Research Progress on the Effect of Dissolved Organic Matter on the Environmental Behavior of Cadmium in the Environmental Remediation
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摘要:
随着经济社会的快速发展和镉(Cd)的持续排放，Cd污染日益成为中国乃至全球面临的重大环境问题。溶解性有机质(DOM)作为有机物中最活跃的组分，其分子量通常在几Da至几百kDa之间。DOM包含的羧基、羟基、酚基等多种活性官能团是环境中诸多重金属的配位体和迁移载体。DOM与Cd之间通过物理吸附、配体交换、表面络合等作用，显著影响着Cd在环境中的形态、生物可利用性、毒性和迁移转化。但从Cd污染修复的角度来看，Cd与DOM的络合作用是控制Cd修复成效的关键因素。DOM可以通过配体交换直接形成DOM-Cd二元络合物。根据DOM、Cd(Ⅱ)和矿物/金属表面阳离子(Mi/Me)的不同桥接位置，也可以形成A型或B型两种三元络合物。DOM来源多样，成分、结构复杂，不同条件下DOM对Cd呈现钝化或活化两种作用，在Cd污染原位钝化修复、淋滤修复或者植物修复中得到广泛应用。本文在总结近年来国内外相关研究基础上，对DOM和Cd的络合作用类型进行了重点评述，分析了DOM分子量、环境pH值、离子强度、温度等因素影响Cd-DOM络合作用及Cd吸附(解吸)机制，在此基础上探讨了DOM在土壤/沉积物Cd污染原位钝化修复、异位修复中的主要应用方向，这些方法有助于降低Cd污染修复环境风险和修复成本。通常情况下，小分子量DOM含有更丰富的官能团和更复杂的络合位点，容易形成可溶性DOM-Cd络合物，特别是对于分子量＜30kDa的DOM 组分，可向环境中释放更多的Cd；在较高pH值环境条件下，则有利于增强DOM-Cd络合物的稳定性和土壤对Cd的吸附，而高离子强度对Cd吸附有很强的抑制作用；在Cd污染修复工作中，选择腐殖化程度较高的较大分子量DOM(＞30kDa)，并配施铁氧化物等无机钝化剂，可明显地提升Cd污染原位钝化修复成效；在Cd的化学淋滤或植物修复中，选择小分子量DOM(＜5kDa)以提高污染修复的成效。未来该领域研究建议关注三方面：①不同分子量DOM与Cd的络合作用研究，精准解析DOM内部不同组分的功能基团与Cd的络合作用。②加强多种因素影响和控制下DOM对Cd吸附与解吸、迁移转化和生物有效性研究。③加强DOM在Cd污染修复技术研究，完善DOM与Cd相互作用的数值模拟模型，为Cd污染长期观测工作提供路径指引和数据支撑，更加精准地揭示Cd在环境中的迁移转化过程。
要点(1)络合反应是溶解性有机质(DOM)与Cd相互作用的主要机制，不同种类DOM对Cd分别具有钝化或活化两种环境效应。
(2)较高分子量DOM、较高环境pH值和温度、较低离子强度有利于增强DOM-Cd络合物稳定性，降低Cd的迁移转化。
(3)腐殖质指数(HIX)较高的大分子量DOM配施无机钝化剂，适用于Cd污染原位钝化修复，而小分子量DOM则适用于Cd污染的淋滤修复和植物修复。
HIGHLIGHTS(1) The complexation reaction is the main mechanism between DOM and Cd, and different types of DOM have two effects on Cd: passivation or activation.
(2) Higher molecular weight DOM, higher environmental pH and temperature, and lower ionic strength are beneficial for enhancing the stability of DOM-Cd complexes, reducing the migration of Cd.
(3) High molecular weight DOM with high humus index (HIX) combined with inorganic passivators is suitable for in-situ passivation remediation of Cd pollution, while low molecular weight DOM is suitable for Cd pollution leaching remediation and plant remediation.
