岩溶区典型石灰土Cd形态指示意义及风险评价——以桂林毛村为例

为了了解岩溶区石灰土中重金属Cd形态分配特征及富集情况,在桂林毛村采集了3种处于不同发育阶段的黑色、棕色和红色石灰土进行研究。通过原子光谱仪测试了Cd质量分数,运用改进的Tessier分析法测定了3种石灰土中Cd的可交换态(EXC)、碳酸盐结合态(CAB)、铁锰氧化物结合态(OXI)、有机结合态(ORG)、残渣态(RES)5种形态,并对其指示意义及风险进行了分析与评价,结果表明,3种石灰土中Cd质量分数从大到小依次为早期黑色石灰土、中期棕色石灰土、晚期红色石灰土。形态测试结果表明:黑色石灰土和棕色石灰土中Cd形态以铁锰氧化态和残渣态为主,占土壤Cd质量分数的63%以上,且5种形态质量分数从大到小顺序均为铁锰氧化态、残渣态、可交换态、碳酸盐结合态、有机结合态;红色石灰土Cd形态以残渣态为主,占土壤Cd质量分数的76%,形态分配特征从大到小为残渣态、铁锰氧化态、可交换态、碳酸盐结合态、有机结合态。Cd稳定度和富集程度评价结果表明:在黑色石灰土、棕色石灰土和红色石灰土中Cd稳定度逐渐减小,环境二次释放风险逐渐降低;富集程度从大到小依次为黑色石灰土、棕色石灰土、红色石灰土,其中Cd在黑色石灰土中呈显著富集状态,在棕色石灰土中呈中度富集状态,在红色石灰土中呈轻微富集状态。潜在生态风险评价和健康风险评价结果表明,由早期黑色石灰土到中期棕色石灰土和晚期红色石灰土,土壤中Cd的生态风险和健康风险均逐渐降低。研究结果可为岩溶区土壤重金属Cd污染修复与治理提供基础数据。     

氟铝交互作用对茶园土壤氟吸附动力学特征的影响

在氟的不同初始浓度及不同水土比情况下,茶园土壤对氟的吸附平衡时间均在25min左右,但对动力学方程拟合效果有一定差异,除了初始浓度为4.0mg/L(水土比10∶1)、20.0mg/L(水土比40∶1)、100.0mg/L(水土比40∶1和20∶1)处理氟的吸附动力学不能用一级动力学方程或二级动力学方程描述外,其余处理均可以用双常数方程、Elovich方程、一级动力学方程、二级动力学方程和抛物线方程这5个动力学方程描述。在铝存在下,不同氟铝比对氟的吸附动力学过程有明显影响,表现为吸附速率下降,吸附平衡时间延长,50min左右达吸附平衡。动力学方程拟合效果虽然有一定差异,但均可以用这5个动力学方程描述。在有无铝存在下,茶园土壤氟的吸附动力学特征用双常数方程和Elovich方程描述的效果更好。     

铅在高岭石表面的解吸动力学

经过酸性条件下（pH=3.1)Pb(Ⅱ）高岭石表面解吸动力学的研究，发现解吸反应与吸附反应动力学相似，也是一个二阶段的过程，即初始的快速解吸之后伴随着一个缓慢的释放过程。在快速解吸阶段，7min内解吸量即已达到41％。吸附铅没有完全解吸，有近38％残留在高岭石表面，即解吸和吸附过程不是完全可逆的。解吸过程可以用扩展Elovich方程、Elovich方程、双常数方程和一级扩散方程较好地似合。     

粘土质白云岩去除水中铜离子的效果及其机制

利用静态吸附实验研究了溶液pH值、反应时间、初始Cu2+浓度等因素对凹凸棒石粘土矿中粘土质白云岩去除Cu2+效 果的影响,将准一级、准二级、Elovich动力学方程与反应动力学进行拟合,再利用Langmuir、Freundlich等温方程对实验数 据进行等温式拟合,并与普通白云岩和凹凸棒石粘土进行了对比研究。结果表明,粘土质白云岩相对于其他两种材料受pH 影响较小,且在pH3~5范围内对Cu2+去除率均大于85%,最佳pH为5;对Cu2+的去除符合准二级动力学模型,粘土质白云 岩对铜的去除速率和去除率均最高;等温数据符合Freundlich模型,对Cu2+的最大去除量（pH=5,30℃）为186.2×10-3。粘 土质白云岩去除水中Cu2+的主要机制为矿物水化与溶解引起的表面沉淀及凹凸棒石与新生碱式碳酸铜[Cu2CO3(OH)2]胶体的静 电吸附。粘土质白云岩中纳米凹凸棒石与亚微米多孔白云石共生,具有较高的化学反应活性,除Cu2+效果明显优于普通白 云岩和凹凸棒石粘土,在处理含Cu2+废水方面具有潜在应用价值。     

