重金属镉在黑土和棕壤中的解吸行为比较

采用一次平衡法对Cd²⁺在黑土和棕壤2种土壤类型中的解吸行为进行了比较研究.结果表明,Cd²⁺在2种土壤中的解吸行为均有明显的滞后性.相对于棕壤,Cd²⁺在黑土中的解吸有更长的滞后阶段.Cd²⁺在2种土壤中的解吸过程是一个快速反应的过程,当解吸平衡时间在30min左右时,吸附态Cd²⁺的解吸量能达到总解吸量的90%以上.Cd²⁺在2种土壤中的解吸效率都比较低,相对于总吸附量而言,Cd²⁺在黑土和棕壤的解吸百分比分别低于9.0%和15.1%.解吸速率随着初始浓度的增加而升高,但随着解吸量和解吸时间增加而下降,土壤性质对解吸速率的下降并没有明显的影响.Freundlich方程是描述Cd²⁺在这2种土壤中等温解吸的最佳方程,而Elovich方程是描述其在这2种土壤中解吸动力学变化的最佳方程.     

重金属铜在黑土和棕壤中解吸行为的比较

采用一次平衡法研究吸附态Cu²⁺在黑土和棕壤上的解吸行为并进行了比较.结果表明,与棕壤相比,黑土吸附态Cu²⁺解吸有更长的滞后阶段,黑土在Cu²⁺的吸附量低于729.00mg·kg^-1(Cu²⁺处理浓度小于40 mg·L^-1),棕壤在Cu²⁺的吸附量低于393.29 mg·kg^-1(Gu²⁺处理浓度小于20 mg·L^-1)时,土壤吸附态Cu²⁺几乎不发生解吸.2种土壤吸附态Cu²⁺的解吸率均较低,尤其是黑土.在试验所采用的Gu²⁺处理浓度范围内,黑土与棕壤吸附态Cu²⁺的最高解吸率分别为6.60%和13.56%.Freundlich方程为描述2种土壤Cu²⁺等温解吸过程的最佳方程.黑土和棕壤吸附态Cu²⁺的解吸速率均较快,在40min左右基本达到平衡.描述黑土和棕壤解吸动力学过程的最优模型为双常数速率方程,其次为Elovich方程.     

β-环糊精/环氧氯丙烷聚合物的制备及其对双酚S的吸附特性

BPS（双酚S）用途广泛,但存在水环境污染问题,容易引起类似于双酚A的雌激素反应,因此需要寻求高效的吸附剂从水溶液中将其脱除.在NaOH水溶液中,以环氧氯丙烷为交联剂,合成了β-CDP（β-环糊精/环氧氯丙烷聚合物）,用于吸附水溶液中的BPS.基于此,考察了吸附时间、pH、初始ρ（BPS）、β-CDP用量对吸附性能的影响以及β-CDP的再生性能,探讨了吸附动力学、等温吸附模型和吸附机理.结果表明:①在温度为298 K、pH为5.4、β-CDP用量为0.05 g、初始ρ（BPS）为100 mg/L、BPS溶液体积为50 mL、吸附时间为60 min的条件下,BPS吸附量为69.7 mg/g,吸附率为69.7%;②吸附动力学符合准二级动力学模型,表明化学吸附为速率控制步骤;③Langmuir吸附等温模型的成功拟合表明,吸附BPS在β-CDP表面上形成了单分子层覆盖;④β-CDP吸附BPS为放热过程,低温有利于吸附的进行;⑤与初始吸附量（69.7 mg/g）相比,β-CDP连续再生6次,BPS吸附量仍可达68.1 mg/g;⑥吸附机理是通过BPS的羟基与β-CDP形成氢键作为推动力,并借助β-CD（β-环糊精）空腔内部的疏水作用,使得BPS进入空腔形成包结物.研究显示,β-CDP对水溶液中的BPS具有良好的吸附性能,再生循环使用稳定性高,具有较高的性价比.      