Abstract:With the rapid development of the economy and society and the continuous emission of cadmium (Cd), Cd pollution has become a major environmental problem faced by China and even the world. As the most active component in organic matter, molecular weight of DOM is usually between several Da and several hundred kDa.The various active functional groups contained in DOM, such as carboxyl, hydroxyl, and phenolic groups, are ligands and migration carriers for many heavy metals in the environment. The interaction between DOM and Cd significantly affects the morphology, bioavailability, toxicity, and migration transformation of Cd in the environment through physical adsorption, ligand exchange, and surface complexation. However, from the perspective of cadmium pollution remediation, the complexation between Cd and DOM is a key factor controlling the effectiveness of Cd remediation. DOM can directly form DOM Cd binary complexes through ligand exchange. According to the different bridging positions of DOM, Cd(Ⅱ), and mineral/metal surface cations (Mi/Me), two types of ternary complexes can also be formed: A or B.DOM has complex and diverse sources, components, and structures, under different conditions, DOM exhibits two effects on Cd: passivation or activation, which has been widely used in in-situ passivation remediation, leaching remediation, or phytoremediation of Cd pollution. Based on the review of relevant research results in recent years, this article evaluates the types of complexation between Cd and DOM, and analyzes the effects of factors such as DOM molecular weight, pH, ion strength, and temperature on Cd-DOM complexation and the mechanism of Cd adsorption and desorption. On this basis, Summarize the application research of DOM in in-situ passivation remediation and ex-situ remediation of soil/sediment Cd pollution. These methods help to reduce environmental risks and remediation costs of Cd pollution remediation. Under normal circumstances, small molecular weight DOM contains richer functional groups and more complex coordination sites, making it easy to form soluble DOM-Cd complexes. Especially for DOM components with molecular weight＜30kDa, which can release more Cd into the environment; Under higher pH environmental conditions, it is beneficial to enhance the stability of DOM-Cd complexes and soil adsorption of Cd, while high ionic strength has a strong