pH和有机酸对氟溶出砖红壤中铝离子的影响

研究砖红壤对F-的吸附反应尤其是随后Al3+的释放过程,有助于增进对土壤酸化过程及其环境影响的理解. 在初步揭示出F-吸附反应以及Al3+释放反应的动力学特征基础上,重点考察了pH和有机酸对上述反应的影响. 结果表明:土壤对F-的吸附反应十分迅速,2 min内吸附量即可达到24 h内总吸附量95%,而土壤中不同含铝矿物的溶解度差异使Al3+的释放过程在前15 min十分迅速,释放量可达24 h内总释放量的80%,随后则逐渐减缓. 降低反应体系pH可促进Al3+释放,但会使F-吸附量减少,这是因为伴随Al3+的释放,部分F-又可以AlF络合物的形态重新进入溶液,尽管在低pH条件下,土壤表面以带正电荷为主而有利于F-吸附. 草酸和抗坏血酸对土壤吸附F-均有抑制作用,但对F-溶出土壤Al3+有促进作用. 此外,草酸对土壤铁氧化物的选择性溶解作用,可使更多F-吸附在土壤铝氧化物位点,并导致Al3+释放量增加.      

亚热带红壤丘陵区茶园土壤中Al和F的分布特征及其影响因素

以化学浸提的方法研究了亚热带红壤丘陵区茶园土壤中活性Al和F的溶出和剖面分布特征.结果表明,各浸提液对Al的浸提能力顺序为:1mol/L HCl>1mol/L NH4AC(pH4.8)>1mol/L KCl(pH5.5)>H₂O(pH6.8).同样,在4种浸提态F中,1mol/L HCl所提取F的含量最高,含量范围为6.62～38.8mg/kg,1mol/L KCl与1mol/L NH₄AC所提取F含量次之,分别为4.57～28.1mg/kg和5.76～32.17 mg/kg,水溶性F的含量最低,含量范围为0.95～4.18mg/kg.各浸提态Al和F主要集中于0～3cm的表层,土壤剖面分布有上高下低的特征.水溶性Al与F存在线性回归关系,其他各浸提态Al和相关浸提态F之间也为显著的正相关关系.土壤中各浸提态Al和F含量随植茶年限的增长而增加,同时也受土壤母质、土壤pH值和有机质影响.     

F-对Al在土壤中吸附-解吸行为的影响

研究了F-对Al在土壤中吸附-解吸行为的影响.结果表明,F-可以通过两种方式来影响土壤对Al的吸附.加入的F-与Al形成F-Al络合物后将减少土壤对铝的吸附量;土壤吸附F-时释放的OH-则将提高土壤对铝的吸附量,一定程度上抑制了前一种方式的影响,但F-将降低土壤对Al的吸附量这一规律没有改变.由于土壤对Al有很强的亲合力,能被1.0M KCl解吸下来的铝数量很小,F-对铝的解吸行为没有产生明显的影响.     

重金属污染的长春水田黑土对菲的吸附作用

以菲为多环芳烃(PAHs)代表物,研究了Pb、Zn、Cu污染后黑土对PAHs的吸附作用.结果表明,分配作用是黑土吸附菲的主要机制,无论重金属污染与否,黑土对菲的等温吸附曲线均呈线性.实验条件下,重金属污染后黑土对菲的吸附作用明显增强,且随重金属含量提高,黑土对菲的吸附系数(Kd)和有机碳标化的吸附系数(Koc)增大.由于重金属的“键桥”作用,黑土吸附菲的平衡溶液中水溶性有机质(DOM)浓度降低,土壤固相有机质含量略有增加(不超过原有有机质含量的0.53%).计算了这部分增加的固相有机质对菲的吸附系数K_Ph/soc,并分析了溶液中DOM对土壤吸附菲的影响.结果显示,溶液中DOM浓度变化及其与菲的结合作用对重金属影响土壤吸附菲的贡献甚微;而K_Ph/soc值则比土壤原有有机质对菲的吸附系数K_d值大2～3个数量级,这是重金属污染导致土壤吸附作用增强的根本原因.     

去除氧化铁对Al在土壤中吸附-解吸的影响

用连二亚硫酸钠-柠檬酸钠-碳酸氢钠(DCB)法研究了去除土壤中的氧化铁后Al的吸附-解吸特征的变化情况.结果表明,在pH值<4.5条件下,去除氧化铁可使土壤对Al的吸附量有所增加,这种变化在赤红壤中尤为明显;而此后随pH值的升高,原土和去铁土对Al的吸附量基本相等.造成该现象的原因可归纳为去除氧化铁能降低土壤的电荷零点(ZPC)和增加土壤表面负电荷的数量,从而增强了土壤表面与离子之间的静电引力.另一方面,去除氧化铁后Al的解吸量也增加.其原因是与原土相比,去铁土吸附Al的机理中包含有部分静电吸附,这从离子强度对去铁土吸附Al的影响实验能得到较好的验证,因为在pH值<4.5时,提高离子强度将降低Al的吸附量,用高岭石做参考材料时也发现了类似的现象.     