Cd2+、Pb2+在根际和非根际土壤中的吸附-解吸行为

采用1次平衡法对Cd²⁺、Pb²⁺在小麦根际和非根际土壤中的吸附-解吸行为进行比较研究.结果表明,根际土对Cd²⁺和Pb²⁺的吸附能力高于非根际土,2类土壤对Cd²⁺的吸附等温线与Freundlich方程有较好的拟合性,Pb²⁺的等温吸附过程可由Langmuir方程与Freundlich方程来描述.双常数方程是描述根际、非根际土Cd²⁺和Pb²⁺吸附动力学行为的最优模型,其次为Elovich方程,最差模型是一级动力学方程.Cd²⁺、Pb²⁺ 的解吸存在滞后现象,相比于非根际土,根际土吸附态Cd²⁺、Pb²⁺ 的解吸率更低,Cd²⁺、Pb²⁺的解吸量与其初始吸附量之间的关系符合2次幂方程.2类土壤Cd²⁺、Pb²⁺的解吸速率随重金属初始浓度的增加而增加,随解吸时间的延长而不断降低.描述根际和非根际土Cd²⁺、Pb²⁺的解吸动力学过程的最优模型均为双常数方程,其次为Elovich方程,一级动力学方程拟合效果不佳.     

土壤-水体系中固/液比对溶解性石油烃吸附的影响

采用批实验的方法,研究了2种土壤在不同的固/液比（solid-to-solution ratio,SSR）条件下对溶解性石油烃（DPH）的吸附-解吸特性.结果表明,DPH在土壤中的吸附-解吸等温线符合线性方程;解吸表现出明显的滞后现象,滞后因子随SSR的升高而增加,随土壤有机碳含量（OC）的升高而减小,对于OC=1.54%的稻田土,当SSR从10.00 g·L^-1变化至75.00 g·L^-1,DPH的解吸滞后因子从1.43升高到2.21;对于OC=15.91%的黑土,当SSR从2.50 g·L^-1变化至5.00 g·L^-1,DPH的解吸滞后因子从1.18升高到1.37.说明吸附的不可逆性随SSR的升高而增强,随土壤有机碳含量的升高而减弱.另外,研究发现由吸附等温线计算得到的k_OC随SSR的升高（不可逆性的增强）而减小,在此基础上建立了固定体系中k_OC与SSR的关系模型,用于预测实际环境中DPH在土-水界面的迁移.     

稀土工业污染土壤对外源钍的吸附行为研究

研究了外源钍在土壤上的吸附行为并评估其对土壤的污染风险.通过静态吸附解吸实验考察土壤样品对不同量外源钍的吸附容量、吸附平衡时间、分配系数和解吸能力.土壤样品对外源钍有很强的吸附能力,在吸附平衡时吸附百分比均大于92%,而解吸率均小于5%;钍在土壤溶液中分配系数最高可达104以上;吸附容量和平衡时间与土壤性质有关.吸附实验结果表明,可用Freundlich吸附等温式和Elovich方程分别描述土壤样品对钍吸附的热力学行为(r≥0.916 7)和动力学过程(R2≥0.898 0).较佳的拟合结果表明,土壤样品对外源钍的吸附是非线性物理化学吸附,吸附反应速率受钍在土壤表面和矿物内层扩散影响.采用形态连续萃取法分析外源钍在土壤上吸附后的赋存形态.由钍形态萃取结果,少量外源钍(10-7~10-6mol.L-1)进入土壤后主要以不稳定非残留态存在,其含量在58%以上;随着外源钍量增加,钍非残留态量增加,同时更多外源钍迁移到稳定残留态.     

黄泥土不同粒径微团聚体对Cd2+的吸附与解吸研究

对采自太湖地区黄泥土进行了低能量超声波分离,采用平衡吸附法研究了不同粒径微团聚体颗粒对重金属Cd²⁺的吸附和解吸特点.结果表明,不同粒径微团聚体对Cd²⁺的吸附特性均符合Freundlich方程,模拟方程得到的K值介于152～503之间,以粘粒级和粗砂级为最大.微团聚体对Cd²⁺的吸附容量与其中游离氧化铁含量、CEC呈显著正相关.不同微团聚体Cd的解吸特点不同,粘粒级的解吸率仅为8.4%,远远低于其它粒径的微团聚体,这些结果有助于了解田间条件下土壤重金属化学行为和微观尺度的化学过程.     