inhibitory effect on Cd adsorption; In the remediation of Cd pollution, selecting larger molecular weight DOM (＞30kDa) with higher humification degree and applying inorganic passivators such as iron oxides can significantly improve the in-situ passivation and remediation effect of Cd pollution; In the chemical leaching or phytoremediation of Cd, small molecular weight DOM (＜5kDa) is selected to improve the effectiveness of pollution remediation. it is recommended to conduct research in the following three areas in the future: firstly, study the complexation between different molecular weights of DOM and Cd, and accurately analyze the complexation between functional groups of different components inside DOM and Cd. Secondly, strengthen the research on the adsorption, desorption, migration, transformation, and bioavailability of Cd by DOM under the influence and control of multiple factors. Finally, Strengthen the research on DOM in Cd pollution remediation technology, improve the numerical simulation model of the interaction between DOM and Cd, provide path guidance and data support for long-term observation of Cd pollution, and more accurately reveal the migration and transformation process of Cd in the environment.
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总溶解氮(TDN)是水中所有溶解性的含氮化合物的总量，包括溶解无机氮(DIN)和溶解有机氮(DON)，其中溶解无机氮还包括硝酸盐氮、氨氮、亚硝酸盐氮等［1］。总溶解氮主要来源于农业施肥、爆炸物、生活污水、大气沉降及动植物和微生物代谢活动等，是评价水质恶化的重要指标，衡量水质被污染及自净状况［1-2］。过量的总溶解氮随水体自然移动，对水质和人类健康造成重大威胁［3］。地热水作为宝贵的液态矿产资源，可用于温泉、发电、生产饮用矿泉水、养殖等［4-5］，近年来被广泛开发利用［6-7］。然而，由于人们的过度开采，导致了地热水中总溶解氮含量过高，地热水水质严重恶化［8］。过高的总溶解氮会导致地热水水体富营养化，影响养殖生物环境及其他方面；同时饮用过量的亚硝酸氮/硝酸氮和氨氮超标的地热矿泉水，对人体分别具有高致癌风险及对淋巴细胞、味觉、嗅觉毒害作用［8-9］，而总溶解氮中氨氮、亚硝酸氮、硝酸氮又可以相互转化，其危害作用不容忽视。为解决地热水中总溶解氮污染问题，精确、快速检测其中总溶解氮的含量十分必要，对于充分研究总溶解氮的生物地球化学循环和地热水的合理开发利用具有重要意义。
溶解无机氮的检测方法有很多，而溶解有机氮的结构、成分复杂，其检测方法尚不明确。总溶解氮主要通过消解前处理，使各个形态的氮转化为硝酸盐氮，再进行定量测定。常见的消解方法有紫外氧化法［10-11］、高温燃烧法［12-14］、碱性过硫酸盐消解法［15-17］等。紫外氧化法存在氧化不完全、回收率较低和变异性大等问题；高温燃烧法的转化效率高，但需要特定的仪器且价格较高。样品中总溶解氮转化为硝酸盐氮后，可采用离子色谱法［18-20］、镉柱还原法［21-23］、紫外可见分光光度法［24-26］等方法测定。离子色谱法无需其他试剂，绿色环保，但分析时间长，效率低。镉柱还原法是将硝酸盐用镉柱还原为亚硝酸盐，还原率较高，但镉的毒性较大，污染环境。紫外可见分光光度法具有适用范围宽、灵敏度高等优点，但存在样品中多组分混合物重叠吸收、定性和定量分析准确度低等问题。
