选矿废水中醚胺的某些环境化学特性研究

通过降解,吸附及土柱淋滤试验等手段,对选矿废水中醚胺的降解规律,降解能力,吸附能力,分配特征以及在土壤中的垂直迁移规律等环境化学特性进行了试验研究。结果表明：（１）醚胺在水体中的降解规律服从一级生物化学反应方程ｃ－ｃｏｅｓｐ（－Ｋｔ）,温度和ｐＨ值是影响降解系数Ｋ的两个主要因素;（２）土壤对醚胺的吸率在９２％以上,吸附方程为ｑ＝５．３３５＋６３．３ｇｃ;（３）醚胺在土壤中的垂直迁移规律为ｃ＝ａｅｘ     

粉煤灰淋溶液中的有害物质对地下水污染的试验研究

粉煤灰中有害物质对土壤的影响试验表明，０．３ｍ的土层对粉煤灰淋溶水中ｐＨ值、Ｆ＾－、全盐量和总碱度有很强的吸附能力，如ｐＨ值的吸附中和量为３．７￣４０，Ｆ＾－吸附率达８７．４％，总盐量的吸附率达７０．９７％，碱度吸附率达９４．３％￣９６．４％，Ｃｒ＾６＋吸附能力较弱。由于贮灰场附近土层远大于０．３ｍ，因此粉煤灰淋溶水不会对地下水产生污染。     

地面水体中无机硫阴离子电化学形态分析方法的研究

建立了地面水体中无机硫阴离子的电化学形态分析方法，利用示波极谱技术在碱性氯化钠（ｐＨ＝１１．３）溶液中测定了硫化物；在ｐＨ＝４．７的醋酸－醋酸钠缓冲溶液中分别测定了硫代硫酸盐和亚硫酸盐；利用铅（Ⅱ）－四（４－三甲铵苯基）卟啉络合吸附波间接吸附伏安法测定了硫酸盐，该方法的优点是操作简便快速，重现性较好，适于地面水体中痕量无机硫阴离子的形态分析。     

pH对镉在土水系统中的迁移和形态的影响

研究了４种红壤和水体系中ｐＨ对镉的迁移影响．结果表明：镉在土水体系中的迁移是一快反应过程，４种土壤对镉的吸附量随土水系统中ｐＨ的变化，可分为３个区域，即低吸附量区、中等吸附区，以及强吸附和沉淀区，在中等吸附区镉吸附量与ｐＨ呈正相关；ｐＨ６以下被吸附的镉中生物有效态镉量随ｐＨ的升高而增加，ｐＨ６以上被吸附的镉中生物有效态镉量随ｐＨ升高而降低．石灰导致镉毒性降低的主要原因是ｐＨ＞７５时镉主要以粘土矿物和氧化物结合态及残留态形式存在．     

Cu~（2＋）对3种农药在Ca－蒙脱石和δ－Al_2O_3上吸附的影响

比较研究了３种农药在两种吸附体上的吸附以及Ｃｕ２＋其吸附的影响．杀虫脒在Ｃａ－蒙脱石上的吸附率很高且随ｐＨ值的升高而降低；在δ－Ａｌ２Ｏ３上的吸附率较低且随ｐＨ值的升高而升高．Ｃｕ２＋对其吸附无影响，毒莠定在Ｃａ－蒙脱石上无吸附，但可被δ－Ａｌ２Ｏ３吸附，吸附率随ｐＨ值的升高逐渐降低，不受Ｃｕ２＋的影响．当ｐＨ值小于５时，草甘磷在Ｃａ－蒙脱石上的吸附随ｐＨ值的升高而略有上升；当ｐＨ值大于５时，则随ｐＨ值的升高而下降，Ｃｕ２＋降低了草甘磷的吸附．当草甘磷与Ｃｕ２＋摩尔比为０．５和１．０时，草甘磷吸附率的降低程度高于摩尔比为２．０时的降低程度．     