生物炭墙对紫色土坡耕地中氟苯尼考迁移影响

采用实验室批量平衡实验,研究紫色土坡耕地土壤中氟苯尼考吸附-解吸特征及生物炭施用的影响,此外,开展野外坡底生物炭（重量占比5%）可渗透反应墙的构建试验,观测自然降雨条件下该反应墙对坡耕地小区中氟苯尼考随地表径流与下渗水迁移的影响.结果表明,氟苯尼考在紫色土中的等温吸附行为符合Freundlich方程,在低浓度范围内（<2mg/L）,生物炭的施用一方面提高了其在紫色土中的吸附量,吸附过程可能以内扩散为主,另一方面,显著降低其解吸量;紫色土坡耕地中的淋溶作用是氟苯尼考的主要迁移方式;坡底生物炭（5%）渗透墙的构建有效地减控了其在紫色土中的淋溶迁移以及深层侧向迁移.     

阳离子类型对土霉素在2种土壤中吸附-解吸影响

以OECD Guideline 106为基础,采用批量平衡方法研究不同阳离子Ca²⁺、K⁺、Na⁺对土霉素在2种土壤(褐土和红壤)中的吸附-解吸影响.结果表明,不同阳离子条件下,土霉素的吸附-解吸不同程度地偏离线性模型,其中Freundlich模型可以对吸附和解吸数据进行良好的非线性拟合,平均拟合相关系数为0.989;除了KCl介质中土霉素在褐土中的吸附等温线呈线性外,其它介质条件下的等温吸附线均属“L”型等温吸附线.在同一阳离子介质中,土霉素在红壤(2.907～3.173)中的吸附容量(lgK_f)始终高于褐土(2.577～2.885),而在红壤(0.672～0.825)中吸附强度(1/n)始终低于褐土(0.713～1.005),且在2种土壤中的吸附均以物理吸附为主.3种阳离子对土霉素在2种土壤中的吸附行为的影响存在较大的差异,同一土壤中阳离子类型对土霉素的吸附容量无显著影响;而与K⁺和Na⁺相比,Ca²⁺的存在显著降低溶液中土霉素在土壤上的吸附强度(p<0.05).土霉素在土壤上的解吸过程存在明显的滞后现象,平均滞后系数HI在0.015～0.053之间.在同一阳离子介质条件下,土霉素在褐土中的滞后系数显著高于红壤(p<0.05);在同一土壤中,不同阳离子对滞后系数的影响不同,其中在褐土中K⁺与Ca²⁺、Na⁺之间的差异达到极显著差异(p<0.01),而3种阳离子对土霉素在红壤中的解吸滞后影响并无显著差异.     

聚天冬氨酸对土壤吸附、解吸汞的机制研究

为揭示土壤中添加聚天冬氨酸（PASP）后其对汞的吸附、解吸过程,探究了不同PASP用量对土壤吸附解吸汞的机制及有机质、pH、汞初始浓度等因素的影响。结果表明,PASP可显著抑制土壤对汞的吸附,促进土壤对汞的解吸,在PASP用量为300 mg时,其吸附量、解吸量分别是未添加PASP时的0.68、27倍;有机质与PASP之间在土壤吸附汞时表现为拮抗作用,在土壤解吸汞时表现为协同作用;在较宽pH范围（4.0～7.0）和不同汞浓度（5～200 mg/L）下,PASP均能抑制土壤对汞的吸附;PASP作用于整个吸附进程;土壤对汞的吸附特征符合Langmuir、Freundlich方程和准二级动力学方程,而PASP的存在均使其特征方程偏离;原土和去除有机质的土壤对汞的最大吸附量（q_m）分别为2.1和2.0 mg/g,比未添加PASP的处理分别下降了65.47%和12.94%。本研究为PASP应用于汞污染土壤的修复奠定了研究基础。     

Effect of biosurfactant on the sorption of phenanthrene onto original and H2O2-treated soils

