腐殖酸-高岭石胶体对铀(Ⅵ)在饱和多孔介质中迁移过程的影响

为探讨可溶性有机质存在条件下黏土矿物胶体对铀(Ⅵ)在饱和多孔介质中迁移的影响,选取2种石英砂(细砂和粗砂)分别构建均质构型的石英砂柱,研究了饱和水流条件下腐殖酸存在时高岭石胶体对铀在2种不同粒径石英砂中迁移的影响。结果表明,示踪溶质在2种均质石英砂柱中的穿透曲线相似且分布对称。当在石英砂柱中只通入铀(Ⅵ)溶液时,铀(Ⅵ)在2种粒径石英砂柱中的穿透量均较小(25%),此时大量的铀(Ⅵ)通过络合作用吸附在石英砂表面上。当通入溶液中存在腐殖酸和高岭石胶体时,铀(Ⅵ)在2种石英砂柱中的穿透量增加,且在600～850μm石英砂中(58.36%)比250～425μm石英砂中(42.68%)穿透量更多。这充分表明腐殖酸—高岭石胶体和石英砂粒径是影响铀(Ⅵ)在地下环境中迁移的重要因素。     

碳酸钙和壳聚糖联用对高pH值石灰性土壤砷污染的钝化

为明确碳酸钙-壳聚糖联用对高pH值石灰性土壤砷污染的钝化效果,该研究采用田间As污染模拟试验,设置对照(CK)、砷污染(As)、砷污染+碳酸钙(As+Ca)、砷污染+碳酸钙+壳聚糖(As+Ca+C)4个处理。研究了碳酸钙和壳聚糖添加对As污染石灰性土壤酶活性影响,污染土壤中As的形态变化,以及As在供试作物玉米体内的迁移特征。结果表明:As污染石灰性土壤上添加碳酸钙(Ca)有利于提高土壤酶活性,碳酸钙和壳聚糖(Ca+C)联用后,土壤脲酶、纤维素酶和过氧化氢酶活性分别显著提高了52.35%、74.92%、8.72%(P0.05)。高pH值石灰性土壤外源As的主要存在形态为残渣态,且残渣态占总砷含量的60%以上。与As处理相比,As+Ca和As+Ca+C处理的水溶态砷分别显著降低17.15%和27.03%(P0.05);As+Ca+C处理的钙-砷、铁-砷和铝-砷分别显著升高了13.97%、14.24%、13.85%(P0.05)。As+Ca和As+Ca+C钝化处理对As钝化率分别达9.78%和18.37%。As污染土壤上种植玉米会导致各部位As积累的增加,但Ca+C联用使玉米籽粒、根、茎、叶的As含量显著降低50%、13.98%、16.51%、14.94%(P0.05)。可见,Ca+C钝化剂联用方法可应用于高pH值石灰性土壤As污染修复。     

腐殖酸-高岭石胶体对铀(VI)在饱和多孔介质中迁移过程的影响

为探讨可溶性有机质存在条件下黏土矿物胶体对铀（VI）在饱和多孔介质中迁移的影响,选取2种石英砂（细砂和粗砂）分别构建均质构型的石英砂柱,研究了饱和水流条件下腐殖酸存在时高岭石胶体对铀在2种不同粒径石英砂中迁移的影响。结果表明,示踪溶质在2种均质石英砂柱中的穿透曲线相似且分布对称。当在石英砂柱中只通入铀（VI）溶液时,铀（VI）在2种粒径石英砂柱中的穿透量均较小（<25%）,此时大量的铀（VI）通过络合作用吸附在石英砂表面上。当通入溶液中存在腐殖酸和高岭石胶体时,铀（VI）在2种石英砂柱中的穿透量增加,且在600~850 μm石英砂中（58.36%）比250~425 μm石英砂中（42.68%）穿透量更多。这充分表明腐殖酸—高岭石胶体和石英砂粒径是影响铀（VI）在地下环境中迁移的重要因素。     

