Potential bioavailability of mercury in humus-coated clay minerals

It is well-known that both clay and organic matter in soils play a key role in mercury biogeochemistry, while their combined effect is less studied. In this study, kaolinite, vermiculite, and montmorillonite were coated or not with humus, and spiked with inorganic mercury (IHg) or methylmercury (MeHg). The potential bioavailability of mercury to plants or deposit-feeders was assessed by CaCl₂ or bovine serum albumin (BSA) extraction. For uncoated clay, IHg or MeHg extraction was generally lower in montmorillonite, due to its greater number of functional groups. Humus coating increased partitioning of IHg (0.5%–13.7%) and MeHg (0.8%–52.9%) in clay, because clay-sorbed humus provided more strong binding sites for mercury. Furthermore, humus coating led to a decrease in IHg (3.0%–59.8% for CaCl₂ and 2.1%–5.0% for BSA) and MeHg (8.9%–74.6% for CaCl₂ and 0.5%–8.2% for BSA) extraction, due to strong binding between mercury and clay-sorbed humus. Among various humus-coated clay particles, mercury extraction by CaCl₂ (mainly through cation exchange) was lowest in humus-coated vermiculite, explained by the strong binding between humus and vermiculite. The inhibitory effect of humus on mercury bioavailability was also evidenced by the negative relationship between mercury extraction by CaCl₂ and mercury in the organo-complexed fraction. In contrast, extraction of mercury by BSA (principally through complexation) was lowest in humus-coated montmorillonite. This was because BSA itself could be extensively sorbed onto montmorillonite. Results suggested that humus-coated clay could substantially decrease the potential bioavailability of mercury in soils, which should be considered when assessing risk in mercury-contaminated soils.     

低浓度范围内聚丙烯酰胺在黏土矿物上的吸附特征

用酰胺基团溴化后碘化镉-淀粉显色分光光度法测定了在0～50mg/L低浓度范围内聚丙烯酰胺(PAM)在高岭土和蒙脱土上的吸附等温线,并考察了电解质浓度和类型对吸附的影响.结果表明,PAM在黏土矿物上有很强的吸附亲合力,吸附等温线为Langmuir型.电解质能大大增强PAM在黏土矿物上的吸附,其中二价离子比一价阳离子更有效.电解质浓度较低时,PAM分子主要以链序态吸附,电解质浓度较高时以链环态、链端态吸附的数量逐渐增多.PAM的吸附只限制在层状黏土矿物的外表面上.在Na⁺介质中,PAM在两种黏土矿物上的吸附量差别不大;而在Ca²⁺介质中,蒙脱土悬浮颗粒产生分裂,为PAM的吸附提供新的外表面积,PAM的吸附量大大高于在高岭土上的吸附量,前者约是后者的2～3倍.     

Amplification of plasmid DNA bound on soil colloidal particles and clay minerals by the polymerase chain reaction

Polymerase chain reaction(PCR)was used to amplify a 600-base pair(bp)sequence of plasmid pGEX-2T DNA bound on soil colloidal particles from Brown soil(Alfisol)and Red soil(Ultisol),and three different minerals(goethite,kaolinite,montmorillonite). DNA bound on soil colloids,kaolinite,and montmorillonite was not amplified when the complexes were used directly but amplification occurred when the soil colloid or kaolinite-DNA complex was diluted,10- and 20-fold.The montmorillonite-DNA complex required at least 100-fold dilution before amplification could be detected.DNA bound on goethile was amplified irrespective of whether the complex was used directly,or diluted 10- and 20-fold.The amplification of mineral-bound plasmid DNA by PCR is,therefore,markedly influenced by the type and concentration of minerals used.This information is of fundamental importance to soil molecular microbial ecology with particular reference to monitoring the fate of genetically engineered microorganisms and their recombinant DNA in soil environments.     

苄嘧磺隆对Cu2+在粘土矿物上吸附-脱附的影响

选择两种粘土矿物Ca－蒙脱石和高岭石作为吸附体，研究Cu^2 的吸附－脱附行为，以及苄嘧磺隆对Cu^2 吸附－脱附的影响，结果表明，Cu62 在比表面积、CEC大的Ca－蒙脱石上吸附量较高；而在比表面积、CEC小的高岭石上吸附量较低，蒙脱石对Cu^2 的吸附主要是静电吸附，吸附的Cu^2 较易脱附；高岭石主要通过专性吸附机制而吸附Cu^2 ，吸附的Cu^2 较难脱附，苄嘧磺隆对Cu^2 在粘土矿物上吸附－脱附的影响显著，苄嘧磺隆增加了Cu^2 在Ca-蒙脱石上的吸附，苄嘧磺隆作为桥而连接Ca-蒙脱石和Cu^2 ，苄嘧磺隆的浓度越高，Cu^2 的吸附量越大，解吸量赵低，苄嘧磺隆对Cu^2 在高岭石上吸附的影响，则是低pH值增加Cu^2 吸附，高pH值时降低Cu^2 吸附，解吸率的变化相反。     

Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectroscopy

This research investigates the adsorption mechanisms of fluoride (F) on four clay minerals (kaolinite, montmorillonite, chlorite, and illite) under different F⁻ concentrations and reaction times by probing their fluoride superficial layer binding energies and element compositions using X-ray photoelectron spectroscopy (XPS). At high F⁻ concentrations (C ₀ = 5–1000 mg·L⁻¹), the amount of F⁻ adsorbed (Q _F), amount of hydroxide released by clay minerals, solution F⁻ concentration, and the pH increase with increasing C ₀. The increases are remarkable at C ₀>50 mg·L⁻¹. The QF increases significantly by continuously modifying the pH level. At C ₀<5–100 mg·L⁻¹, clay minerals adsorb H⁺ to protonate aluminum-bound surface-active hydroxyl sites in the superficial layers and induce F⁻ binding. As the C ₀ increases, F⁻, along with other cations, is adsorbed to form a quasi-cryolite structure. At C ₀>100 mg·L⁻¹, new minerals precipitate and the product depends on the critical Al³⁺ concentration. At [Al³⁺]>10^−11.94 mol·L⁻¹, cryolite forms, while at [Al³⁺]<10^−11.94 mol·L⁻¹, AlF₃ is formed. At low C ₀ (0.3–1.5 mg·L⁻¹), proton transfer occurs, and the F⁻ adsorption capabilities of the clay minerals increase with time.     

热处理对天然富钙粘土矿物除磷能力的影响

以天然富钙粘土矿物（海泡石和凹凸棒）为研究对象,采用热处理的方法对其进行活化,并利用X-射线衍射（XRD）分析了矿物结构的变化,同时研究了热处理粘土矿物的除磷能力和机制.结果表明,热处理能够显著改变海泡石和凹凸棒的矿物组成,大幅提高其对磷的吸附能力,并分别在900 ℃和800 ℃的活化条件下对磷的吸附能力达到最佳,吸附量分别可达37.7 mg·g^-1和30.9 mg·g^-1.Freundlich方程和准二级方程能较好地拟合热处理粘土对磷的吸附热力学和动力学过程.同时还发现,pH值（3~10）对热处理粘土除磷能力基本无影响.热处理富钙粘土的除磷机制主要是与溶液中的磷生成钙磷沉淀.     

黏土矿物原位修复镉污染稻田及其对土壤氮磷和酶活性的影响

分别以黏土矿物坡缕石和海泡石作为钝化材料,对重金属镉污染的酸性水稻土壤进行原位钝化修复田间示范试验,考察了两种黏土矿物在不同添加剂量下对稻谷产量、糙米镉含量及土壤中有效态镉含量等变化的影响,用以表征修复效果.同时,深入研究了两种黏土矿物对土壤pH、土壤水解氮、有效磷含量及相关酶活性的影响以表征其对土壤环境质量的影响,并对各项理化指标之间的相关性进行分析.结果表明,田间示范条件下两种黏土均提高了土壤pH,降低了土壤中镉的生物有效性,明显降低了糙米中镉含量.其中,经2.00 kg·m-2坡缕石和2.25 kg·m-2海泡石处理后,糙米镉含量最大降幅分别为54.6%和73.5%,分别降低至0.32和0.18 mg·kg-1.土壤过氧化氢酶、脲酶、酸性磷酸酶及蔗糖酶的活性均得到不同程度的提高,表明经钝化修复后土壤中相关代谢反应得到恢复;两种黏土矿物对土壤中水解氮含量无明显影响,但降低了土壤有效磷含量.综合总体表现,两种黏土矿物可被推荐作为镉污染酸性稻田土壤的原位钝化修复材料.     

