CN108745001B - 沉积物中甲基汞和金属汞离子的dgt固定膜、制备方法、dgt装置和洗脱液 - Google Patents
沉积物中甲基汞和金属汞离子的dgt固定膜、制备方法、dgt装置和洗脱液 Download PDFInfo
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Abstract
本发明公开了一种沉积物中甲基汞和金属汞离子的DGT固定膜、制备方法、DGT装置和洗脱液，所述固定膜由聚丙烯酰胺、水合氢氧化锆和异硫脲功能化大孔交联聚苯乙烯树脂的混合液经过成膜凝胶而成。本发明能高效、快速对湿地土壤沉积物中的汞金属进行吸附和洗脱从而测定汞含量。
Description
技术领域
本发明属于环境湿地土壤重金属的检测分析技术，尤其涉及湿地土壤间隙水中CH3Hg+和Hg2+的薄膜扩散梯度技术DGT固定膜及制备方法。
背景技术
目前，我国的水体污染十分严重，沉积物(湿地土壤)污染是重要起因。沉积物中累积了大量的污染物，当环境条件发生变化时，污染物从沉积物中释放到水体，对水体造成持续的、高强度的污染，威胁生态平衡和供水安全。沉积物间隙水作为溶解态部分，是反映沉积物变化的敏感指标。获取污染物在间隙水中的含量和垂直分布信息，是评价其污染水平、定量估算污染通量的重要资料。
对间隙水中污染物信息的获取，通常采用破坏性的采样方法，即直接从水底取出沉积物，通过离心或压榨的方法获得间隙水样品，用于污染物含量的分析。沉积物在水底长期处于还原环境，当从水底取出后，沉积物直接与空气接触氧化，导致性质发生较大变化，影响到间隙水中离子的含量分布。因此，采用破坏性方法得到的污染物含量信息有很大的不确定性，直接在沉积物原位采集间隙水是科学的方法。薄膜扩散梯度技术(Diffusivegradients in thin films，DGT)是一种非破坏性、原位获取沉积物中污染物分布和活性的技术，能够利用固定膜富集并测定沉积物活性离子浓度，但目前DGT测定中所用的固定膜绝大部分为单一吸收功能的固定膜，即只能吸收单一组分，造成分析测定效率低下，同时运行成本高；且目前还未有针对湿地土壤中甲基汞离子和金属汞离子的的固定膜组分。
发明内容
发明目的：本发明所要解决的技术问题是提供了一种沉积物中甲基汞和金属汞离子的DGT固定膜、制备方法、DGT装置和洗脱液，从而能高效、快速对湿地土壤沉积物中的汞金属进行吸附和洗脱从而测定汞含量。
发明内容：为解决上述技术问题，本发明所采用的技术手段为：所述固定膜由聚丙烯酰胺、水合氢氧化锆和异硫脲功能化大孔交联聚苯乙烯树脂的混合液经过成膜凝胶而成。
进一步的，所述水合氢氧化锆与异硫脲功能化大孔交联聚苯乙烯树脂的质量比为0.2～0.8:1。
本发明还提供了一种上述固定膜的制备方法，包括以下步骤：
(1)首先将TCH-95树脂经过球磨机进行研磨使TCH-95树脂的粒径在10～50μm范围内，然后在水含量为30％的聚丙烯酰胺水溶液中，加入0.05～0.15g/ml的水合氢氧化锆，然后加入0.25～0.3g/ml的经过研磨后TCH-95树脂，搅拌混合得到成膜液；
(2)接着在步骤(1)得到的成膜液中，继续加入5～30ml/l的低粘度聚氨酯分散剂，并经过5～20KHz的超声振荡24h以上；
(3)在步骤(2)得到的成膜液中，继续加入适量的四甲基二乙胺和过硫酸铵，并在2～4℃的温度下水平放置保持1～10min，待氢氢氧化锆和TCH树脂颗粒自由沉积富集在液膜最底层后，升温至40～50℃，直到成膜液胶凝成膜；
(4)将得到凝胶薄膜经过去离子水浸泡12h以上，完成。