针铁矿/水界面反应性的实验研究

选择针铁矿对Pb2+、Cu2+、Cd2+等3种重金属离子的吸附实验,开展矿物/水界面反应性研究.金属离子(M2+)在矿物-水溶液间分配有多种表面反应机制,这些表面反应发生作用的条件主要取决于吸附质水化学性质和矿物表面荷电性,因此,溶液pH值是影响矿物/水界面反应性的关键因素.在不同pH值条件下, 表面羟基可通过发生质子化或去质子化反应而使得矿物表面产生荷电性并发生改变,而金属离子的水解则可显著加快金属羟基配合物的形成,从而进一步增强了矿物/水界面反应.本实验条件下针铁矿表面对重金属离子的吸着量随pH值升高而升高,在一个较窄的pH值范围内吸附率急剧升高,呈S形分布.针铁矿对3种不同的重金属离子的吸附能力的强弱顺序是Cu2+＞Pb2+＞Cd2+.无论是Langmuir方程还是Freundlich方程,都能较好拟合针铁矿对重金属离子的等温吸附过程.Freundlich方程的n值均在0.1～0.5之间,说明重金属离子在针铁矿表面的吸附并不能简单地归结为单配位或双配位模式,可能存在着多种吸附结合形态.表观吸附常数KM值的变化规律,说明重金属离子与针铁矿表面反应模式及其表面吸附形态发生了变化,具体的吸附形态还有待谱学研究进一步证实.     

石灰土盐基离子迁移对模拟酸雨的响应

为揭示酸雨条件下石灰土盐基离子迁移特征及其缓冲性能,对石灰土进行了室内模拟酸雨淋溶试验,探讨酸雨酸度、土层厚度、土表覆被对石灰土酸化/石灰土抗酸性以及盐基离子迁移的影响。结果表明:（1）在pH=3.5、4.5、5.5的酸雨淋溶下,石灰土盐基离子迁移量差异不显著,对酸雨具有极强的缓冲能力。期间,Ca2+与Mg2+释放呈显著线性相关。（2）土壤厚度对石灰土抗酸性有极显著影响,土壤越厚,对酸雨的抗性越大,反之越小。（3）土厚比1∶2.5∶5的石灰土盐基离子淋失状况为K+淋失量1∶1.43∶2.06,Ca2+淋失量为1∶1.63∶3.13,Mg2+淋失量为1∶1.64∶3.15,表明土厚的增加能大大降低酸雨对盐基的淋溶。（4）石灰土土表覆盖不同,其盐基离子迁移淋溶量差异明显,但并不对土壤酸化效应产生显著影响。      

污灌土壤对铅的吸附和解吸特性

为了解污灌土壤对铅的吸附-解吸机制,进行不同条件下的吸附-解吸试验。结果表明：污灌土壤对铅的吸附量随铅初始浓度的增大,呈现先强烈吸附再缓和的过程。Langmuir模式对污灌土壤等温吸附铅的拟合效果最好,其饱和吸附量为7.84 mg/g。亚砷酸盐的存在会阻碍污灌土壤对Pb²⁺的吸附,亚砷酸盐加入前后污灌土壤对铅的吸附率从99.9％～100％下降到97.8％～99.0％。加亚砷酸盐条件下污灌土壤对铅的等温吸附模式以Freundlich模式的拟合效果最好。污灌土壤对吸附态铅的解吸量随解吸振荡时间的延长而不断增加,且解吸率随时间增加总体趋于降低。Elovich方程和幂函数方程均能很好地拟合污灌土壤对铅的解吸动力学过程,尤其是Elovich方程的拟合效果最为显著。     

海带对Pb2+吸附动力学及热力学研究

以海带作为吸附剂,从动力学和热力学角度讨论了海带对水溶液中pb2+的吸附情况以及溶液的pH值对吸附的影响.实验数据利用准一、准二级动力学模型以及Langmuir和Freundlich吸附等温式等进行拟合.实验表明,海带对pb2的吸附反应更符合准二级动力学方程及Langmuir吸附等温线;吸附速率较快,60min内,溶液中pb2+的去除率可达90％.     