铁改性生物炭抑制土壤中As的迁移

砷(As)的毒性极强,为了治理含As土壤,该研究通过室内土柱模拟试验,研究铁改性生物炭对土壤中As迁移能力和形态的影响。结果表明:添加1%~8%生物炭和铁改性生物炭后,能显著降低土柱灌水后渗滤液中As的含量,增加土壤表层(0~20 cm) As的含量,降低土壤深层(>20~50 cm) As的含量,促进土壤中有效态As向稳定态As转化,生物炭的添加量越大,土壤中R-As的含量就越高。对比铁改性生物炭和生物炭发现,生物炭负载Fe3+后,其吸附和固持能力更强,更能促进有效态As向R-As转化,进而降低As污染的风险。因此,在治理含As土壤时,可在表层土壤施加2%的铁改性生物炭,达到吸附和固化As的目的,进而提高土壤的安全性。     

硅酸盐菌剂对污染土壤中砷、硅活性的影响效应研究

采用摇床短期培养和梯度长期土壤培养方法,研究硅酸盐菌剂(含胶质芽孢杆菌)对砷污染土壤固相中砷、硅向液相释放或迁移的影响效应,并筛选调控土壤砷有效性的菌剂适宜添加量。采用自然土和砷污染土为研究对象的摇床短期培养结果表明,添加硅酸盐菌剂处理的自然土、砷污染土的土壤浸提液中As浓度较CK(灭菌培养基)分别降低了92.8%和65.5%;较硅酸盐菌剂的灭菌菌液处理分别降低了54.4%和37.0%,这说明硅酸盐菌剂对土壤中砷有钝化作用,降低了土壤中砷的活性;自然土、污染土的土壤浸提液中Si浓度较CK(灭菌培养基)分别降低了40.6%和53.5%,较灭菌菌液分别降低了42.5%和54.3%,即硅酸盐菌剂也降低了土壤固相硅向液相的释放。另外,梯度长期土壤培养试验结果表明,添加菌剂量在10~100ml的范围内,土壤溶液中硅浓度并没有随着菌剂量的增加而增加,而添加10ml菌剂的处理土壤溶液中As浓度较添加菌剂50ml,100ml处理分别降低了29.3%和85.6%,因此钝化污染土中砷活性的硅酸盐菌剂适宜用量为10ml。     

4种形态砷在盆栽水稻中的分布与转化研究

用盆栽实验研究了As(Ⅲ)、As(V)、MMAV和DMAV 4种形态的砷在水稻中的分布和转化规律。通过向土壤中添加4种分别5个浓度的砷,种植5种水稻300盆,获得了水稻根、茎、叶、穗、米中的As(V)、As(Ⅲ)、MMAV、DMAV和总砷的22 500个数据;对比分析了4种形态砷对水稻的生理影响、在水稻中的迁移和转化情况及土壤中的砷与稻米中砷含量的关系。结果表明,4种形态砷的转移转化规律差异较大,对砷的风险评估不能一概而论,应将砷分形态开展研究,科学评价不同形态砷毒性和控制水稻砷风险。     

Cr(VI)和As(V)在东北地区不同类型土壤中的迁移特征研究

利用土柱淋溶实验研究Cr(VI)和As(V)在不同类型土壤中的垂向迁移特征。结果表明,Cr(VI)和As(V)在含砂砾和砾石的河流冲积物中迁移速度最大,而在粘粒含量较高的黄土中迁移速度最小。土壤砂粒含量和pH值越高,Cr(VI)和As(V)的迁移速度越大。粉粒、粘粒、铁氧化物和锰氧化物含量越高,越不利于Cr(VI)和As(V)的迁移,说明以上因素对于Cr(VI)和As(V)在土壤中的吸附具有很大的贡献。总有机碳(Total Organic Carban,TOC)的含量升高不利于Cr(VI)和As(V)的迁移,但是影响不大。     