Cr(VI)离子在TiO_2表面的吸附与光催化还原消除

随着体系ｐＨ值增大，Ｃｒ（ＶＩ）离子在ＴｉＯ２表面的吸附下降．当Ｃｒ（ＶＩ）离子初始浓度为３００μｍｏｌ／Ｌ时，其在ＴｉＯ２表面具有最大值吸附．Ｈ２ＰＯ４－阴离子及乙酸的存在对Ｃｒ（ＶＩ）离子的吸附有阻抑作用，甲酸存在会提高Ｃｒ（ＶＩ）离子的吸附．Ｃｒ（ＶＩ）离子在ＴｉＯ２半导体催化剂表面的光催化还原受体系的酸度影响较大．Ｈ２ＰＯ４－阴离子或Ｍｎ２＋离子存在会降低Ｃｒ（ＶＩ）离子的光催化还原效率．在太阳光照下，Ｃｒ（ＶＩ）离子在ＴｉＯ２上的光催化还原也可实现．通过调节反应结束后水溶液的酸碱度，Ｃｒ（ＶＩ）离子得以消除．反应后催化剂经酸处理，其活性恢复并可重复使用．     

铜─丙酮─三乙醇胺络合物吸附波对环境水样的测定研究

铜─丙酮─三乙醇胺络合物吸附波对环境水样的测定研究张林（四川会东铅锌矿中心试验室）在ｐＨ１０的ＮＨ４Ａｃ－ＮａＯＨ介质溶液中，铜离子与丙酮络合物在单扫描示波极谱仪上，于Ｅｐ＝－０．４１Ⅴ（对饱和甘汞电极）处产一灵敏的吸附波。其浓度在８．５×１０－９～...     

La3+、Yb3+在土壤和矿物中的吸附特征及其环境意义

实验研究了轻稀土镧离子Ｌａ~３＋和重稀土镱离子Ｙｂ~３＋在赣南稀上矿区的土壤及风化次生矿物中的吸附特性，结果表明，土壤和矿物对稀土元素的吸附过程符合Ｌａｎｇｍｕｉｒ和Ｆｒｅｎｄｌｉｃｈ等温吸附方程，ｐＨ值是影响吸附作用的主要因素。随着ｐＨ值的变化，Ｌａ~３＋和Ｙｂ~３＋在土壤和次生矿物上的吸附能力也发生变化。Ｌａ~３＋与Ｙｂ~３＋在土壤和次生矿物中的吸附等势点ｐＨ值分别为６．２６和５．２８．在等势点ｐＨ值以下，Ｌａ~３＋的吸附势大于Ｙｂ~３＋；在等势点ｐＨ值以上，Ｙｂ~３＋的吸附势相对较高。土壤和次生矿物对轻、重稀土元素的吸附特征以及对稀士元素的分布、分异、成矿和生态效应具有重要意义。     

甲磺隆除草剂的测定方法及其吸附行为研究

采用批量平衡法系统研究了甲磺隆除草剂在几种土壤（熟化红壤、砖红壤性红壤、红筋泥、砖红壤）和矿物（高岭石、针铁矿、和Ca²⁺、Al³⁺、Cu²⁺单离子饱和蒙脱石）上的吸附行为.建立了硼酸-硼砂缓冲液体系的毛细管电泳测定甲磺隆的分析方法.甲磺隆在本实验条件下能够与土壤中的杂质达到基线分离,迁移时间为4.6 min.对比实验表明,毛细管电泳法测定甲磺隆与高效液相色谱法具有一致性.然而,毛细管电泳法能显著节省测试时间和成本,在本类吸附实验研究中具有很好的应用价值.吸附实验数据分析表明甲磺隆的吸附行为都可以用Freundlich模型描述,矿物和土壤的K_f值分别在0.82～199.69和1.97～10.48范围.在几种影响甲磺隆吸附的因素中,pH的影响作用最为显著,说明静电作用可能是甲磺隆在土壤及矿物上吸附的主要机理.     

农业废弃物对土壤中N_2O、CO_2释放和土壤氮素转化及pH的影响

用一种丹麦农业土壤作为供试材料，在室内培养条件下探讨了施用４种常见农业废弃物（猪粪泥浆、牛粪泥浆、黑麦秸秆、小麦秸秆）对土壤中Ｎ_２Ｏ、ＣＯ_２释放和土壤氮素转化及ｐＨ的影响。试验结果表明，施用４种农业废物均会明显增加Ｎ_２Ｏ、ＣＯ_２释放量。培养２周后，土壤中Ｎ_２Ｏ的释放量分别为：猪粪＞牛粪＞黑麦秸秆＞小麦秸秆；ＣＯ_２的释放量为：黑麦秸秆＞小麦秸秆＞牛粪＞猪粪。施用４种农业废物均会显著促进ＮＯ_３－Ｎ的转化和ＮＨ_４－Ｎ、ＮＯ_２－Ｎ的累积。施用４种废物均会改变土壤ｐＨ，其中施用秸秆的２个处理中ｐＨ显著降低，但施用牲畜粪便的２个处理中ｐＨ则稍微升高。     