碱性过硫酸盐消解法是一种被广泛应用的湿法化学消解方法，具有使用设备简单、氧化效率高等优点，过硫酸盐被热分解成毒性较小的硫酸盐，消解后样品中总溶解氮全部转化为硝酸盐氮。但在实际应用中，消解时间、消解温度、过硫酸盐用量等均影响总溶解氮的测定，一些研究［16，27］表明消解时间长达40～60min，严重降低了测定效率。与其他水体相比，地热水具有化学成分复杂多变、盐度大的特点，采用行业标准《水质 总氮的测定 碱性过硫酸钾消解紫外分光光度法》(HJ 636—2012)测定总溶解氮时，干扰组分多，准确度低。而紫外二阶导数光谱法［28-30］是解决干扰因素多的最佳方法，其紫外二阶导数光谱图峰型好，灵敏度和分辨率高；而关于碱性过硫酸盐消解法和紫外二阶导数光谱法联用测定总溶解氮的报道较少［27］。基于此，本文采用碱性过硫酸盐消解-紫外二阶导数光谱法联用测定地热水中总溶解氮，其二阶导数光谱图可消除大部分干扰因素，是测定地热水中总溶解氮的理想方法，其中总溶解氮以硝酸根-氮的形式定量测定。实验主要研究了紫外二阶导数光谱图确定定量测定硝酸根-氮含量的特征吸光度，通过单因素水平实验和双因素方差分析实验，优化碱性过硫酸钾消解反应中的消解时间、稀释步骤等参数。考察了地热水中高含量共存离子的干扰情况和标准曲线的拟合度及线性范围后，通过实际样品加标回收实验以及与行业标准方法进行对比，对方法的可靠性和准确性进行了验证。
1. 实验部分
1.1 仪器与主要试剂
实验主要使用仪器为紫外可见分光光度计(UV2550型，日本岛津公司)，波长范围为190～800nm；石英比色皿光程10mm；高压蒸汽灭菌器(最高温度不低于120℃)；具塞磨口玻璃比色管容量25mL等。
硝酸钾标准储备溶液：BWZ7192—2016，1000mg/L，以氮计。
水中总氮标准储备溶液：GBW(E)083307，1000mg/L，以氮计。
水中氨氮标准储备溶液：GBW(E)083304，1000mg/L，以氮计。
水中尿素氮标准储备溶液：GBW(E)085011，1000mg/L，以氮计。
硝酸钾标准使用溶液(10.0mg/L，以氮计)：由硝酸钾标准储备溶液逐级稀释而成。
碱性过硫酸钾溶液(40.0g/L)：称取40.0g过硫酸钾和15.0g氢氧化钠于超纯水中，定容至1.0L。
过硫酸钾、氢氧化钠、浓盐酸、氯化钠、硫酸钠、碳酸氢钠等试剂皆为优级纯。10%盐酸溶液。实验用水为超纯水，电阻率为18.2MΩ·cm。
1.2 实验方法
精确移取0、0.20、0.50、1.00、2.00、3.00、5.00硝酸钾标准使用溶液(10.0mg/L，以氮计)于25mL玻璃比色管中，用超纯水定容体积至10mL。上述溶液中硝酸根(以氮计)的浓度分别为0.00、0.20、0.50、1.00、2.00、3.00、5.00mg/L，再分别加入5.00mL碱性过硫酸钾溶液(40.0g/L)，塞紧管塞，用塑料膜和皮筋扎紧管塞，置于高压蒸汽灭菌器中进行消解反应，温度升至120℃后保持20min，冷却至室温后，加入1.0mL 10%的盐酸溶液，用超纯水定容体积至25mL，摇匀后上机测定。
本实验采用紫外二阶导数光谱法，总溶解氮以硝酸根-氮的形式定量测定。以空白溶液作参比，采用10mm石英比色皿，波长扫描范围为190～270nm，选定并记录硝酸根(以氮计)在波长226.6nm处二阶导数吸收值。以标准溶液吸光度为横坐标，硝酸根(以氮计)含量为纵坐标绘制校准曲线，使用校准曲线对所有样品进行定量分析。样品溶液取样量为10.00mL，实验方法同硝酸根(以氮计)标准系列，同时做空白对照实验。如样品中总溶解氮含量过高，超出标准曲线最大值，可将样品溶液稀释后重新测定。
2. 结果与讨论
2.1 紫外二阶导数光谱分析及波长的确定
地热水样品普遍矿化度较大，样品中各物质成分复杂，存在胶体、悬浮物及有机物，通过紫外可见分光光度法分析总溶解氮含量时特征峰值不明显，干扰因素多，相互重叠，且双波长紫外分光光度法也无法完全这些消除干扰。而紫外二阶导数光谱法则是解决这些问题的有效方法，具有放大微弱吸收峰、提高灵敏度和分辨率、消除噪声干扰等能力。
紫外二阶导数光谱法中，波长的确定十分重要，波长的作用有提高灵敏度和分辨率，减少背景干扰等。图1为硝酸根-氮标准溶液和地热水样品溶液的紫外光谱图、一阶和二阶导数光谱图。其紫外光谱图峰型杂乱且不对称，特征吸收峰值不明显，干扰物质多；一阶导数光谱出现负峰，进行二阶导数处理后，其二阶导数光谱图分辨率高，大部分干扰因素消除，图像更为灵敏，在波长226.6nm处存在特征吸收值，且不受其他成分干扰的影响。本实验中硝酸根-氮二阶导数光谱图波形及出峰时间与王静敏等［28］、陈晓伟等［29］、Ferree等［27］研究获得的规律大致相同，进一步说明了方法的可靠性。图2为不同浓度的硝酸根-氮标准溶液的二阶导数光谱图，在波长226.6nm处峰型好，稳定性高，其特征吸收值与硝酸根-氮浓度成正比。因此，确定波长226.6nm对应的二阶导数值为定量测定硝酸根-氮含量的特征吸光度。
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图 1 硝酸根-氮标准溶液和地热水样品溶液的紫外光谱图(a)、一阶(b)和二阶导数光谱图(c)Figure 1. UV spectra (a), first derivative spectra (b) and second derivative spectra (c) of nitrate-nitrogen standard solution and geothermal water sample solution![]()
图 2 不同浓度的硝酸根-氮标准溶液的二阶导数光谱图Figure 2. Second derivative spectra of nitrate-nitrogen standard solutions with different concentrations2.2 碱性过硫酸钾消解反应参数的优化
碱性过硫酸钾消解反应中，消解参数的选择对于准确定量测定地热水中总溶解氮至关重要。消解反应中，其中消解温度、消解时间、碱性过硫酸钾溶液体积、样品体积与稀释步骤是5个最为关键的因素。本实验中，逐级稀释配制总溶解氮(TDN)、溶解无机氮(DIN)-氨氮和溶解有机氮(DON)-尿素质控样品，其浓度分别为15.0、10.0、21.0mg/L，利用上述质控样品进行消解时间、消解温度、碱性过硫酸钾溶液体积的单因素水平实验，结果如图3所示。
