天然勃姆石热相变体(γ-Al_2O_3)的阴离子交换-吸附性能的研究

天然勃姆石热相变体(γ-Al_2O_3)对阴离子交换-吸附序列为:OH~-、S_~(2-)、PO_4~(3-)、F~-、Cr_2O_7~(2-)、NO_3~-、HCO_3~-,Cl~-,SO_4~(2-)。它表明γ-Al_2O_3对这些阴离子交换-吸附的相对能力。γ-Al_2O_3吸附或交换溶液中阴离子时,也对阳离子发生吸附或交换作用。溶液的pH值是影响阴离子交换-吸附作用的重要因素。γ-Al_2O_3对阴离子的交换-吸附及其可解脱性,具有潜在应用价值。     

水溶液中金属阳离子对土层吸附铜的影响规律究研

本文在大量实验资料的基础上,系统地研究了溶液中多种阳离子对土壤吸附铜定量的影响规律,建立了金属离子单独干扰的二元溶液吸附模型和多种离子共同干扰的多元溶液吸附模型,并对各金属离子的影响程度进行了评价。最后指出其环境水文地质意义。     

有机酸对几种土壤吸附铜的影响

在一定离子强度和pH值下,向几种不同的土壤中加入外源有机酸,研究有机酸对土壤吸附Cu2+的影响,结果表明:几种土壤对铜的吸附量随着铜浓度的增加而增加,但当铜浓度达到一定值时,吸附量不再发生变化。几种土壤对铜的最大吸附量的大小顺序为黄棕壤> 砖红壤> 红壤> 赤红壤;有机酸对土壤吸附铜既有促进作用,又有抑制作用,即吸附曲线呈峰型;不同有机酸对土壤吸附铜的影响不同,其中柠檬酸对吸附的抑制和促进作用都很强烈,草酸对吸附的促进作用较弱,抑制作用较强,而乙酸对吸附所起的作用则与草酸正好相反;同种有机酸对不同土壤吸附铜的影响不同。其中三种有机酸对黄棕壤吸附铜的促进作用都很弱,而对砖红壤吸附的促进作用则强。      

用3,5-diBr-PADAT-H_2O_2分光光度测定微量铜

本文试验了3.5-diBr-PADAT有H_2O_2存在下和铜离子显色时,温度酸度及阴离子的影响情况。试验结果认为,显色反应适宜的pH值在3.2—3.8。络合物的组成比为1∶1,克分子吸光系数为8.6×10~4。又对其它条件作了些试验,用2—噻吩甲酰基代三氟丙酮(HTTA)—苯萃取铜,能使干扰元素分离,用于微量矿物和土壤中微量铜的测定,与其它方法比较结果满意。     

土壤对可溶性油的吸附作用及其影响因素分析

在沈(阳) 抚(顺) 灌区土-水-作物系统石油污染调查的基础上, 根据土壤非饱和带的结构和组成, 选择代表性的土壤剖面分别采集表土和底土, 分析土样的主要物理和化学性质, 系统测定不同土样对可溶性油吸附的动力学曲线和吸附等温线, 并分析了有机质、粘粒含量和含盐量对吸附作用的影响.结果表明, 土壤对可溶性油的吸附平衡时间为20~24h, 而且不同土样的吸附等温线均为直线型理想吸附.另外, 通过试验发现, 当水相中可溶性油低于一定浓度时, 不但不产生吸附, 反而使土壤中的残留油分释放出来.      