The objective of this study was to examine the effect of biosurfactant on the sorption of phenanthrene (PHE) onto the original or H2O2-treated black loamy soil (typic isohumisols) and red sandy soil (typic ferralisols). The sorption isotherms were performed with the original and “soft” carbon-removed soils in the presence and absence of biosurfactant (200 mg/L). The sorption and degradation of biosurfactant were investigated. The result showed that organic matter played an important role in PHE sorption onto the black loamy and red sandy soils, and the PHE sorption isotherms on the “soft” carbon-removed soils exhibited more nonlinearity than those on the original soils. The values of partition coe cient (Kd) on the original black loamy soil with or without 200 mg/L biosurfactant were 181.6 and 494.5 mL/g, respectively. Correspondingly, in the red sandy soil, Kd was 246.4 and 212.8 mL/g in the presence or absence of biosurfactant, respectively. The changes of Kd suggested that biosurfactant inhibited PHE sorption onto the black loamy soil, but facilitated PHE sorption onto the red sandy soil. The nonlinearity of PHE sorption isotherm was decreased in the presence of biosurfactant. Site specific sorption might occur during PHE sorption onto both the original and the “soft” carbon-removed soils in the presence of biosurfactant. It was noted that biosurfactant could also be sorbed onto soils. The maximal sorption capacity of the red sandy soil for biosurfactant was (76.9 0.007) g/g, which was 1.31 times that of black loamy soil. Biosurfactant was degraded quickly in the two selected soils, and 92% of biosurfactant were mineralized throughout the incubation experiment for 7 d. It implied that biosurfactant should be added frequently when the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils was conducted through PAH desorption approach facilitated by biosurfactant.     

改性土壤对模拟含油废水中油的吸附

研究季铵盐阳离子表面活性剂四甲基铵离子 ( TMA)和十六烷基三甲基铵离子 ( HDTMA)改性的土壤 (黑土、黄棕壤、红壤 )对水中油的吸附作用 .结果表明 :改性土壤和未改性土壤均可吸附水中的油 ,但改性土壤对水中油的吸附能力明显高于未改性土壤 .改性土壤吸附油能力的顺序依次为 :1 CEC- HDTMA黑土 >1 CEC-HDTMA黄棕壤 >1 CEC- HDTMA红壤 >1 CEC-TMA黑土 >1 CEC-TMA黄棕壤 >1 CEC- TMA红壤 .未改性土壤和 HDTMA改性土壤对油的吸附通过分配来进行 ,吸附等温线可由 Henry方程表示 ,得出 logK_SOM为 2.69,logK_HDTMA为 3.35;TMA改性土壤对油的吸附符合 Langmuir方程 ,其对油的饱和吸附量分别为 1150 mg/kg( TMA黑土 ) ,751 mg/kg( TMA黄棕壤 ) ,172 mg/kg( TMA红壤 )     

Effect of biosurfactant[0] on the sorption of phenanthrene onto original and H2O2-treated soils

The objective of this study was to examine the effect of biosurfactant on sorption of phenanthrene (PHE) onto the original or H2O2-treated black loamy soil (typic isohumisols) and red sandy soil (typic ferralisols). The sorption isotherms were performed with the original and "soft" carbon-removed soils in the presence and absence of biosurfactant (200 mg/L). The sorption and degradation of biosurfactant were investigated. The result showed that organic matter played an important role in PHE sorption onto the black loamy and red sandy soils, and the PHE sorption isotherms on the "soft" carbon-removed soils exhibited more nonlinearity than those on the original soils. The values of partition coefficient (Kd) on the original black loamy soil with or without 200 mg/L biosurfactant were 181.6 and 494.5 mL/g, respectively. Correspondingly, in the red sandy soil, Kd was 246.4 and 212.8 mL/g in the presence or absence of biosurfactant, respectively. The changes of Kd suggested that biosurfactant inhibited PHE sorption onto the black loamy soil, but facilitated PHE sorption onto the red sandy soil. The nonlinearity of PHE sorption isotherm was decreased in the presence of biosurfactant. Site specific sorption might occur during PHE sorption onto both the original and the "soft" carbon-removed soils in the presence of biosurfactant. It was noted that biosurfactant could also be sorbed onto soils. The maximal sorption capacity of the red sandy soil for biosurfactant was (76.9 ± 0.007) μg/g, which was 1.31 times that of black loamy soil. Biosurfactant was degraded quickly in the two selected soils, and 92% of biosurfactant were mineralized throughout the incubation experiment for 7 d. It implied that biosurfactant should be added frequently when the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils was conducted through PAH desorption approach facilitated by biosurfactant.     