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图 3 消解时间(a)、消解温度(b)和碱性过硫酸钾溶液体积(c)对总溶解氮(TDN)、溶解无机氮(DIN)和溶解有机氮(DON)质控样品测定结果的影响Figure 3. Effect of digestion time (a), digestion temperature (b) and volume of alkaline potassium persulfate solution (c) on the determination of total dissolved nitrogen (TDN), dissolved inorganic nitrogen (DIN) and dissolved organic nitrogen (DON) in quality control samplesFerree等［27］指出消解时间为60min时，总溶解氮的回收率高于消解时间30min的回收率。由图3a可以看出，本实验结果与刘振超等［17］改进测定水质总氮方法中对消解时间的讨论结果大致相同。在消解时间为0～60min范围内，消解时间为0时，所有质控样品中硝酸根-氮回收值为0，说明样品不经过高温高压反应，各种形式的氮无法转换成硝酸盐-氮。当消解时间＜10min时，各质控样品回收值都偏低，且相对偏差大；当消解时间≥20min后，三种质控样品的回收值皆趋近理论值。如图3b所示，消解温度为105℃时，总氮和无机氮质控样品回收值偏大，其原因可能是温度过低，碱性过硫酸钾氧化不完全，干扰总氮的测定；当温度达到110℃后，三种质控样品的回收值与理论值没有显著差异。碱性过硫酸钾溶液体积对消解反应的影响如图3c所示，碱性过硫酸钾溶液体积为1.0～4.0mL时，三种质控样品的回收值皆有低于理论值的情况；当体积为5.0～6.0mL时，其回收值皆接近理论值。综合考虑质控及实际样品，实验推荐消解温度为120℃，消解时间为20min，碱性过硫酸钾溶液体积为5.0mL。
对样品体积与稀释步骤进行双因素方差分析实验，结果如图4所示。消解后稀释的样品，各质控样品的回收值显著低于理论值；而样品体积对测定结果影响不大。稀释步骤是影响总溶解氮测定最重要的因素，与Ferree等［27］的实验结果相同。考虑样品稀释的倍率及相对误差，实验选择样品体积为10.0mL，稀释步骤安排在样品消解前。
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图 4 样品体积与稀释步骤对总溶解氮(TDN)、溶解无机氮(DIN)和溶解有机氮(DON)质控样品测定结果的影响Figure 4. Effect of sample volume and dilution time on analytical results of total dissolved nitrogen (TDN), dissolved inorganic nitrogen (DIN) and dissolved organic nitrogen (DON) quality control samples.2.3 共存离子的干扰与消除
地热水矿化度较高，基体成分复杂，样品消解后采用紫外二阶导数光谱法测定总溶解氮(TDN)时，可能有其他共存离子产生干扰。地热水中高含量离子主要以钠离子(Na+)、氯离子(Cl−)、硫酸根离子(SO42−)、碳酸氢根离子(HCO3−)、溴离子(Br−)、碘离子(I−)和氟离子(F−)为主。结合实际样品中各离子的浓度范围，实验配制了6组分别含有2000mg/L氯化钠、2000mg/L硫酸钠、800mg/L碳酸氢钠、10mg/L溴离子、10mg/L碘离子、10mg/L氟离子的总溶解氮质控样品(3.0mg/L)，通过比较这6组质控样品中总溶解氮的测定值，以评估各共存离子对总溶解氮测定的影响，结果如图5所示。6组总溶解氮质控样品中，含有10mg/L溴离子的质控样品回收值偏高，其他离子对总溶解氮分析的干扰不明显。在分析溴含量高的样品时，可以将样品先过银型预处理柱或者其他方法除去溴离子后，再进行定量分析。
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图 5 共存离子对总溶解氮测定结果的影响Figure 5. Effect of coexisting ions on the determination of total dissolved nitrogen2.4 校准曲线及线性范围
在0.20～5.0mg/L线性范围内，配制硝酸根(以氮计)标准系列溶液浓度分别为0.00、0.20、0.50、1.00、2.00、3.00、5.00mg/L，按照本文1.2节实验方法进行测定，绘制校准曲线。校准曲线线性回归方程为Y=1599.1X+0.0267，其中X为标准溶液紫外二阶导数光谱图在波长266.6nm处吸光度，Y为标准溶液硝酸根(以氮计)浓度(mg/L)，决定系数R2=0.9996，线性拟合度令人满意，符合实验分析的要求。
地热水中总溶解氮含量目前没有确定范围，取决于不同的用途及地质条件、污染因素等。参考《地表水环境质量标准》(GB 3838—2002)规定，Ⅰ类水、Ⅱ类水、Ⅲ类水、Ⅳ类水、Ⅴ类水中总溶解氮限值(mg/L)分别为≤0.20、≤0.5、≤1.0、≤1.5、≤2.0。因此，0.20～5.0mg/L线性范围可满足总溶解氮的分析测定要求，部分因污染因素而导致含量特别高的样品可稀释后测定。