本发明还提供了一种应用于上述固定膜的洗脱液，采用盐酸与硫脲的混合液。
进一步的，所述盐酸的浓度为0.1mol/L，硫脲的质量百分比浓度为2％
有益效果：相比于现有技术，本发明具有以下优点：
1)本发明的固定膜制作过程优化，固定膜在吸附性能和物理强度方面均有着优异的性能。本发明固定膜的制备过程中，氢氧化锆和TCH-95能够充分沉降到表面，并在表面形成致密且均匀的分布，能确保膜保持稳定的形状，不易变形，吸附剂颗粒不脱落。
2)固定膜对金属汞和甲基汞具有极高的吸附率，具有足够的选择性和吸附容量。
3)还提供了一种高效的洗脱液，提高了汞离子的回收率和洗脱检测效率。
附图说明
图1为本发明所述DGT固定膜对CH3Hg+和Hg2+的效率效率对比图；
图2为本发明所述DGT固定膜对CH3Hg+和Hg2+的检出容量图。
图3为本发明所述DGT固定膜应用在太湖表层沉积物样品中CH3Hg+和Hg2+的垂直分布图。
具体实施方式
下面结合附图并以具体实施例，进一步阐明本发明。应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
本发明中，首先将TCH-95树脂经过球磨机进行研磨使TCH-95树脂的粒径在20～30μm范围内，然后用30％质量浓度的聚丙烯酰胺作为凝胶成膜液，在其中加入0.1g/ml的经过改性的水合氢氧化锆粉末用于提高凝胶强度，经过研磨15min以上，然后加入0.25g/ml的异硫脲功能化大孔交联聚苯乙烯树脂TCH-95(经过研磨)，混合得到成膜液。未经过研磨细化的TCH-95在沉降到凝胶底层表面时速度过快，在表面占据位置后出现内应力，容易造成成膜后凝胶膜发生卷曲现象，从而降低和质量成品率。加入氢氧化锆可以增强膜的物理强度，否则容易被撕裂。
接着加入12ml/L的低粘度聚氨酯分散剂ACRYSOLTMRM-2020NPR(市购)，并在10KHz的超声振荡24h以上过夜。由于TCH-95经过研磨后表面带有经典，在凝胶沉降成膜过程中容易发生团聚现象，本发明通过加入分散剂(并具有抗静电作用)从而利用抗静电和强分散的协同作用，提高TCH-95在凝胶中的均匀分散，从而确保对甲基汞和金属汞离子的均匀固定。
继续加入12ml/L的过硫酸铵和6ml/L的四甲基二乙胺，持续搅拌并注入模具中，放入抽真空设备中进行抽真空排掉薄膜内的气泡，并在2℃左右静置10分钟左右，待水合氢氧化锆和TCH-95沉降至底部富集；然后继续升温至45℃左右，保持半小时以上行程凝胶薄膜，然后在去离子水中浸泡12h，得到固定膜。
利用PTFE制成底座和固定圈，同时采用1.5％的琼脂糖制成扩散膜，并采用0.45μm孔径的PVDF作为滤膜，依次设在底座内，并将固定圈将三层膜固定，得到DGT检测装置。发明人在进行研究时发现，DGT装置材料本身对甲基汞和金属汞离子有选择吸附，会影响最终的检测结果。因此将原ABS材质替换成PTFE材质，大大降低了材料的吸附。通过比较可知，ABS材料对CH3Hg+和Hg2+的吸附率分别为7％和50％，而PTFE材料的吸附率分别为3％和12％。以下是通过TCH-95制备的固定膜与其他几种官能团固定膜的吸附率比较，见表1：
表1不同固定膜对CH3Hg+和Hg2+的吸附效率
从吸附动力学表现比较(图1)可知，本发明TCH-95固定膜对CH3Hg+和Hg2+具有足够快的吸附速率，是同时富集CH3Hg+和Hg2+的理想固定膜。