Mg/Al LDH对UO22+的高效吸附研究

由于放射性污染物的不合理处置及核泄漏事件的发生,对生态环境和人类健康造成了严重危害.本研究采用共沉淀法制备了不同Mg/Al比(物质的量比)的Mg/Al LDH(层状双氢氧化物),研究其对UO_2~(2+)的吸附行为.同时,考察了吸附剂投加量、p H、吸附时间、初始浓度对吸附的影响,并采用XRD、FTIR、SEM、XPS等技术对吸附前后LDH材料进行表征与分析.结果表明:Mg/Al比为2∶1的Mg/Al LDH对UO_2~(2+)吸附效果要比Mg/Al比为4∶1的Mg/Al LDH好,Mg/Al比为2∶1和4∶1的Mg/Al LDH对UO_2~(2+)吸附容量分别为301.28和263.85 mg·g-1,对UO_2~(2+)具有优良的吸附性能,可以作为高浓度放射性污染废水的吸附材料和核泄漏事件的应急吸附材料.Mg/Al LDH对UO_2~(2+)的吸附更符合Langmuir等温吸附模型和Pseudo-second-order动力学模型.吸附后Mg/Al LDH的Mg/Al比降低,Mg/Al LDH对UO_2~(2+)的吸附机理是UO_2~(2+)与材料中氢氧根、碳酸根相互作用,形成三元的络合物而被去除.     

磷酸盐对土壤吸附一硫代砷的影响

通过设计批实验和表征分析,探究不同浓度的磷酸盐影响下,一硫代砷酸盐（MTA）在土壤上的吸附特征和机理.结果发现,Elovich动力学模型和Langmuir等温吸附模型可较好地拟合MTA在土壤中的吸附过程,相关系数R²分别为0.983和0.994,表明土壤吸附MTA发生在局部位置,吸附过程主要以非均相扩散为主,拟合所得最大单层吸附量为254.214mg/kg.MTA与磷酸盐共存时,随着溶液中磷酸盐初始浓度的增大,土壤对MTA的平衡吸附量逐渐下降,对磷酸盐的吸附量逐渐增大;SEM-EDS结果表明无论是否添加磷酸盐,反应后的土壤表面都能检测到少量As,但添加磷酸盐条件下土壤表面的As含量则相对较低,证实磷酸盐的存在降低了土壤对MTA的吸附;XRD结果表明MTA能与土壤中的铁铝矿物发生络合反应生成内球络合物－[2Al （H₂AsO₄）₃]、≡Al₂O₂AsO （SH）和－[2Fe （H₂AsO₄）₃],而磷酸盐会与土壤表面的羟基形成内球络合物,导致土壤对MTA的吸附能力减弱.     

化学沉淀分离-置换法提纯Al13的工艺研究

采用A1Cl3溶液和Na2CO3粉末在不同温度下制备了不同浓度的聚合氯化铝(PACl).以选定的中等浓度、高Al13含量的PACl为原液,研究了Al13与硫酸盐沉淀反应过程中SO4/Al摩尔比、反应体系起始总铝浓度的影响以及Al13硫酸盐与Ba(NO3)2置换反应过程中的Ba/SO4摩尔比、超声、温度等因素的影响.实验结果表明,在制备温度为50℃条件下,浓度在0.4～0.6mol/L范围的PACl含有较高的Al13.沉淀分离反应的最佳SO4/Al摩尔比为0.6∶1;生成的Al13硫酸盐沉淀物为正四面体状晶体.在Al13硫酸盐与Ba(NO3)2溶液置换反应过程中,Ba/SO4的最佳摩尔比为1∶1,反应温度及超声作用对置换反应的影响较小;提高Ba(NO3)2的起始浓度可以得到相应较高浓度的纯化Al13溶液.所得Al13纯度的统计平均值为92.1%.     

植物多酚物质原位钝化污染土壤重金属的研究 I.对土壤Cu吸持与溶出的影响

研究了两种缩合类植物多酚L和Y对土壤中污染元素Cu的吸持解吸的影响．结果表明植物多酚具有明显促进土壤吸持Cu，抑制土壤Cu的溶出作用，而且在潮上上效果更大在所研究的Cu和多酚浓度范围内，多酚Y都比多酚L作用显著．Cu的吸持等温线可用Freundlich方程定量描述有多酚存在的条件下土壤对Cu的吸持量比对照处理(不加多酚)高3—6倍．两种土壤对Cu吸持率随着多酚溶液浓度增加也随之增加，特别是在0-400mg(C)/L的多酚溶液浓度范围内，多酚Y和多酚L的浓度每提高100mg(C)/L，可分别使红壤对Cu的吸持率提高33.3％和56．60%，而使潮土提高14．1％和21．4％在土壤对Cu的吸附率相对比较低时(如pH2—5)，添加植物多酚显著增加土壤对Cu吸附．随着多酚溶液浓度的提高，两种土壤中Cu的溶出率都随之降低。     