源自腐殖土的溶解性有机质组分对棕壤和黑土吸附苯并三唑的影响

溶解性有机质(DOM)影响着有机污染物在土壤中的吸附行为.将从腐殖土中提取的DOM(DOMbulk)用XAD-8树脂和阴/阳离子交换树脂进行分级,用红外光谱、元素分析、紫外分光光度计和电位滴定的方法对DOM不同组分特征进行分析.用吸附批次实验方法研究了DOM不同组分对棕壤和黑土吸附苯并三唑(BTA)的影响.结果表明,DOMbulk中疏水酸性(HOA)、疏水中性(HON)、亲水酸性(HIA)、亲水碱性(HIB)和亲水中性(HIN)组分比例分别为61%、17%、6%、2%和14%.由于黑土有机碳(OC)含量高于棕壤,黑土对BTA和DOM组分的吸附能力均大于棕壤.相对于黑土,棕壤吸附DOM的标化分配系数Koc较高,其原因是棕壤中含有较多的对吸附DOM起重要作用的黏粒和粉砂.由于水分子占据DOM结合点位,DOM组分与BTA在溶液中结合较弱.DOMbulk中HIN在土壤上吸附最强.HIN的吸附增加了土壤吸附BTA的点位,增加点位的促进吸附作用大于HIN与BTA的竞争吸附作用,最终表现为促进吸附.疏水组分在土壤上的吸附较弱,产生的新吸附点位较少,主要通过竞争吸附作用抑制土壤对BTA的吸附.DOMbulk由78%的疏水组分构成,对土壤吸附BTA的影响与疏水组分相似.     

天然土壤中菲的解吸行为特征研究

选取天然土壤样品,以菲作为代表性污染物,利用批量吸附-解吸实验考察不同初始浓度、不同吸附时间条件下菲解吸行为的滞后性特征.实验数据采用Freundlich方程式拟合,并由基于热力学的TII指数表征.结果表明,天然土壤吸持菲的比例随其初始浓度的增加而减少.在土壤多次解吸过程中,每次释放菲的比例随其初始浓度的升高而增加,随解吸次数的增加而减少.吸附过程的拟合指数n大于解吸过程的对应值,并随初始固相浓度的加大而增加.天然土壤吸附-解吸过程的滞后性特征表现为初始固相浓度越高,TII值越接近0,滞后性越弱;反之,则TII值越接近1,滞后性越强.另外,吸附平衡时间30 d对应的n值小于5 d的,而两者的TII值随初始浓度增高则呈现降低趋势.就同一浓度而言,吸附平衡30 d所对应的TII值高于5 d的.     

芘在土壤中的长期吸附和解吸行为

研究了芘在6种不同性质土壤中长期吸附解吸及不可逆吸附行为.实验结果表明:长期实验中芘在土壤中的吸附和解吸都存在快过程和慢过程2个阶段.不同吸附平衡时间下,有机质含量高于1%时,不同土壤的吸附平衡常数随有机质含量的增加而增加;有机质含量低于1%时,黏粒含量对土壤的吸附能力有着重要影响;平衡时间由2d增加到180d后,6种土壤的Kd值增加了35.1%～557.9%,其中土壤有机质对Kd值有不同程度的影响,而黏粒对Ka值影响最大,平衡时间对部分土壤Kd值影响不容忽视.长期解吸过程中,6种土壤慢解吸部分占总解吸量的12.05%～41.00%,有机质含量越高,慢解吸对解吸过程的贡献越大.不考虑老化的影响,有机质含量对不可逆吸附容量的贡献明显高于黏粒的贡献,与有机质对慢解吸过程的影响有一致性.     