2.5 实际样品测定及加标回收
为了验证采用本文方法测定地热水中总溶解氮(TDN)的可靠性，分别选取甘肃兰州、山西晋中、四川甘孜藏族自治州、河南安阳4个地区地热水样品，按照上述方法测定样品中的总溶解氮，同时加入不同含量的总氮标准溶液，其回收结果列于表1。扣除本底值后，各样品总溶解氮的加标回收率皆在94.0%～103.5%之间，相对偏差在0.83%～3.36%之间，说明本文方法检测结果准确可靠。
表 1 实际样品的测定及加标回收率Table 1. Determination of the actual samples and spiked recovery样品编号 总溶解氮含量(mg/L) 相对偏差
(%)回收率
(%)本底值 加标量 理论测定值 实际测定值 1# 0.33 0.50 0.83 0.81 2.41 96.0 1.00 1.33 1.37 3.01 104.0 2.00 2.33 2.40 3.00 103.5 2# 1.45 0.50 1.95 1.92 1.54 94.0 1.00 2.45 2.40 2.04 95.0 2.00 3.45 3.52 2.03 103.5 3# 0.49 0.50 0.99 0.97 2.02 96.0 1.00 1.49 1.44 3.36 95.0 2.00 2.49 2.42 2.81 96.5 4# 1.92 0.50 2.42 2.40 0.83 96.0 1.00 2.92 2.86 2.05 94.0 2.00 3.92 3.83 2.30 95.5 2.6 方法对比
目前暂时缺乏地热水标准样品，因此本实验根据地热水中各离子的大致浓度范围，自配2个含有不同浓度总溶解氮的地热水标准样品（编号SI和S2），样品中常规离子大致浓度为：钾(20mg/L)、钠(2000mg/L)、钙(200mg/L)、镁(100mg/L)、氯离子(2500mg/L)、硫酸根(1300mg/L)、重碳酸根(500mg/L)，总溶解氮浓度为1.60mg/L和4.50mg/L。分别采用本文方法和行业标准方法《水质 总氮的测定 碱性过硫酸钾消解紫外分光光度法》(HJ 636—2012)进行6次平行测定，计算的相对标准偏差(RSD)、与理论值偏差、两种方法测定结果相对偏差列于表2。由于自配样品化学成分相对简单，不含有胶体、有机物等干扰成分，两种方法的测定结果偏差不大，相对偏差分别为1.83%和2.18%，但是本文方法测定值的RSD及与理论值的偏差皆优于行业标准方法。
表 2 方法对比实验(n=6)Table 2. Comparison of analytical results obtained by different methods (n=6)样品编号 总溶解氮含量理论值
(mg/L)本文方法 碱性过硫酸钾消解紫外分光光度法 测定结果相对偏差
(%)测定值
(mg/L)RSD
(%)与理论值偏差
(%)测定值
(mg/L)RSD
(%)与理论值偏差
(%)S1 1.60 1.62 1.85 1.25 1.65 2.89 3.12 1.83 S2 4.50 4.54 1.69 0.89 4.64 3.57 3.11 2.18 3. 结论
建立了碱性过硫酸盐消解-紫外二阶导数光谱法测定地热水中总溶解氮的方法，总溶解氮以硝酸根-氮的形式定量分析。通过研究硝酸根-氮紫外二阶导数光谱图确定特征吸光度，其特征吸光度与硝酸根-氮浓度呈现良好的线性关系。通过单因素水平实验和双因素方差分析实验，优化消解反应中的条件参数，降低了基体干扰，提高了分析效率和准确性。消除共存离子干扰后，采用本文方法建立标准曲线，测定实际样品中总溶解氮含量，同时与行业标准方法进行对比实验，其重现性好，准确性高。
本文方法具有强抗干扰能力，可解决地热水样品化学组成复杂、干扰因素多的问题，需要的样品量小，仪器成本低，为地热水中总溶解氮的测定提供了一种高效、适用的分析方法。该方法也适用于分析地表水、生活饮用水等其他水样中的硝酸根和总溶解氮含量，后续工作可以进一步探索研究。
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图 1 元素Cd在自然环境中的吸附、解吸和迁移转化过程
Figure 1. The adsorption, desorption, migration and transformation processes of Cd in natural environment
表 1 三元络合体系对Cd的吸附机理和影响因素
Table 1 Adsorption mechanism and influencing factors of Cd in the ternary complexation system
吸附系统 影响Cd吸附的因素 吸附效果 主要吸附作用类型 参考文献 针铁矿-柠檬酸-Cd pH 增加 B-tc，矿物吸附 ［16］ 蒙脱石-HA-Cd Cd浓度 增加 B-tc，矿物吸附 ［29］ 纤铁矿-FA-Cd pH，RO/M，时间 增加 Cd-DOM，B-tc，矿物吸附 ［30］ 高岭石-HA/FA-Cd pH，时间，Cd浓度 增加 静电作用，A-tc，矿物吸附 ［31］ 氯磷灰石-纤维素-Cd pH，IS，DOM浓度 增加 B-tc，矿物吸附 ［32］ 膨润土/沸石-DOM-Cd RM/O，Cd浓度 降低 Cd-DOM，B-tc，矿物吸附 ［33］ 铁氢氧化物-HA-Cd pH，时间，RM/O 不详 Cd-DOM，B-tc，矿物吸附 ［34］ 
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