A note on the consumption of acid through cation exchange with clay minerals in atmospheric precipitation

The first estimates of the consumption of potentially available strong acid in atmospheric precipitation through the mechanism of cation exchange with clay minerals have been obtained for three climatically different regions of the world: (1) Antarctica (South Pole); (2) continental Europe (north of the Alps); and (3) the continental Mediterranean.From the calculations involving the ranges of the concentrations of potentially available strong acid and of clay minerals of low-to-medium cation exchange capacity for each of the three regions it is suggested that the above process of acid consumption may almost always be insignificant in liquid (or liquified) precipitation over Antarctica and continental Europe.On the other hand, it is only under the most favourable conditions—involving the maximum stipulated cation exchange capacity of the clay minerals—that the same process could possibly lead to a maximum acid consumption in precipitation water up to ∼30% in the eastern Mediterranean region.The cation exchange process is also considered briefly in relation to the probable recycling of clay minerals of aeolian origin through evaporating clouds. Application of the first principles of cloud physics to the qualitative discussion suggests that clay minerals acting as freezing nuclei may have the best chance of participating in cation exchange, and hence, in acid consumption in clouds.     

苏北闵桥含油玄武岩中粘土矿物的组合特征及其应用

苏北闵桥地区含油玄武岩的主要次生蚀变粘土矿物为：皂石，绿泥石，蒙脱石，伊利石，伊利石／蒙脱石混层，高岭石，方沸石等，不同类型的玄武岩中粘土矿物组合不同，最具特征的组合为：致密玄武岩－皂石（为主）＋其它矿物；淬碎玄武岩－蒙脱石（为主）＋伊利石＋伊利石／蒙脱石混层＋高岭石，碎裂玄武岩－皂石（为主）＋绿泥石＋方沸石，蚀变玄武岩中，随着蚀变作用由弱到强，这些粘土矿物可以分成四个带，皂石带－绿泥石带－蒙脱石带－高岭石带，这种分带性与夏威夷玄武岩中热液成因的粘土矿物的分布性具有可比性，在一个玄武岩岩流单元不同部位，特征粘土矿物为：底部－蒙脱石；中倍位－皂石，顶部位－伊利石＋伊利石／蒙脱石混层，风化带特征粘土矿物为蒙脱石，少量高岭石，本文还对利用粘土矿物组合特征在玄武岩含油性，古地理及古环境等方面的应用进行了探讨。     

黏土矿物不同腐殖质组分团聚体对苯酚的封存特征

为探讨不同腐殖质组分团聚体对苯酚封存能力的影响,应用国际腐殖酸协会推荐的方法提取腐殖质,以Ca²⁺、Al³⁺、Fe³⁺为桥键离子,制备了高岭石、蒙脱石不同腐殖质组分团聚体,并采用平衡吸附/解吸试验、应用饱和吸附量与最大解吸量差减法研究了不同腐殖质组分团聚体对苯酚的封存特征.结果表明,团聚体对苯酚的吸附等温线可用Freundlich吸附/解吸方程（R²=0.991~0.998）和Langmuir吸附/解吸方程（R²=0.993~0.999）描述.高岭石不同腐殖质组分团聚体对苯酚的封存量（Q_m^irr）排序为：富里酸团聚体（（133.71±6.14）mg·kg^-1） > 胡敏酸团聚体（（49.59±8.93）mg·kg^-1） > 胡敏素团聚体（（21.68±2.95）mg·kg^-1）;封存系数（SR）排序为：富里酸团聚体（0.53±0.04） > 胡敏酸团聚体（0.27±0.05） > 胡敏素团聚体（0.18±0.03）;蒙脱石不同腐殖质组分团聚体对苯酚的封存量（Q_m^irr）排序为：富里酸团聚体（（319.44±8.95）mg·kg^-1） > 胡敏酸团聚体（（92.96±22.10）mg·kg^-1） > 胡敏素团聚体（（36.22±6.36）mg·kg^-1）;封存系数（SR）排序为：富里酸团聚体（0.76±0.02） > 胡敏酸团聚体（0.32±0.09） > 胡敏素团聚体（0.23±0.05）.考查腐殖质团聚体对苯酚的封存能力时不但要考虑腐殖质的含量,更要考虑腐殖质的赋存形态,它也是影响团聚体对苯酚封存能力的重要因素.富里酸、胡敏酸和胡敏素与黏土矿物结合形成有机矿质复合体后,对苯酚的封存能力发生了显著改变,团聚体对苯酚的封存系数与团聚体有机碳含量和内表面积呈显著正相关（p<0.01）,团聚体对苯酚的吸附/解吸分配系数（k/k_d）与团聚体有机碳含量和内表面积呈显著正相关（p<0.01）,土壤/沉积物团聚体的有机碳含量和内表面积是影响对苯酚封存特征的重要因素.研究显示,不同腐殖质组分团聚体对苯酚的封存能力排序为：富里酸团聚体 > 胡敏酸团聚体 > 胡敏素团聚体.     