土壤中砷的生物转化及砷与抗生素抗性的关联

砷是一种广泛存在于自然环境中毒性较强的类金属元素,农田生态系统中的植物(尤其水稻)很容易吸收积累土壤环境中的砷。植物中的砷沿食物链向高等动物传递,威胁人类健康。除土壤本身的理化性质外,土壤中砷的生物转化也强烈影响砷的生物有效性。目前研究发现异化砷酸盐(As(V))呼吸性还原、细胞质As(V)还原、亚砷酸盐(As(III))氧化、As(III)甲基化和有机砷的去甲基化在土壤砷的生物地球化学过程中起重要作用。随着分析化学和分子生物学技术的进步,最新研究发现土壤生物也参与了砷糖、砷糖磷脂、砷甜菜碱、砷代草丁膦、硫代砷等有机砷的合成,其中三价一甲基砷和砷代草丁膦可作为新型抗生素,但其合成机制及生态学功能有待进一步研究。本文还详细介绍了为适应复合污染环境微生物通过自身的进化对抗生素和重金属形成的四种共选择抗性机制:共抗性,交叉抗性、共调控和生物膜感应,特别提出了土壤中砷污染与抗生素抗性相关联这一新的研究方向。最后对砷生物转化和砷与抗生素共抗机制的未来研究方向做了展望。     

外源As（Ⅲ）、As（Ⅴ）在石灰性土壤中的转化及其对有机碳降解酶活性的影响

砷在土壤中的转化积累特性与其生物有效性密切相关。然而,外源As(Ⅲ)、As(Ⅴ)添加对石灰性土壤中砷的动态转化及其生态毒理的影响仍不清楚。通过设置不同剂量(0、20、50、100、180、280、450和800 mg kg-1)砷的土壤培养试验,采用连续浸提方法、物料袋方法研究了As(Ⅲ)、As(Ⅴ)在石灰性土壤中的动态转化特征及土壤生物学性状对As(Ⅲ)、As(Ⅴ)响应的剂量效应。结果表明:(1)土壤交换态砷(AE-As)浓度随培养时间延长而下降,而铝型砷(Al-As)、铁型砷(Fe-As)、钙型砷(Ca-As)浓度则明显升高,说明水溶性砷逐渐转化为难溶性砷,且以Ca-As为主,As(Ⅲ)和As(Ⅴ)处理间差异不显著。(2)过氧化氢酶活性随外源As(Ⅲ)和As(Ⅴ)剂量增加而呈下降趋势(30 d和100 d),蔗糖酶活性随As(Ⅲ)和As(Ⅴ)添加剂量而明显上升(30 d),说明As(Ⅲ)和As(Ⅴ)对过氧化氢酶有抑制作用,对蔗糖酶有刺激作用;As(Ⅲ)和As(Ⅴ)添加对多酚氧化酶活性影响不明显;As(Ⅴ)处理的过氧化氢酶、多酚氧化酶及蔗糖酶平均活性分别比As(Ⅲ)处理高13.7%、1.9%、1.2%,说明As(Ⅲ)生态毒性大于As(Ⅴ)。此外,通过对土壤各形态砷含量与酶活性进行相关分析可知,蔗糖酶对土壤砷的响应较过氧化氢酶和多酚氧化酶更敏感,可作为石灰性土壤砷污染的指示酶。(3)添加于土壤中的大豆秸秆的降解率随外源砷剂量增加而下降,但As(Ⅲ)和As(Ⅴ)处理间差异不显著。综上可以得出如下结论:不同形态的砷在石灰性土壤中转化、转化为以Ca-As为主,As(Ⅲ)和As(Ⅴ)处理间差异不显著;外源As(Ⅲ)和As(Ⅴ)对土壤有机碳降解均有明显抑制作用,且As(Ⅲ)对碳转化相关酶的生态毒性大于As(Ⅴ)。     

磺胺嘧啶在土壤及土壤组分中的吸附/解吸动力学

抗生素在土壤中的吸附/解吸及迁移过程受其理化性质的强烈影响,其中土壤中的矿物成分,如高岭石、蒙脱石及腐殖酸等是重要控制因素。本文主要研究了磺胺嘧啶在土壤、高岭石、蒙脱石和腐殖酸中的吸附/解吸动力学过程,并对反应前后的高岭石、蒙脱石和腐殖酸进行傅里叶红外光谱(Fourier transform infrared, FTIR)表征,探讨其可能的吸附机理。结果表明:磺胺嘧啶的吸附(解吸)动力学过程,可以分为快速吸附(解吸)、吸附解吸动态平衡和吸附(解吸)平衡3个阶段;磺胺嘧啶在土壤及其3种组分中的吸附(解吸)均可在24 h内达到平衡,其浓度高低会导致土壤及其组分的吸附差异,不同土壤组分中的官能团含量、带电性质及氢键是造成吸附差异的主要原因;分别用伪一级动力学模型、伪二级动力学模型和Elovich模型对其吸附过程进行拟合,其动力学吸附过程更符合伪二级动力学模型,R20.99,主要受控于物理化学吸附;FTIR图谱表明磺胺嘧啶与高岭石以物理吸附为主,并有少量氢键作用,与蒙脱石之间主要以氢键作用完成吸附,而在腐殖酸中存在表面络合和π–π共轭作用。     