内分泌干扰物的环境危害:雌激素及其硫酸盐在土壤中的吸附规律

雌激素(E1)及其硫酸盐化合物(E1-3S)是能改变生物机体内分泌功能并对机体引起有害效应的内分泌干扰物,主要表现为危害人类的生殖机能、造成发育异常及引发某些癌症等。其大量存在于直接暴露的放牧草场中,主要是动物粪便中。由于雌激素性质不稳定,当被土壤吸附后易被代谢为其他物质,造成了对土壤吸附作用过高的估计,使得难以准确评估其对人体的危害程度。为此,笔者以质量浓度为555mg/L的CaCl2溶液(混合态)以及动物尿液(自由态)2种不同类型溶液作为雌激素载体,研究了尼日利亚纳萨拉瓦州3个不同地区农业土壤介质对不同形态雌激素的吸附规律。结果表明:2类物质的吸附均符合Freundlich非线性等温线过程,土壤对E1-3S的分配系数(2.4～6.4L/kg)比E1(34.2～46.8L/kg)中小一个数量级;3种土壤中,由于有机碳质量分数(分别为Lafia:8.2%;Doma:4%;Azara:5%)、矿物成分以及pH值的不同,致使它们对物质的吸附系数差别较大;雌激素在相同土壤、不同溶液中的吸附系数差别也较大,其在Azara土壤中CaCl2溶液及动物尿液中的分配系数分别为71.7L/kg和39.8L/kg。传统方法中以CaCl2溶液作为载体获得的吸附含量用于评价雌激素污染风险是不合理的,需采用实际载体溶液进行的实验结果才有应用价值。     

广东揭阳市土壤铜的分布特征及其影响因素

以广东省揭阳市土壤为研究对象,测定了1 330个表层土壤样(0~20 cm)和331个深层土壤样(150~200 cm)的Cu含量,据此研究土壤Cu的分布特征和影响因素。利用富集因子、GIS空间分析和方差分析等方法,综合分析了研究区土壤铜富集特征、空间分布特征及其影响因素,遵循国家标准评价了土壤铜污染风险。结果表明:表层土壤铜含量均值为9.49 mg/kg,远低于《土壤环境质量农用地土壤污染风险管控标准》(GB15618—2018)中Cu风险筛选值(50 mg/kg);表层土壤铜的富集程度处于未富集和轻微富集水平,不存在明显的铜富集情况;表层土壤铜高值区主要分布在榕城区中部、揭西县东南部以及惠来县西部和北部;成土母质和土地利用方式是研究区表层土壤铜含量的主要影响因素,土壤类型对其也有一定影响,不同成土母质中,第四纪沉积物土壤铜含量最高;不同土地利用方式下,建筑用地土壤铜含量显著高于其他土地利用方式;不同土壤类型中,水稻土土壤铜含量最高。     

土壤中铅铜锌镉的吸附特性

以徐州王庄矿（WZK）、奎河（KH）、背景-1（BG-1）和背景-2（BG-2）等4个土壤样品为供试对象，加入不同浓度梯度的铅、铜、锌、镉离子，通过静态实验研究了铅、铜、锌、镉的吸附特性。结果表明，土壤对4个重金属的吸附量与加入到土壤中的重金属离子浓度呈正相关性，它们之间大部分满足线性相关关系。在4个土壤样品中加入铅、铜、锌、镉离子的初始浓度比为10：10：10：1时，平衡浓度为Czn〉Ccu〉CPh〉Ccd，吸附量为Scd〉SPh〉Scu〉Szn，4个土壤样品对铅、铜、锌、镉离子的吸附能力依次为WZK〉KH〉BG-2〉BG-1。在所选实验条件下，土壤对铅、铜、锌、镉的吸附能力受土壤中铅、铜、锌、镉的含量、土壤有机质含量、阳离子交换量、土壤饱和含水量和土壤的pH值影响较大。     

封闭消解-阳离子交换分离-电感耦合等离子体质谱法测定铜铅锌矿石中的铼

阴离子交换树脂已被应用于酸法消解-电感耦合等离子体质谱(ICP-MS)测定铜铅锌矿石等地质样品中铼的分离富集,样品溶液中的ReO_4~-用树脂交换吸附后再用洗脱剂将ReO_4~-选择性洗脱,该方法流程长,影响其稳定性和准确性。本文以基体元素为吸附交换目标,用8 g的732强酸型阳离子交换树脂在2%硝酸介质条件下静态吸附1.5 h,可有效地消除基体元素的影响。用空矿(石英)稀释低含量铼的样品做空白试验,获得方法检出限为0.004μg/g,精密度(RSD)小于6%,加标回收率为96%~104%。本方法应用的732强酸型阳离子交换树脂在适宜酸度条件下,对矿石中除钨、钼以外的金属元素吸附率高达95%以上,降低了样品溶液离子强度和干扰元素浓度,实现了ICP-MS的直接测定,操作方法比阴离子交换吸附法简便。     