Adsorption of chloroacetanilide herbicides on soil and its components Ⅲ. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca2 + -, Mg2 + -. Al3 + -and Fe3 + -saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor ＞ acetolachlor ＞ alachlor ＞ propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg2+ ＜ Ca2+ ＜ Al3+ ≤ Fe3+ which coincided with the iucreasing aciditv of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.     

新农药HW-02在土壤中的吸附

采用振荡平衡法研究了新型除草剂HW-02在5种不同土壤中的吸附特性. 结果表明:土壤对HW-02的吸附性强;HW-02在黑钙土、白浆土、草甸土、砂性土和黏壤土等5种土壤中的吸附可用Freundlich等温式较好地描述,其吸附系数(K_F)分别为332.65,103.32,672.97,577.96和289.60,吸附自由能变绝对值(ΔG)分别为16.55,22.73,18.32,18.48和22.86 kJ/mol,说明HW-02在土壤中的吸附以物理吸附为主;HW-02在5种土壤中的有机质吸附常数(K_OM)为796.57～10 197.18,说明其在土壤中迁移性很弱. HW-02在土壤中的吸附系数与土壤w(有机质),pH和w(黏粒)相关性较好,而与阳离子交换量(CEC)的相关性差,说明土壤w(有机质),w(黏粒)和pH是影响HW-02在土壤中吸附的主要因素.      

Adsorption of chloroacetanilide herbicides on soil and its components Ⅲ. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca²⁺-, Mg²⁺ -. Al³⁺ -and Fe³⁺ -saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor ＞ acetolachlor ＞ alachlor ＞ propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg²⁺ ＜ Ca²⁺ ＜ Al³⁺ ≤ Fe³⁺ which coincided with the iucreasing aciditv of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.     

原油在土壤中的吸附和解吸研究

用振荡平衡法研究了原油在土壤中的吸附和解吸行为，测得了吸附常数，给出了吸附等温线。结果表明，Linear吸附关系可较好地描述原油在土壤中的吸附状况；土壤有机质含量影响原油的吸附量；其解吸行为则明显受到溶液pH的影响，表面活性剂的加入有助于原油解吸。     

挥发性氯代烃在湿润土壤中的平衡吸附研究

吸附是挥发性氯代烃(volatile chlorinated hydrocarbons,VCHs)赋存于土壤的主要机制之一.开展动态吸附实验,研究了4种常见VCHs污染物在我国8种典型土壤中的吸附平衡关系.结果表明,土壤在干燥条件下对VCHs气体的吸附能力要远大于湿润条件,且随含水率的升高吸附能力急剧下降,在含水率达到10%以后土壤吸附量趋于稳定.湿润土壤对三氯乙烯(TCE)、四氯乙烯(PCE)、1,1,1-三氯乙烷(MC)气体的吸附等温线符合Henry型吸附等温式,而1,1,2-三氯乙烷(1,1,2-TCA)符合Freundlich模型.VCHs在湿润土壤中的吸附量总体上与土壤有机碳(soil organic carbon,SOC)含量呈正相关,且受SOC类型和化合物极性影响较大.弱极性的TCE、PCE在土壤中的吸附能力与SOC含量呈严格正相关,而极性的MC、1,1,2-TCA在黑土等高碳土壤中不仅与SOC含量有关,还受到SOC物质组成的影响.建立了TCE和PCE在湿润土壤中的平衡吸附量预测模型,预测值与实测值相关性良好(n=80,R2=0.98).     

除草剂草甘膦在土壤中的吸附行为

研究了除草剂草甘膦在3种土壤中的吸附行为, 观察了pH和离子强度等因素对吸附的影响. 结果表明:草甘膦在3种土壤中的吸附过程均符合一级动力学规律, 吸附等温线均为直线,吸附常数K_d 2.2207～3.5280mL/g; 随着离子强度的降低, 草甘膦在3种土壤中的吸附量明显增大; 随着pH(9～3)逐渐减小, 草甘膦在呼和浩特特市土壤和东胜土壤中的吸附量增大, 在杭锦2号土中的吸附量先增大, 在pH=7时达到最大值, pH=5时开始下降, 下降到4时的吸附量与pH=9时的相等.     