类水滑石Mg/Zn/Al焙烧产物对高氯酸盐的吸附

利用类水滑石Mg/Zn/Al的焙烧产物对ClO-4进行吸附性能研究,通过类水滑石表面结构X射线衍射分析并探讨其吸附等温、动力学模型,并研究了焙烧温度、Mg/Zn/Al质量比、溶液pH值、吸附时间及吸附剂投加量等因素对类水滑石Mg/Zn/Al吸附ClO-4的性能影响.结果表明在500℃下焙烧4 h,Mg/Zn/Al质量比为2∶1∶1的类水滑石对ClO-4去除效果较好,吸附容量最大且对溶液pH值有较好的适用范围.经500℃焙烧的类水滑石吸附ClO-4的动力学拟合结果符合二级反应动力学模型,吸附等温线符合Langmuir及Freundlich吸附等温模型.     

酸性溶液中铝-氟反应动力学

研究了酸性溶液中铝氟反应的动力学，结果表明，铝氟之间的反应速率随温度和ｐＨ的升高而增加．低ｐＨ下以Ａｌ３＋＋Ｆ－＝ＡｌＦ２＋反应为主，较高ｐＨ下由于ＡｌＯＨ２＋参与反应及ＯＨ－的催化作用，反应速率加快．在铝的浓度比氟过量１０倍的情况下，铝氟之间的反应可以用一级反应动力学方程来拟合，即为假一级反应．当ｐＨ＜３８时，柠檬酸和草酸的存在使反应速度加快，而当ｐＨ＞３８时，有机酸使铝氟反应速度变慢．有机酸在不同的ｐＨ下存在不同的作用机制．     

土壤与酸性含氟溶液相互作用特征及机理研究

通过反复多次提取实验方法模拟了酸性含氟溶液与红壤和赤红壤相互作用过程。结果表明：在相互作用过程中，土壤中氟含量不同对土壤溶液pH有明显不同的影响。当氟含量较低时氟离子对土壤溶液pH的影响不明显；当浓度较高时则可大大提高土壤溶液的pH，缓冲土壤酸化。在第一次提取中因氟的大量吸附可减少溶液中铝的浓度，且氟含量越高铝浓度越少量越大。随提取次数增加土壤溶液中铝、氟浓度同时增加，且氟含量越高铝浓度越大，其中氟以AI－F络合物为主。     

低分子量有机酸对几种可变电荷土壤吸附氟的影响

用一次平衡法研究了四种低分子量有机酸对几种可变电荷土壤吸附氟的影响，结果表明，低分子量有机酸可以通过竞争吸附作用抑制土壤对氟的吸附，化学结构相对简单的草酸和丙二酸对氟吸附的抑制作用大于柠檬酸和苹果酸。有机酸对氟吸附的抑制作用随土壤氧化铁含量的增加而增加，并随体系pH的增加而增强。在低pH和氟加入量较高的情况下，有机酸通过与氟竞争可溶性铝而增加土壤对氟的吸附量，这在对铝溶解度较高的酸性土壤中尤为明显。     

Effects of fluoride on the removal of cadmium and phosphate by aluminum coagulation

This study focuses on the effects of pH and fluoride at different molar ratios of fluoride to Al (R_F:Al) on the removal of cadmium (Cd²⁺) and phosphate by Al coagulation. Fluoride at R_F:Al ≥ 3:1 inhibits the removal of Cd over wide Al dose ranges from 5 to 10 mg/L as Al. The removal of phosphate decreases significantly at high R_F:Al of 10:1 whereas at lowered R_F:Al (i.e., ≤ 6:1), an adverse effect is observed only at insufficient Al doses below 2 mg/L. Fluoride shows inhibitive effects towards the removal of Cd at pH 7 and 8 and that of phosphate at pH 6. Fluoride decreases the ζ-potential in both systems, and the decreasing extent is positively correlated to the elevated R_F:Al. The Al fluoride interactions include the formation of Al–F complexes and the adsorption of fluoride onto Al(OH)₃ precipitates, i.e., the formation of Al(OH)_nF_m. Al–F complex formation inhibits Al hydrolysis and increases residual Al levels, and a more significant increase was observed at lower pH. Al–F complexes at high R_F:Al complicate the coagulation behavior of Al towards both negative and positive ionic species. Moreover, fluoride at low R_F:Al shows little effect on Al coagulation behavior towards Cd^2 + and phosphate, and the spent defluoridation adsorbent, i.e., aluminum (Al) hydro(oxide) with adsorbed fluoride at R_F:Al of below 0.1:1, may be reclaimed as a coagulant after being dissolved.     