两类矿物前体对As(Ⅲ)阴离子吸附机制的实验研究

通过两类矿物前体对A s(Ⅲ)阴离子的吸附反应的实验研究发现:这两类矿物前体在吸附反应过程中pH值均发生了明显变化,它们对A s(Ⅲ)的吸附均属于化学吸附。M g-A l-LDO从环境中获取阴离子以恢复重建LDH的结晶结构,并释放OH-使溶液pH升高;F e(OH)3凝胶改变了A s(Ⅲ)的络合配位数,同时产生H+离子,使溶液pH降低;M g-F e-LDO兼有二者的特点。在室温条件下,M g-A l-LDO和M g-F e-LDO对A s(Ⅲ)的吸附容量分别为83.2×1-0 3和87.45×1-0 3,而F e(OH)3凝胶为204.9×1-0 3。矿物前体对溶液中阴离子污染物的吸附能力大大高于对应的矿物,主要原因是它们的吸附机理不同,前者为化学吸附,而后者以物理吸附为主。     

九连墩楚墓青铜器锈蚀产物的拉曼光谱分析

利用拉曼光谱对几件九连墩楚墓出土青铜器的腐蚀产物进行了测试。结果表明,九连墩楚墓出土的青铜器上主要的锈蚀产物为孔雀石[CuCO_3·Cu(OH)_2],存在部分蓝铜矿[2CuCO_3·Cu(OH)_2]和少许副氯铜矿[Cu_2(OH)_3Cl];此批青铜器锈蚀情况比较复杂,锈蚀种类比较丰富。在此基础上,探讨了科学保护此批青铜器的方法。     

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric (Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic (Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine (Skeletonema costatum) and freshwater (Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ^65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria (Rhodobacter sp.), cyanobacteria (Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria (P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ⁶⁵Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ⁶⁵Cu (solid-solution) = −1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ⁶⁵Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively.Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu²⁺ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution.Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.     

Copper contamination of soils and vegetables in the vicinity of Jiuhuashan copper mine,China

Copper contamination in soils and vegetables in the vicinity of an abandoned copper mine in China was investigated. The Cu concentrations of 93 soil samples ranged from 30.4 to 3,191 mg kg⁻¹ soil for a mean of 816.8 mg kg⁻¹ soil. Among 15 samples from a 0 to 20-cm soil layer used for the toxicity characteristic leaching procedure (TCLP) test, the highest value of Cu-TCLP was 133.8 mg kg⁻¹ soil and the TCLP values were positively correlated with the total Cu content of the soils. The sequential extraction of soils in the 0–20-, 20–40-, and 40–60-cm soil layers showed that Cu existed mainly in the Fe–Mn oxide fraction, sulfide/organic fraction, and residual fraction. The copper contamination of 21 species of vegetables from in situ sampling was also examined. Cu concentrations in the edible portions of Brassica chinensis and Solanum melongena were higher than the FAO/WHO standard (40 mg kg⁻¹ DW). The health risk of copper for local inhabitants from consuming these vegetables was assessed on the basis of the target hazard quotient. Enriched concentrations of copper were also found in situ in eight cultivars of B. chinensis planted in the fields, with two levels of Cu concentration. The results showed that there is severe copper contamination in this mine area, and the pollutant in soils show a high risk of leaching into the groundwater and diffusing through the food chain.     

