天然有机质对土霉素在西北灰钙土上吸附行为的影响

抗生素被广泛应用于日常生活中,大量含有抗生素的废弃物通过多种途径进入土壤给人类健康和土壤环境带来了严重危害,因此,探索抗生素类有机污染物在土壤中的吸附机理对土壤污染防治具有重要意义.以西北灰钙土为研究对象、以OTC（oxytetracycline,土霉素）为目标污染物,采用批量法分析灰钙土在添加有机质前、后对OTC的吸附动力学、热力学特征及其影响因素.结果表明:OTC的动力学吸附过程分快吸附阶段（0~2 h）和慢吸附阶段（2~10 h）,10 h之后吸附基本达到平衡,吸附过程拟合均符合准二级动力学模型.对不同温度下OTC在灰钙土上的吸附过程进行拟合显示,Langmuir和Freundlich热力学模型拟合的R2分别在0.930~0.985和0.967~0.973之间;对于不同初始ρ（OTC）在添加有机质灰钙土上的等温吸附过程,Langmuir和Freundlich热力学模型拟合的R2分别在0.952~0.988和0.936~0.971之间,表明这两种模型均可较好地解释此吸附过程;热力学参数ΔGθ（吉布斯自由能变）小于0,ΔHθ（焓变）和ΔSθ（熵变）均大于0,表明吸附为自发进行的混乱程度增大的吸热反应.添加外源性有机质HA（humic acid,胡敏酸）和FA（fulvic acid,富里酸）能增加OTC的吸附量,且自制有机质的促进作用大于市售有机质,HA的促进作用大于FA.随着初始ρ（OTC）的增大,吸附量呈增加趋势;Ca2+和Na+的加入均使OTC的吸附量减小,且离子浓度越高、价态越高,抑制效果越明显;不同pH对OTC吸附的影响均较小.研究显示,不同来源、种类的有机质均可促进OTC吸附,但不会改变吸附平衡时间;HA的疏水性较FA强,对OTC的吸附量较高;溶液pH对OTC吸附影响不显著,但不同价态、浓度的金属阳离子对OTC的吸附有较大影响.      

pH和有机质对土壤中锌的吸附-解吸特性影响研究

采用批次平衡法和Freundlich模型研究了锌在黑土和潮土中的吸附解吸行为,分析了p H和有机质对Zn在供试土壤中吸附解吸的影响。结果表明:黑土和潮土对Zn都具有较强的吸附能力,吸附-解吸等温线符合Freundlich模型,黑土和潮土的吸附-解吸常数(K_f)分别为1 882.03和1 546.66;在pH为4.6～7.4范围内,土壤对锌的吸附能力随pH值的升高而增强;土壤有机质去除后,K_f变小且经验常数(1/n)变大,吸附的非线性较强。     

天然地质样品有机质组成对菲吸附-解吸的影响

以2种有机碳含量、结构和性质都相差较大的天然样品Chelsea土壤和Paxton页岩为吸附剂,以菲为吸附质进行一系列的吸附-解吸实验。结果显示,当土壤有机质是以腐殖酸为主时(Chelsea土壤),样品对疏水性有机化合物的吸附很容易达到平衡,解吸与吸附之间的滞后现象不是很明显。相反,对以干酪根为主要组成的Paxton页岩样品,吸附与解吸之间有明显滞后现象发生,吸附与解吸是一个完全不可逆过程。这说明土壤有机质组成和结构上的差异可能会成为决定有机污染物环境行为的主要因素。      

水-土体系中溶解有机质对菲解吸动力学的影响

土壤解吸过程是影响污染物生物有效性和土壤修复的重要因素.采用人工添加方法制备加菲(PHE)老化1个月的土壤.考察水-土体系中溶解有机质(DOM)对PHE解吸动力学的影响和相互关系.结果表明.DOM与PHE的解吸释放浓度表现出相似的先增后减、最后趋于平衡的动力学过程(双尾显著性水平0.000,Spearman 秩相关系数0.778).PHE 解吸动力学常数量级的变化范围在10-5～10-6s-1之间,而且转折变化发生在峰值释放量所对应的时间点(2.5 h 左右).另外,紫外光谱表征参数E4/E6<5说明解吸进入水相的 DOM 主要为胡敏酸,另一参数A254,SUV 的变化趋势与PHE解吸动力学过程相一致.在不同pH条件下,PHE解吸浓度的关系为:碱性>中性>酸性.因酸性条件下溶解释放的胡敏酸(DHA)发生沉淀而无法判定其与PHE释放浓度的相关性;在其它pH条件下DOM、A254,,SUV>都分别与PHE的解吸浓度显著相关.这些结果说明DOM是影响PHE解吸动力学的重要因素.     