土壤酸化及天然土壤溶液中铝的形态

采用真空式土壤溶液采样器收集了宜昌、巫山松树林中天然土壤溶液,采用高效液相色谱法Al－Lumogallion柱后荧光检测,分析测试了土壤溶液中可溶性铝的形态,研究了由于土壤酸化引起天然土壤溶液中不同形态铝的迁移转化结果表明,天然土壤溶液中含有不同形态的铝,主要是有机铝、 AISO₄⁺、AIF₂⁺、Al（OH）²⁺、Al³⁺等．宜昌、巫山地区土壤溶液中活性铝（Al³⁺、AlOH^2+F）的含量比较低．土壤的酸化使得天然土壤溶液中总铝含量增加、铝形态的优势态发生变化,即土壤的酸化使得天然土壤溶液中活性铝－Al³⁺、AlOHF²⁺含量和比例增加．土壤酸化还降低了大然土壤溶液中的BC/Al比值,这些变化的结果都增加了对森林潜在的危害．     

水稻土团聚体Cu2+吸附过程中铝的溶出及土壤溶液pH变化

采用低能量超声波分散和冷冻机干燥法提取太湖地区水稻土(黄泥土)不同粒径团聚体颗粒,用平衡吸附法研究团聚体对重金属Cu2+吸附过程中铝的溶出及土壤溶液pH变化,以及不同pH的Cu2+溶液中铝的溶出量的变化.结果表明,团聚体对Cu2+的吸附过程,发生铝的溶出和土壤溶液pH下降,溶出量和pH下降幅度随Cu2+吸附量增加而增加,相同条件下铝溶出量和pH下降幅度大小顺序为:粗粉砂级>粉砂级>砂粒级>黏粒级,与氧化铁和有机质含量大小顺序相反.Cu2+溶液pH下降,铝的溶出量增加显著.氧化铁和有机质对Cu2+吸附过程铝的溶出和土壤溶液pH下降具有一定的抑制和缓冲作用.     

Mechanism and kinetics of aluminum dissolution during copper sorption by acidity paddy soil in South China

Soil aggregates were prepared from a bulk soil collected from paddy soil in the Taihu Lake region and aluminum (Al) dissolution, solution pH changes during copper (Cu^2 +) sorption were investigated with static sorption and magnetic stirring. Kinetics of Cu^2 + sorption and Al dissolution were also studied by magnetic stirring method. No Al dissolution was observed until Cu^2 + sorption was greater than a certain value, which was 632, 450, 601 and 674 mg/kg for sand, clay, silt, and coarse silt fractions, respectively. Aluminum dissolution increased with increasing Cu^2 + sorption and decreasing solution pH. An amount of dissolved Al showed a significant positive correlation with non-specific sorption of Cu^2 + (R² > 0.97), and it was still good under different pH values (R² > 0.95). Copper sorption significantly decreased solution pH. The magnitude of solution pH decline increased as Cu^2 + sorption and Al dissolution increased. The sand and clay fraction had a less Al dissolution and pH drop due to the higher ferric oxide, Al oxide and organic matter contents. After sorption reaction for half an hour, the Cu^2 + sorption progress reached more than 90% while the Al dissolution progress was only 40%, and lagged behind the Cu^2 + sorption. It indicated that aluminum dissolution is associated with non-specific sorption.     

Removal of fluoride from water using titanium-based adsorbents

Three adsorbents including TiO₂, Ti-Ce, and Ti-La hybrid oxides were prepared to remove fluoride from aqueous solution. The Ti-Ce and Ti-La hybrid adsorbents obtained by the hydrolysis-precipitation method had much higher sorption capacity for fluoride than the TiO₂ adsorbent prepared through hydrolysis. Rare earth (Ce and La) oxides and TiO₂ exhibited a synergistic effect in the hybrid adsorbents for fluoride sorption. The sorption equilibrium of fluoride on the three adsorbents was achieved within 4 h, and the pseudo-second-order model described the sorption kinetics well. The sorption isotherms fitted the Langmuir model well, and the adsorption capacities of fluoride on the Ti-Ce and Ti-La adsorbents were about 9.6 and 15.1 mg·g⁻¹, respectively, at the equilibrium fluoride concentration of 1.0 mg·L⁻¹, much higher than the 1.7 mg·g⁻¹ on the TiO₂. The sorption capacities of fluoride on the three adsorbents decreased significantly when the solution pH increased from 3 to 9.5. The electrostatic interaction played an important role in fluoride removal by the three adsorbents, and Fourier transform infrared (FTIR) analysis indicated that the hydroxyl groups on the adsorbent surface were involved in fluoride adsorption.     

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.