Utilizing surfactants to control the sorption, desorption, and biodegradation of phenanthrene in soil-water system

An integrative technology including the surfactant enhanced sorption and subsequentdesorption and biodegradation of phenanthrene in the soil-water system was introduced and tested. For slightly contaminated agricultural soils, cationic-nonionic mixed surfactant- enhanced sorption of organic contaminants onto soils could reduce their transfer to plants, therefore safe-guarding agricultural production. After planting, residual surfactants combined with added nonionic surfactant could also promote thedesorption and biodegradation of residual phenanthrene, thus providing a cost-effective pollution remediation technology.0ur results showed that the cationic-nonionic mixed surfactantsdodecylpyridinium bromide (DDPB) and Triton X-100 (TX100) significantly enhanced soil retention of phenanthrene. The maximum sorption coefficient Kd* of phenanthrene for contaminated soils treated by mixed surfactants was about24.5 times that of soils without surfactant (Kd ) and higher than the combined effects of DDPB and TX100 individually, which was about 16.7 and 1.5 times Kd , respectively.0n the other hand, TX100 could effectively remove phenanthrene from contaminated soils treated by mixed surfactants, improving the bioavailability of organic pollutants. Thedesorption rates of phenanthrene from these treated soils were greater than 85% with TX100 concentration above2000 mg/L and approached 100% with increasing TX100 concentration. The biodegradation rates of phenanthrene in the presence of surfactants reached over 95% in30days. The mixed surfactants promoted the biodegradation of phenanthrene to some extent in 10-22days, and had no obvious impact on phenanthrene biodegradation at the end of the experiment. Results obtained from this study provide some insight for the production of safe agricultural products and a remediation scheme for soils slightly contaminated with organic pollutants.     

Impacts of soil organic matter, pH and exogenous copper on sorption behavior of norfloxacin in three soils

Norfloxacin (Nor) sorption and the factors (soil organic matter (SOM), pH, and exogenous copper (Cu) influencing the sorption were investigated in a black soil (soil B), a fluvo-aquic soil (soil F), and a red soil (soil R). With increasing of Nor concentrations, sorption amount of norfloxacin increased in both the bulk soils and their SOM-removed soils, but the sorption capacity in SOM-removed soils was higher than that of their corresponding bulk soils, indicating that the process of norfloxacin sorption in soil was influenced by the soil properties including SOM. The sorption data in all bulk soils and SOM-removed soils were fitted to Freundlich and Langmuir models. The correlation coefficients suggested that the experimental data fitted better to Freundlich equation than to Langmuir equation. Furthermore, the data from soil F and SOM-removed F could not be described by Langmuir equation. The norfloxacin sorption amount decreased in soil B and soil F, whereas it increased in soil R as solution pH increased. The maximum KD and KOC were achieved in soil R when the equilibrium solution pH was 6. And the norfloxacin sorption was also influenced by the exogenous Cu2+ ions, which depended on the soil types and Cu2+ concentrations. With increasing of Cu2+ concentrations in solution, generally, sorption amount, KD and KOC for norfloxacin in soils increased and were up to a peak at 100 mg/L Cu2+, and then the sorption amount decreased regardless of norfloxacin levels.     

土壤有机质和镉对金霉素吸附-解吸的影响

金霉素已经广泛应用于兽药生产和疾病治疗.由于动物废弃物的土地应用和其它输入来源,重金属与四环素类抗生素往往共存于土壤环境中.基于OECD 106号指导准则,采用批量平衡实验方法,研究了金霉素及其与镉复合后在褐土及去有机质褐土中的吸附和解吸行为.结果表明,在单一和复合污染条件下,金霉素在褐土和去有机质褐土中的吸附和解吸等温线都可以用Freundlich模型进行良好地拟合.在金霉素单一污染和金霉素-镉复合污染条件下,去除有机质能够增加金霉素在褐土中的吸附容量(Kf)和吸附强度(1/n).金霉素在土壤上的解吸过程存在明显的滞后现象,在单一污染物情况下,金霉素在去有机质褐土的解吸滞后现象增强,其HI从0.81增加到1.06;而加镉后这种现象反而有所减弱,其HI从1.11减低到0.84.本研究为建立更加完善的模型以预测金霉素环境浓度或评价其环境风险,提供了可利用的数据和参数.