灭草松在土壤中吸附的支配因素

通过振荡平衡法测定了灭草松在6种土壤中的吸附等温线,计算了灭草松在吸附过程中平均偏摩尔自由能的变化值.结果表明灭草松在其中5种土壤上的吸附等温线为直线,分配常数Kd 0.14～0.31mL·g^-;土壤吸附灭草松的强弱次序为:德清水稻土＞安吉水稻土(pH4.79)＞余杭水稻土＞临安红壤＞安吉水稻土(pH7.36)＞德清黄壤.土壤性质与分配常数的相关分析,发现支配灭草松在土壤上吸附的主要因素是pH值和土壤有机质含量.灭草松在土壤上的吸附主要是中性灭草松及其阴离子在土壤有机质中的分配,与有机质性质关系不大.     

挥发性氯代烃在干燥土壤中的平衡吸附研究

吸附是挥发性氯代烃（volatile chlorinated hydrocarbons,VCHs）污染土壤的主要机制之一.采集长三角地区3类典型水稻土,用静态平衡吸附实验进行干燥土壤对6种VCHs的平衡吸附研究.结果表明,干燥土壤的平衡吸附等温线难以用Langmuir方程和BET方程描述,但用Dubinin-Astak...     

Adsorption kinetics of the herbicide safeners, benoxacor and furilazole, to activated carbon and agricultural soils

Chloroacetamide herbicides, namely acetochlor and metolachlor, are common herbicides used on corn and soybean fields. Dichloroacetamide safeners, namely benoxacor and furilazole, are commonly used in formulations containing chloroacetamide herbicides. Extensive reports on adsorption of chloroacetamide herbicides are available, yet little information exists regarding adsorption potential of co-applied safeners. Herein, the adsorption and desorption characteristics of selected herbicide safeners to granular activated carbon (GAC) and in agricultural soils are reported. Further, soil column studies were performed to understand the leaching behaviour of the herbicide Dual II Magnum. Equilibrium sorption experiments of safeners to three agricultural soils and one GAC showed that adsorption was best fitted by the Freundlich isotherm. The Freundlich adsorption constant, K_f, for benoxacor and furilazole sorption onto three agricultural soils ranged from 0.1 to 0.27 and 0.1 to 0.13 (mg/g) × (mg/L)?(1/n), respectively. The K_f for benoxacor and furilazole to GAC was 6.4 and 3.4 (mg/g) × (mg/L)?(1/n), respectively, suggesting more favorable sorption of benoxacor to GAC than furilazole to GAC. The sorption to soils was reversible as almost 40%–90% of both safeners was desorbed from three soils. These results were validated in four replicated soil column studies, where S-metolachlor was shown to leach similarly to the safener benoxacor, originating from the herbicide formulation. The leaching of S-metolachlor and benoxacor was influenced by soil texture. Cumulatively, these results show that safeners will move through the environment to surface waters similarly to the active ingredients in herbicides, but may be removed during drinking water treatment via GAC.     

湿地土壤对硝基苯的吸附-解吸作用

应用平衡法研究硝基苯在湿地土壤中的吸附-解吸特性.结果表明,湿地土壤对硝基苯具有较强的吸附能力,其吸附行为可以用Linear和Freundlich型吸附等温式描述,不同类型湿地土壤对硝基苯的吸附和解吸能力有所不同.将吸附常数Kf与湿地土壤的理化性质进行相关性分析表明,土壤有机质含量与硝基苯吸附系数显著相关(r=0.888,P<0.01,n=7),其中泥炭沼泽土表层有机质含量最高,其吸附系数也最大(86.44 mg·kg-1).硝基苯在湿地土壤中的吸附自由能变化量为10.68～13.45 kJ·mol-1,表明其吸附以物理吸附为主.不同类型湿地土壤对硝基苯的解吸能力也有一定的差别,其中草甸白浆土的解吸率最大(41.87%),泥炭沼泽土表层解吸率最小(11.79%).