经过甲基汞和金属汞离子吸附后的固定膜，需要通过洗脱液进行汞离子洗脱，从而测定CH3Hg+和Hg2+的浓度，洗脱效率需要足够高。而现有技术中，通常采用王水溶液、盐酸、硝酸等溶液进行洗脱，但洗脱效率低下。本发明针对汞离子与含硫官能团的强烈结合特性，通过试验筛选，选择相对巯基具有更高吸附效果的硫脲并在强酸环境中得到洗脱液，具有从本发明TCH固定膜上洗脱甲基汞和金属汞离子的溶液。如表2所示，为本发明洗脱液与现有技术中其他几种洗脱液的洗脱率比较。
Table 2文献中提到的洗脱液对CH3Hg+和Hg2+的洗脱率
从表2可知，最优选方案洗脱液为2％硫脲和0.1m盐酸的混合溶液。该洗脱液可完全回收CH3Hg+，而Hg2+的回收率高于50％(53.6％)。
DGT容量决定了湿地土壤汞含量的检测上限值。如图2所示，本发明固定膜对于CH3Hg+和Hg2+获得的实际和理论的对应，浓度分别高达11.34mg·L-1和12.88mg·L-1。将本发明应用于太湖表层沉积物中总汞和甲基汞含量的测定，如图3所示，沉积物中CH3Hg+和Hg2+的浓度分别处于ng·L-1和μg·L-1水平，在沉积物剖面上表现出较大差异。CH3Hg+浓度从沉积物-水界面(SWI)到SWI以下-20mm迅速升高，然后从-20m到-40mm迅速降低。在-20mm和-56mm出现局部峰，之后浓度没有显著变化，-80mm以下趋于稳定。沉积物中汞的甲基化是厌氧细菌特别是产甲烷菌、硫酸盐和铁还原菌等甲基化的结果，微生物与沉积物中甲基汞的分布呈显著正相关，有机物含量影响微生物的数量和代谢，为汞的甲基化提供了可能。DGT测得的浅层CH3Hg+浓度在0--20mm逐渐增加，可能是因为表层沉积物含有丰富的有机质，甲基化水平相对较高。另外，固相补给也是沉积物中CH3Hg+的局部来源，由沉积物固相补给的量可由DGT测得。CH3Hg+在-56mm处的局部峰值可能反映了CH3Hg+从深层沉积物固体中的释放，可能存在其他释放机制如生物扰动。因此通过本发明固定膜能快速准确的对沉积物中CH3Hg+和Hg+的浓度，对CH3Hg+和Hg+的影响因素理论分析提供帮助。
Claims (3)
1.一种沉积物中CH3Hg+和Hg2 +的DGT固定膜，其特征在于：所述固定膜由聚丙烯酰胺、水合氢氧化锆和异硫脲功能化大孔交联聚苯乙烯（TCH-95）树脂的混合液经过成膜凝胶而成；
所述固定膜的制备方法，包括以下步骤：
（1）首先将TCH-95树脂经过球磨机进行研磨使TCH-95树脂的粒径在10~50μm范围内，然后在水含量为30%的聚丙烯酰胺水溶液中，加入0.05~0.15g/ml的水合氢氧化锆，然后加入0.25~0.3g/ml的经过研磨后TCH-95树脂，搅拌混合得到成膜液；
（2）接着在步骤（1）得到的成膜液中，继续加入5~30ml/l的低粘度聚氨酯分散剂，并经过5~20KHz的超声振荡24h以上；
（3）在步骤（2）得到的成膜液中，继续加入适量的四甲基二乙胺和过硫酸铵，并在2~4℃的温度下水平放置保持1~10min，待氢氧化锆和TCH-95树脂颗粒自由沉积富集在液膜最底层后，升温至40~50℃，直到成膜液胶凝成膜；
（4）将得到凝胶薄膜经过去离子水浸泡12h以上，完成。
2.根据权利要求1所述沉积物中CH3Hg+和Hg2 +的DGT固定膜，其特征在于：所述水合氢氧化锆与异硫脲功能化大孔交联聚苯乙烯树脂的质量比为0.2~0.8:1。
3.一种基于权利要求1或2所述固定膜的DGT装置，其特征在于：包括底座，依次设在底座内的固定膜、扩散膜和滤膜，以及套在底座上的固定圈，所述底座和固定圈的材质为PTFE，所述扩散膜为1.5%的琼脂糖制成，所述滤膜为孔径为0.45微米的PVDF滤膜。
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