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.     

玉米秸秆生物炭对灰钙土吸附金霉素的影响

为研究生物炭(BC)添加对灰钙土(HGT)吸附金霉素(CTC)的影响,本文以玉米秸秆为原料分别在200、400和600℃下制备BC.采用批平衡法,研究CTC在HGT和HGT+BC上的吸附行为.结果表明,HGT对CTC的吸附平衡时间为240 min,添加BC使平衡时间相对延长,符合准二级动力学模型.CTC的总体吸附速率由表面扩散和颗粒内扩散共同控制,且表面扩散速率更快,疏水分配作用促进吸附进行.3种等温吸附模型拟合对CTC在HGT和HGT+BC中的吸附均呈现较好相关性.添加BC使HGT对CTC的吸附分配系数Kd值增大,亲和力增强.不同温度时分配系数Kd的差异性表明吸附过程为放热反应.吸附满足不同等温线型(L型和S型),是以化学吸附为主的非均质复杂吸附过程,伴随静电引力、氢键相互作用等表面吸附和物理吸附.pH=3时,CTC+与土壤表面的负性位点大量结合,发生阳离子交换与静电吸引作用,吸附量最大.pH增大,CTC存在形态改变,HGT和BC对其吸附能力减弱.BC在不同pH下始终增强HGT对CTC的吸附,且添加量越大,CTC的吸附分配系数Kd值越大.吸附是由HGT和BC的有机质含量、矿物组成、理化性质及CTC存在形态和环境因素共同作用的结果.研究表明适量添加BC对HGT吸附CTC具有积极影响,裂解温度200℃时作用最显著,可以有效促进HGT对CTC的吸附与固定作用.     

土壤有机质对土霉素在土壤中吸附-解吸的影响

采用批量平衡方法,研究了土霉素在原土及去除有机质土壤中的吸附和解吸.结果表明,土霉素在原土和去除有机质土壤中的吸附和解吸等温线均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,在不同土壤以及不同土壤处理中的拟合相关系数(r)均达到极显著水平.去除有机质能够降低土霉素在土壤中的吸附容量(lgKf),但增加了吸附强度(1/n).土霉素在土壤上的解吸过程存在明显的滞后现象,在所设土霉素浓度范围内,土霉素在褐土和红壤中的平均滞后系数(HIa)分别为0.039和0.015;去除有机质后的褐土和红壤对土霉素的解吸滞后现象显著增强(P<0.01),其HIa分别增加到0.068和0.028.     

溶解性有机质对芘在土壤中吸附解吸的影响

从腐解不同阶段的水稻秸秆提取溶解性有机质(DOM),用DAX-8树脂分组的方法分析了其亲疏水性,并研究了提取到的DOM对芘在土壤中吸附-解吸行为的影响.结果表明,随秸秆腐解时间的延长,产生DOM中亲水性组分减少,疏水性组分增多.在本试验所研究的吸附解吸实验条件下,芘在土壤中的吸附解吸均可用线性方程进行描述.加入DOM后,芘的吸附受到显著抑制(p0.01),并且随腐解时间延长,抑制作用增强;芘在土壤中存在解吸迟滞现象,加入DOM后迟滞现象减弱,促进了芘在土壤中的解吸.随腐解作用的进行,DOM促进芘解吸的作用增强,解吸迟滞系数减小.这是由于随秸秆腐解作用的进行,产生DOM中疏水性组分含量增多,其对芘的增溶作用增强所致.     

