代换量15.6 cmol/kg，pH值4.5。土壤中苯并(a)芘为1.18 mg/kg。
1.2 试验设计
1.2.1水分条件实验
土壤水分设4个水平：分别为田间持水量的21.7%、43.4%、65.1%和86.8%。称取供试土壤50.0 g于150 mL玻璃三角瓶中，加入所需量的无菌蒸馏水混匀后放置28℃恒温培养箱中避光培养。每个处理3次重复。在培养第10、20、30、50和80天取样，经冷冻干燥后过60目筛，4℃保存供苯并(a)芘的分析。
1.2.3温度条件实验
称取100 g供试土壤，加入20 mL无菌蒸馏水，混匀后装入250 mL玻璃三角瓶，再用滴管滴加5.0 mL蒸馏水，塞上硅胶塞，分别在温度为25℃、40℃恒温培养箱中避光培养，每个处理设3次重复。在培养第10天、20天、40天和60天取样，经冷冻干燥后过60目筛，4℃保存供苯并(a)芘的分析。
1.2.3 优化条件验证实验
称取供试土壤50.0 g，加10 mL无菌蒸馏水混匀，装入150 mL玻璃三角瓶，再滴加2.5 mL蒸馏水，盖上瓶塞，40℃避光培养，设3次重复。28天后结束培养，样品经冷冻干燥后测定苯并(a)芘含量。
1.2.4 扩大培养实验
称取污染土壤5.0 kg，加1000 mL无菌蒸馏水混匀后平铺成厚度为8 cm左右的土层，再均匀加水250 mL，放置40℃恒温培养箱中遮光培养40天。
1.3 土壤中苯并(a)芘的分析
称取过60目筛的土壤样品2.00 g，按1:1比例与无水硫酸钠充分混匀，用滤纸包好放入索氏提取管，用60 mL二氯甲烷在53℃下连续提取24 h。然后将二氯甲烷在38℃，413 mbar压力下旋转蒸发至干，再加入2.0 mL环己烷溶解。另称1.0 g经400℃下处理8 h的干燥硅胶于小烧杯中，加10mL正已烷浸泡15min，然后装硅胶柱。移液器吸取环已烷溶液0.50 mL过柱。用1:1正已烷和二氯甲烷混合液进行洗脱，首次1.0 mL洗脱液弃去，再接2.0 mL洗脱液于刻度试管中，用高纯氮气吹干。加2.0 mL乙腈溶解，用高效液相色谱测定。。
高效液相色谱分析条件：色谱柱为岛津VP-ODS 150×4.6，流动相为乙腈和水，0.8 mL/min，梯度洗脱程序为：80%乙腈 20min 100%乙腈，柱温30℃，进样量20μL，激发波长296 nm，检测波长404 nm，外标法定量。方法检出限小于0.1 μg/L，在1.0 μg/L—1000.0 μg/L范围内线性良好。
1.4 结果分析
1.4.1 水分的影响
在不同水分条件下土壤中苯并(a)芘的含量动态变化如附图1所示。培养80天后，21.7%、43.4%、65.1%和86.8%水分条件下土壤中苯并(a)芘的降解率分别为42.5%、96.6%、96.3%和34.3%。在低水分（21.7%）和高水分（86.8%）条件下，土壤中苯并(a)芘的降解速率显著低于土壤水分为43.4%和65.1%的处理。
1.4.2 温度的影响
两种温度条件下土壤中苯并(a)芘的含量变化如附图2所示。在土壤水分为60%田间持水量，40℃培养20天，土壤苯并(a)芘的去除率达到75.5%，显著高于25℃培养的13.7%。处理60天后，25℃和40℃下，土壤苯并(a)芘分别去除了86.1%和90.6%。可见，40℃更有利于土壤中苯并(a)芘的去除。
1.4.3 优化方法的处理效果
在水分为60%田间持水量，温度为40℃条件下处理28天后，土壤中苯并(a)芘含量降低了99.1%（对污染农田土壤的监测显示，25个月后，土壤中苯并(a)芘的自然衰减量为7.9%）。可见，恒温恒湿的综合处理方法对污染土壤中苯并(a)芘具有快速的去除效果。
1.4.4 扩大培养效果
对5.0kg污染土壤按照本方法处理40天后，取样分析结果表明，土壤苯并(a)芘残留量仅为6.7±4.7μg/kg，去除率超过99%。
实施例2：
1、从某钢铁厂附近农田采集污染土壤，经风干后过2 mm筛，经测土壤苯并(a)芘含量为124 μg/kg。
2、称取风干污染土壤50.0 g，加10 mL无菌蒸馏水混匀，装入150 mL玻璃三角瓶，再滴加2.5 mL蒸馏水，盖上瓶塞，40℃避光培养，设3次重复。28天后结束培养，样品经冷冻干燥后测定苯并(a)芘含量。
3、测试土壤苯并(a)芘含量为75μg/kg，去除率为37.8%。
实施例3：
1、从某焦化厂附近采集污染土壤，经风干后过2 mm筛，经测土壤苯并(a)芘含量为251 μg/kg。
2、称取风干污染土壤50.0 g，加10 mL无菌蒸馏水混匀，装入150 mL玻璃三角瓶，再滴加2.5 mL蒸馏水，盖上瓶塞，40℃避光培养，设3次重复。28天后结束培养，样品经冷冻干燥后测定苯并(a)芘含量。
3、测试土壤苯并(a)芘含量为84μg/kg，去除率为66.5%。
以上分析结果表明，该苯并(a)芘污染土壤的异位修复方法不破坏土壤微生物结构与功能，修复效果好，所需时间短、可行性强，是一项很有发展潜力的环保型土壤修复技术。
Claims (1)
1.一种苯并(a)芘污染土壤的异位修复方法，其特征在于采用土壤pH、水分和温度的调控措施，具体修复方法为：
a.首先对污染土壤进行风干碾碎到粒径约2 mm；
b.然后用盐酸调节土壤pH到4.5~5.5；
c.再采用二步法调节土壤水分，第一次调节土壤水分到40±5%田间持水量，混匀铺平后再浇水到60±5%田间持水量；
d.土层厚度为8~10 cm；
e.培养温度维持在40±2℃，环境空气要流通；
f.连续培养土壤30~40天。
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| CN101195123A (zh) * | 2007-11-29 | 2008-06-11 | 北京师范大学 | 利用环糊精异位修复多环芳烃污染土壤的方法 |
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| 《土壤学报》 20100331 刘世亮等 污染土壤中苯并[a]芘的微生物共代谢修复研究 第364－369页 1 第47卷, 第2期 2 * |
| 《环境科学》 20100831 刘世亮等 真菌对污染旱地红壤中苯并[a]芘共代谢降解研究 第1944－1950页 1 第31卷, 第8期 2 * |
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