用炼油厂废白土制备有机膨润土的研究(I)──废白土的提纯

对炼油厂废白土的脱蜡脱油工艺及脱蜡脱油后度白土的湿法提纯工艺进行了实验研究,并用阳离子交换容量（CEC）和吸蓝量（M．B．）来表征提纯废白土的活性和蒙脱石含量,找到了废白土提纯的最佳工艺条件,为进一步利用提纯废白土合成有机膨润土提供了合格的原料     

用炼油厂废白土制备有机膨润土的研究(Ⅰ)--废白土的提纯

对炼油厂废白土的脱蜡脱油工艺及脱蜡脱油后废白土的湿法提纯工艺进行了实验研究     

Reduction of VOC released by pore-forming precursors during firing of clay ceramic

In the ceramic industry, burning of pore-forming agents in clay materials during firing leads to the emission of pollutant volatile organic compounds (VOC). Afterburning of such kinds of organics in a separate carbonization chamber for tunnel kilns is a possible solution for their further transformation into non-polluting species (H₂O, CO₂, …). However, this requires important investments to be made in relation to major kiln modifications. Therefore, in this paper, we propose an alternative method of organic conversion through the addition of oxidizing agents such as peroxide and dioxide in the raw materials.     

改性黏土絮凝海洋原甲藻对水体中氮、磷的影响研究

通过对比研究典型有害微藻海洋原甲藻(Prorocentrum micans Ehrenberg)自然消亡(A1组)及改性黏土絮凝(A2组)两种体系,考察两体系中氮、磷等主要水质因子的变化情况.结果表明,改性黏土能有效去除P. micans并影响其后期生长状态,0.4g/L改性黏土添加3.5h后去除率可达60%以上,且藻密度无二次增长.改性黏土絮凝藻华过程中能有效去除水体营养元素, A2组DIP和DIN较A1组分别降低85%和35%.另外,添加改性黏土对水体有机氮、磷影响值得关注,第33d A2组TON和TOP较A1组分别减少约120, 6μmol/L. 改性黏土对有机氮、磷存在一定的埋存保护作用,通过吸附絮凝、螯合等作用使有机氮、磷脱离水体系统,而自然消亡体系中的微藻消亡后将通过分解、矿化等过程快速进入水体参与再循环.该研究系统阐述了改性黏土絮凝P. micans对水体营养环境的影响,以期为现场治理提供理论支持.     

海上溢油在破碎波作用下的乳化作用

本文研究了海上溢油在破碎波作用下的乳化作用。结果表明，溢油乳化后在水体中浓度的垂直分布呈指数函数下降。通过乳化油定量的测定，得到一个波高为０．３８ｍ破碎波的任凭深度为０．３５ｍ。通过室内模拟实验并利用尼斯模式，计算了海上５级海况下溢油乳化后，在０．４ｍ水层的乳化率约为５９％。     

嗜酸性氧化亚铁硫杆菌介导的次生铁矿物形成的影响因素分析

酸性矿山废水(AMD)具有酸度高并含有大量可溶性Fe、硫酸根及重(类)金属的特点,采用生物矿化法促使AMD中Fe向羟基硫酸铁次生矿物转变,对AMD后期石灰中和减少氢氧化铁和废石膏的产生,提高中和效率具有实际意义.本研究模拟AMD,考察了初始pH、Fe~(2+)浓度、Fe/Na摩尔比对嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)体系中Fe~(2+)氧化率、总Fe沉淀率、次生铁矿物矿相的影响.结果表明,高浓度Na~+会抑制A.ferrooxidans的氧化能力,当Na~+浓度在A.ferrooxidans耐受范围内时,其不影响Fe~(2+)氧化及总Fe沉淀去除效果,表现在160、80、20 mmol·L~(-1)的Fe~(2+)分别在72、48、48 h内被完全氧化,培养至终点时平均总Fe沉淀率分别为20.04%、16.43%、0.99%.此外,在Fe~(2+)浓度为160mmol·L~(-1)体系中,当Fe/Na摩尔比为1.0、2.0时,pH为2.0~2.6时获得次生铁矿物均为纯净施氏矿物.而当Fe/Na摩尔比降至0.5时,次生铁矿物的合成途径开始向黄钠铁矾转移,且其特征衍射峰随着Na~+浓度提高而愈加显著.本研究结果可为生物合成次生铁矿物工艺的优化及其在AMD治理领域的有效应用提供必要的参数支撑.