Zn2+改性丝光沸石对甲基橙的吸附性能研究

采用盐熔融法,将Zn2+交换丝光沸石分子筛制备Zn2+改性丝光沸石吸附材料。通过该材料对甲基橙的吸附动力学和吸附热力学研究,了解其吸附机理。研究结果表明:Zn2+改性丝光沸石对甲基橙的吸附动力学可用拟二级动力学方程来描述,计算值与试验值吻合较好,相关系数达到0.99;Zn2+改性丝光沸石对甲基橙的吸附等温线均符合Langmuir和Freundlich方程,室温下相关系数均大于0.9。根据不同温度下的热力学平衡常数,推算出Zn2+改性丝光沸石对甲基橙的吸附吉布斯自由能变ΔG0<0,吸附焓变ΔH0>0,表明吸附为自发的吸附过程,升温有利于吸附的进行,且吸附过程主要是物理吸附。     

水稻土中重金属元素Cd、Pb的竞争吸附——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量（B）也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数（K）都大于Cd的健合能常数（K）,混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

冻融作用对黑土和棕壤中Pb、Cd吸附/解吸特征的影响

冻融作用对土壤理化性质具有重要影响,进而影响了土壤中重金属迁移转化过程和环境效应。通过实验模拟研究了冻融作用对黑土和棕壤中Pb、Cd吸附/解吸特征的影响。结果表明：黑土对Pb和Cd的吸附能力大于棕壤;冻融作用降低了土壤对Pb和Cd的吸附能力,这与冻融作用改变了土壤的理化性质有关;随着Pb和Cd吸附量的增大,黑土和棕壤中Pb和Cd的解吸量和解吸率也相应增大;冻融作用促进了黑土和棕壤中Pb和Cd的解吸,并且在同一冻融条件下黑土的解吸能力小于棕壤;冻融作用使得黑土和棕壤对Pb和Cd的解吸量大于未冻融土壤,这与冻融作用使解吸溶液pH的下降幅度增大有关。冻融作用降低了土壤对Pb和Cd的固持能力,增加了土壤中Pb和Cd的生态风险。     

Sorption behaviour of pentachlorophenol in sub-Saharan tropical soils: soil types sorption dynamics

In order to predict exposure risks as well as appropriate remediation strategies for pesticides in soils, knowledge of pesticides sorption processes onto various representative soils is vital. Hence, laboratory batch experiments were carried out to study sorption of a pesticide, pentachlorophenol (PCP), on five soils obtained from different sub-Saharan agro-ecological zones (AEZs) in order to understand sorption equilibrium, kinetics, and thermodynamics. Experimental data showed that sorption equilibrium was attained within 24 h. The fitting of kinetic results and equilibrium data to different models suggested partly surface adsorption and partly partitioning of PCP within voids of the various soil components. Sorption was mainly attributed to sharing or exchange of valence electrons between negatively charged PCP molecules and positively charged soil sorption sites. The sorption process was spontaneous and accompanied by decreased entropy, but was pH and temperature dependent, reducing with increase in pH and temperature. The various soils’ PCP sorption capacities were directly proportional to their cation exchange capacities. The low PCP sorption observed in these soils suggested high risk of PCP being present in soil water solution, especially at higher temperatures, which can lead to contamination of the aquifer. This risk may be higher for soils obtained from AEZs with warmer natural temperatures.     

Kinetics of DTPA extraction of Zn,Pb, and Cd from contaminated calcareous soils amended with sewage sludge

The aim of this study was to determine the influence of sewage sludge (SLU) amendment on the desorption characteristics of zinc (Zn), lead (Pb), and cadmium (Cd) in contaminated calcareous soils. Three levels of SLU (0, 1, and 3% w/w) were added to the two calcareous contaminated soils. Samples were incubated for 30 days and equilibrated with 0.005 M DTPA for 0.25 to 240 h. The addition of SLU significantly increased the amount of DTPA-extractable Zn in soils. While the amounts of Cd, Pb, dissolved organic carbon (DOC), and pH showed a significant increase only in 3% w/w of SLU, with the exception of Cd desorption in 1% w/w of SLU, kinetics of Zn, Pb, and Cd extraction increased together with an increase in the level of applied SLU. The best models for describing desorption data were explicitly power function and Elovich. The rate constants of Zn and Pb had significant correlations with DTPA-extractable Zn and Pb, DOC and pH, which affect Zn and Pb desorption. Also, the rate constants of Cd had significant correlations with CEC that can be deemed as equivalent to the fact that Cd desorption is controlled by surface adsorption, particularly in the lower sludge application amount. These results can be used for management of sewage sludge application in contaminated calcareous soils.     