施加牛粪有机肥对灰钙土吸附阿特拉津的影响机制

有机肥在改良土壤的同时也会改变农药的环境行为. 为明确施加牛粪有机肥对灰钙土吸附阿特拉津(ATZ)的影响作用及机制,采用批平衡试验,分析其吸附动力学、热力学以及牛粪施加量、pH、离子强度等因素对ATZ吸附的影响. 结果表明:①ATZ在灰钙土与施加牛粪灰钙土上的吸附均可分为快吸附、慢吸附直至平衡的过程,准二级动力学模型可较好地描述其吸附过程,施加有机肥增加了ATZ在灰钙土上的平衡时间,吸附速率受颗粒内扩散和外部液膜扩散共同控制. ②施加牛粪有机肥后,灰钙土对ATZ的吸附热力学更符合Freundlich模型,1/n在0.42~0.64之间,吸附属“L型”模式,低温和高温均会抑制ATZ在灰钙土上的吸附. ③pH和共存离子是影响ATZ在灰钙土上吸附的重要因素,随pH的升高,ATZ在灰钙土与施加牛粪灰钙土上的吸附量降低,这是由于碱性情况下,ATZ以阴离子存在,与带负电的灰钙土产生静电排斥作用;灰钙土施加牛粪有机肥后,共存阳离子对ATZ的吸附抑制作用明显,增加离子强度可能导致竞争吸附的存在,从而抑制有机离子在灰钙土上的吸附,且离子浓度越高,抑制越明显. 研究显示,土壤施加牛粪有机肥后,ATZ的吸附量增加,吸附由疏水性分配转变为多分子层化学吸附为主,表明施加牛粪有机肥会改变ATZ在灰钙土上的吸附行为和机制,降低ATZ在灰钙土中的迁移风险. 研究结果将为贫瘠黄土土壤改良风险和三嗪类农药的管控提供理论依据.      

溶解性有机质对菲在沉积物上吸附与解吸性能的影响

采集了北京通州凉水河(标记为L)以及广东东江流域(标记为D)的沉积物,并进行菲(Phe)的连续吸附-解吸实验,研究了不同含量及组成的溶解性有机质(DOMs)对其吸附与解吸性能的影响.结果表明,DOMs能明显抑制菲在沉积物上的吸附,在实验浓度范围内(0~110mg/L),菲在沉积物上的吸附量与DOC浓度呈显著的负线性相关,并且DOC浓度越高,对吸附作用的抑制越显著.在溶解性有机质存在条件下,菲在2种沉积物上的吸附均呈线性吸附特征,kd值随加入沉积物浸出液DOC浓度的减小呈增大的趋势.菲在2种沉积物上的解吸过程均呈现一定的迟滞性,其解吸迟滞性可用热力学指数TII来描述.随着菲初始浓度的增加,TII值先减小后增加,其变化可以用吸附在高低位点上的菲分子比例以及菲分子是否能够被禁锢在吸附剂微孔内部来加以解释;溶解性有机质的存在,能促进菲从沉积物上的解吸,从而使菲的解吸滞后性减弱, 增强其在水环境介质中的迁移与传输能力.     

Comparison of zinc complexation properties of dissolved organic matter from surface waters and wastewater treatment plant effluents

Abstract: Unlike natural organic matter(NOM), wastewater organic matter(WWOM) from wastewater treatment plant effluents has notbeen extensively studied with respect to complexation reactions with heavy metals such as copper or zinc. In this study, organic matter trom sunface waters and a wastewater treatment plant effluent were concentrated by reverse osmosis(FIC)) method. The samples were treated in the laboratory to remove trace metals and major cations. The zinc complexing properties of both NOM and the WVVOM were studied by square wave anodic stripping voltammetry(SWASV). Experimental data were compared to predictions using the Windermere Humic Aqueous Model(WHAM) Version Ⅵ. We found that the zinc binding of WVVOM was much stronger than that of NOM and not well predicted by WHAM.This suggests that in natural water boodies that receive wastewater teatment plant effluents the ratio of WWOM to NOM must be taken into account in order to accurately predict ferr zinc activities.     

水溶性有机质对土壤及底泥中汞吸附行为的影响

以重庆市2种耕作土(黄壤和中性紫色土)及鱼塘底泥为试验材料,分别添加提取自腐殖土的DOM(DOMh),提取自稻草的DOM(DOM)和提取自污泥堆肥的DOM(DOMa),研究DOM对土壤及底泥中Hg的吸附行为的影响.结果表明.DOM对土壤及底泥中汞的吸附行为均有一定的抑制作用,这种抑制作用与DOM种类和试验材料的性质有关.添加不同来源的DOM,对Hg的抑制作用具体表现为:DOMh>DOMr>DOMa;添加同一种DOM时,对Hg吸附的抑制作用表现为鱼塘底泥>紫色土>黄壤.     