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe₂O₃) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO₄H_n)ⁿ⁻⁶ and binuclear (Cu₂O₆H_n)ⁿ⁻⁸ complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH)₆ polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe₂(OH)₂(H₂O)₈Cu(OH)₄and Fe₃(OH)₄(H₂O)₁₀Cu₂(OH)₆ clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO₄H_n)ⁿ⁻⁶ and Fe(O,OH)₆ polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH)₂. Having identified the bidentate (FeOH)₂Cu(OH)₂⁰ and tridentate (Fe₃O(OH)₂)Cu₂(OH)₃⁰ surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions

     

新疆阿舍勒铜矿区及外围表生地球化学分散特征

研究了阿舍勒铜矿区及外围区域岩石-土壤-水系沉积物风化作用体系的地球化学特征,发现:①Ca是研究区最活跃的元素,在土壤40-200cm深度上形成碱性碳酸盐地球化学障──钙积层.②不同地质背景对元素表生活动有制约作用,背景区和异常区元素的表现有明显差异.③从风化岩石→土壤→水系沉积物,Cu、Zn的存在形式发生明显变化,从以硫化物相为主变成以有机相为主.④大多数铜矿化指示元素都富集在<0.5mm的水系沉积物中,并可沿水系迁移到矿区下游7km以外.     

与花岗质岩浆系统有关的石英脉型钨矿和斑岩型铜矿成矿流体特征比较

文中对比了与S型花岗岩有关的石英脉型钨矿和与I型（及少数A型）花岗岩类有关的斑岩型铜矿床的成矿流体特征。它们的共同点在于成矿流体都由岩浆流体演化而来,在后期逐渐有大气降水的加入。差异性在于：（1）石英脉型钨矿成矿流体主要属于中—中高温、中—中低盐度的NaCl-H2O±CO2体系,而斑岩型铜矿属于中高-高温、高盐度的Na...     

磷灰石及其变体交换吸附阴离子的模式

研究磷灰石及其变体交换吸附阴离子的模式,可丰富矿物的阴离子交换吸附理论。本文采用静态振荡法及动态往交换法详细研究了磷灰石及其变体与F-、CO32-、OH-的离子交换性能。研究结果表明,磷灰石及其变体与含有F-、CO32-、OH-的溶液作用时,溶液中的阴离子可与它们结构中的阴离子发生交换作用;预先用适当浓度的H2SO4溶液浸泡磷灰石及其变体,伴随着固相中少量PO43-及Ca2 的化学溶蚀作用,SO42-可进入磷灰石及其变体的结构中。磷灰石及其变体中非PO43-阴离子（例如F-、CO32-、OH-、SO42－）的存在,是它们具有阴离子交换性能的根源所在,且随着这些阴离子含量的增加,其离子交换容量也相应增加。     

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO₄H_n)ⁿ⁻⁶ and binuclear (Cu₂O₆H_n)ⁿ⁻⁸ inner-sphere complexes on variable-charge ≡AlOH sites and as Cu²⁺ on ion exchangeable ≡X--H⁺ sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH)₆ polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH)₂Cu(OH)₂⁰, tridentate (≡Al₃O(OH)₂)Cu₂(OH)₃⁰ and ≡X--Cu²⁺ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

     

黏土掺入生物炭后的持水特性及其影响机制

生物炭具有疏松多孔、高比表面积和强吸附等特性,在土体改良以及修复受污染土体方面展现出应用潜力。添加生物炭可改善土体结构,进而增强土体持水特性等,其中,生物炭掺量和粒径对改良效果有较大的影响。为了研究生物炭掺量和粒径对生物炭?黏土混合土持水特性的影响,通过蒸汽平衡法控制土样的吸力,确定吸力平衡后土样的含水率和体积等,得到吸湿过程中不同生物炭掺量（0%、5%、10%和15%）、不同粒径范围（＞74、40～74、20～40 μm和＜74 μm）生物炭?黏土混合土在高吸力（3.29～286.7 MPa）范围的土?水特征曲线,并结合扫描电镜（SEM）和压汞（MIP）试验结果分析其微观孔隙结构。试验结果表明：（1）当掺入生物炭的粒径较小时,随着生物炭掺量的增加,土样的持水特性有较明显的提高,随着掺入生物炭粒径的增大,生物炭掺量对土样的持水特性影响不大。（2）当生物炭的掺量较少时,不同粒径生物炭?黏土混合土的土?水特征曲线基本相同,随着生物炭掺量提高,小粒径生物炭对混合土持水特性的影响逐渐显现。（3）由生物炭?黏土混合土微观孔隙结构的演变规律进一步阐释生物炭掺量、粒径对生物炭?黏土混合土持水特性的影响机制。