江汉平原旱地和水田土壤镉的吸附与解吸特征及影响因素

为揭示旱地和水田土壤镉的吸附解吸特征,以江汉平原黄豆地、棉花地以及水稻田土壤为研究对象,开展土壤镉的吸附动力学实验、等温吸附?解吸实验以及有机质的影响实验.结果表明:江汉平原土壤对镉的吸附是一个较为复杂的吸附动力学过程且以化学吸附为主,研究区土壤镉的初始吸附速率总体上表现为水田土壤大于旱地土壤;旱地土壤对Cd2+具有较...     

Competitive adsorption of trace elements in calcareous soils as affected by sewage sludge,poultry manure,and municipal waste compost

The competitive adsorption of trace elements is a key issue in assessing the mobility of trace elements in calcareous soils and can be affected by disposal of sewage sludge, municipal waste, and poultry manure. The effect of municipal sewage sludge, poultry manure, and municipal waste compost on the sorption of cadmium (Cd), copper (Cu), zinc (Zn), and nickel (Ni) in surface samples of three calcareous soils was studied. As the applied concentrations increased, Cu and Cd adsorption increased, while Zn and Ni adsorption decreased in all treatments. Based on the distribution coefficient (K _d) values and proportion of increase or decrease in metal adsorption, the selectivity sequence in control and amended soils found was Cu ≫ Cd ≫ Ni > Zn and Cu ≫ Cd ≫ Zn > Ni, respectively. In general, among control and amended soils, control soils showed the highest K _d for Cd, Cu, and Ni, while sludge, poultry manure, and composted waste-amended soils had lowest K _d for Cd, Cu, and Ni, respectively. In the case of Zn, composted waste-amended and control soils had highest and lowest K _d, respectively. The present experimental results indicated that the addition of organic amendments to these calcareous soils reduced the sorption of Cd, Cu, and Ni. Thus, the effects of preferential adsorption and organic matter should be considered in assessing the risk associated with applying sewage sludge, poultry manure, and composted material to calcareous soils.     

蔗渣生物质炭对喀斯特农田石灰性土壤氮转化过程的短期影响

生物质炭对于土壤中不同形态氮库的含量影响已有较多研究,但对西南喀斯特区石灰性土壤氮素形态,尤其是控制氮素形态的转化过程研究较为缺乏。本研究设置土壤中添加1%(C1)和3%(C2)蔗渣生物质炭2个用量水平,并以不施用蔗渣生物质炭作为对照(CK),共3个处理,通过 15 NH 4 NO 3 和NH^15 4 NO 3 成对标记技术,结合MCMC氮素转化模型研究了不同用量的蔗渣生物质炭对石灰性土壤氮转化过程的短期影响,为该地区蔗渣资源化利用和土壤氮保持提供理论支撑。结果表明,与CK相比,添加蔗渣生物质炭能够快速提高土壤pH和有机碳含量。添加生物质炭并没有显著改变土壤氮的矿化、铵态氮(NH^+ 4 )和硝态氮(NO^- 3 )的微生物同化和异养硝化速率,但NH^+ 4 吸附速率随生物质炭用量的增加而提高,以添加量最高的C2处理最大。添加生物质炭同样提高了土壤NH^+ 4 释放速率,但C1和C2处理的土壤NH^+ 4 释放速率并无显著性差异。与CK和C1处理相比,施用高量蔗渣生物质炭通过抑制自养硝化速率而显著降低了硝态氮净产生速率。这些结果表明,施用高量蔗渣生物质炭于石灰性土壤中可快速实现对NH^+ 4 吸附,降低自养硝化速率,减少NO^- 3 产生,从而降低了其损耗和淋失风险。     

水稻土中重金属元素Cd、Pb的竞争吸附 ——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

Sorption capacity on lead,copper and zinc by clay soils from South Wales,United Kingdom

The sorption capacity of five clay soils from South Wales in the United Kingdom was investigated using two main tests; physico-chemical and batch equilibrium (BET). The physico-chemical property results show that soil weathered mudrocks (MR1), glacial till (GT1), and estuarine alluviums (NEA4, PEA3 and CEA3) are capable of being used as landfill liners and are chosen for further sorption tests. The batch tests (i.e. sorption tests) on soil suspension produce adsorption-pH curves, showing increasing adsorption at higher pH levels. The sorption data are also presented using adsorption isotherm curves and are best fitted using the Langmuir adsorption equation that yields the maximum adsorption capacity of the soils. The sorption capacity of soils are ranked as estuarine alluvium soils>glacial till>weathered mudrocks. Estuarine alluvium soils show a good buffering capacity and high sorption capability compared to glacial till and weathered mudrocks. The study also discovers that the maximum sorption capacities are highly influenced by the chemical properties of the soils.