土壤组分对磷形态和磷吸附-解吸的影响——基于三峡库区消落带落干期土壤

通过选择性去除土壤组分的方法,探讨了三峡库区消落带落干期3种典型土壤中有机质、铁氧化物组分对磷形态和磷吸附-解吸的影响.结果发现,三峡库区消落带落干期3种典型土壤去除的有机质以易氧化组分为主,去除有机质后,土壤中各种磷形态的含量变化较小.然而,去除游离铁氧化物后,土壤中各种磷形态的含量均发生明显降低.同时,去除有机质、游离铁氧化物组分后并未改变土壤中各种磷形态的相对大小顺序,均为：钙结合磷（Ca-P） > 有机磷（OP） > 铁/铝结合磷（Fe/Al-P）.此外,黄壤（FJ）、紫色潮土（KX）和灰棕紫泥（FL）去除有机质后对磷的吸附能力较原始土壤仅分别降低0.5%、2.3%、6.5%（P=0.017<0.05,显著性差异）,表明3种土壤中有机质组分对磷吸附的影响较小;而去除游离铁氧化物后对磷的吸附能力分别降低45.6%、51.7%、43.9%（P=0.004<0.05,显著性差异）,表明土壤中游离铁氧化物组分是决定磷吸附大小的重要因素.另外,3种土壤去除游离铁氧化物后较原始土壤吸附磷的解吸能力明显增加,表明游离铁氧化物组分是控制3种土壤吸附磷的解吸的重要因素.FL土壤去除有机质组分后较原始土壤吸附磷的解吸能力略有降低,而KX和FJ土壤去除有机质组分后较原始土壤吸附磷的解吸能力无明显差异,表明有机质组分对土壤吸附磷的解吸的影响与土壤类型有关.     

Effect of organic matter and pH on mercury release from soils

An investigation was conducted on the effect of organic matter(OM)and pH on mercury(Hg)release from soils.Hg release flux was measured using the dynamic flux chamber(DFC)combined with the Lumex multifunctional mercury analyzer in both laboratory experiment and field monitoring.The results showed that Hg emission from the OM-added soils was apparently low because of the high affinity of OM to Hg,resulting in the reverse order as the amount of OM addition.Meanwhile,Hg release flux from different pH value soils exhibited the same trend for both Hg~(2 )and Hg_2~(2 )treatment,increasing the Hg flux with pH value of soils increasing.The trend of Hg release in the pH dependence experiment has been well in agreement with that from the field test.In addition,Hg release seemed to be related to its species in the soil,the flux from Hg~(2 )-added soil was obviously higher than that of Hg_2~(2 )-added soil by the laboratory experiment.     

Sorption of dissolved organic matter and its effects on the atrazine sorption on soils

IntroductionApplication of organic amendments, such as sewagesludge to agricultural soils, has been considered as aneffective way to improve the soil physico chemical propertiesand organic matter compositions. Dissolved organic matter(D…     

Effect of dissolved organic matter on adsorption and desorption of mercury by soils

Effects of dissolved organic matter (DOM) on adsorption and desorption of Hg were investigated in two kinds of soils, Xanthi-Udic Ferralosols (XUF) and Typic Purpli-Udic Cambosols (TPUC). The DOM was obtained from humus soil (DOMH), rice straw (DOMR), and pig manure (DOMP). The presence of DOM obviously reduced Hg maximum adsorption capacity with up to 40% decreases over the control, being an order of DOMH (250.00 mg/kg)< DOMR (303.03 mg/kg) < DOMP (322.58 mg/kg) < CK (control 416.67 mg/kg) for the XUF and ...     

Effects of dissolved organic matter from sewage sludge on sorption of tetrabromobisphenol A by soils

Sorption of tetrabromobisphenol A (TBBPA) by soil influences its fate and transport in the environment. The presence of dissolved organic matter (DOM) may complicate the sorption process in soil. The effects of DOM from sewage sludge on TBBPA sorption by three soils were investigated using batch equilibration experiments in the study. DOM was observed to be sorbed on the soils and the isotherms could be fitted by the Langmuir model. The effects of DOM on TBBPA sorption were dependent on the characteristics ...     

施用有机物料对污染土壤水溶性有机物和铜活性的动态影响

采用黑麦草盆栽研究施用绿肥、污泥和猪粪后，对Cu污染土壤水溶性有机物(DOM)和土壤Cu环境行为动态的影响．施用有机物料后土壤DOM含量比对照增加0.4—7.5倍，尤以绿肥和猪粪最明显．但随时间延长DOM降解明显，尤其在第一周内．污染土壤中水溶性Cu浓度随DOM的降解而相应减少研究发现，施用污泥有利于降低污染土壤中水溶性Cu浓度和黑麦草对Cu的吸收量，这是污泥固相有机质对Cu吸持使其活性降低和污泥DOM使Cu活性提高二者综合作用的结果．与此相反，施用绿肥和猪粪后，黑麦草体内的Cu含量却明显提高，其中潮土上提高1．4～2．1倍，红壤上提高1．4-1．6倍．因此．施用有机物料改良重金属污染地需格外谨慎。     

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.