胶体颗粒对不同粒径饱和多孔介质渗透性的影响

探讨胶体颗粒在多孔介质中迁移所发生的物理、化学及生物作用过程,在许多学科中具有重要的科学意义。采用室内石英砂柱实验,开展了定水头条件下不同浓度和粒径的胶体颗粒在饱和多孔介质中的运移行为研究。共使用了3种胶体粒径、3种浓度的胶体溶液和3种粒径范围的石英砂。实验表明:多孔介质的相对渗透系数K/K0(K为各时刻计算所得的渗透系数,K0为初始渗透系数)减小程度与颗粒浓度成正比;胶体颗粒越大,越易在表层沉积,而小颗粒易向下部迁移,但总体来看粒径效应没有浓度效应明显;当胶体颗粒在不同粒径的饱和多孔介质中迁移时,粒径大的多孔介质各段K/K0均有明显降低,而粒径小的只在表层变化明显。不同条件下总体相对渗透系数与时间之间呈二次方相关关系,但当多孔介质粒径较小时,相关性不显著。介质渗流流速及砂柱不同位置胶体颗粒浓度变化与介质渗透性变化相对应。用扫描电镜(Scanning Electron Microscope,SEM)进行定性表征,进一步说明胶体颗粒会堵塞多孔介质孔隙影响其渗透性。实验中发现当输入浓度C0小于0.5 g·L–1且dp/Dp>0.018(dp为胶体颗粒粒径,Dp为石英砂算数平均粒径)时,会出现多孔介质局部K/K0增大的现象。     

生物膜和土壤矿物对人工纳米颗粒在饱和多孔介质传输的影响

本文探究了人工纳米颗粒(NPs)在饱和多孔介质中的传输规律和影响机制，重点阐明生物膜和土壤矿物对纳米颗粒传输的影响及其机制。结果表明，在干净的石英砂介质中，不同种类和粒径NPs的传输效率具有明显差异，不同种类NPs传输效率表现为ZnO> CeO2>Fe2O3；对于报告粒径在20～100 nm之间的CeO2 NPs，粒径的增加有助于其在多孔介质的传输。溶液离子强度的增大会降低Zn O NPs的传输，而NPs浓度的增大不利于其在饱和多孔介质的传输，传统的DLVO理论能够很好地解释NPs在无涂层饱和多孔介质中的传输。生物膜和土壤矿物均能抑制纳米颗粒在饱和多孔介质的传输，其主要通过对纳米颗粒的吸附和异质聚集作用影响纳米颗粒的传输，非DLVO相互作用以及介质涂层的表面特性对增强纳米颗粒沉积有很大贡献。     

Soil solid phases effects on the proteomic analysis of Cupriavidus metallidurans CH34

Cupriavidus metallidurans CH34 is a completely sequenced soil-borne beta-proteobacterium with known genome and proteome. Comparative 2-D electrophoresis and protein mass spectrometry were used to compare the proteome of C. metallidurans CH34 from liquid culture and after incubation for 1, 3, and 12?days in microcosms containing quartz sand, kaolinite, montmorillonite, or an artificial soil. Results showed that proteome from liquid culture was similar to CH34 proteins extracted from sand and kaolinite, whereas the proteins extracted from artificial soil differed significantly and no proteins were detected from C. metallidurans CH34 incubated in the montmorillonite microcosms. Protein recovery decreased on prolonging incubation time in all microcosms. Mass spectrometry identification showed that the trend of lower recovery upon incubation time was independent on the putative function of protein. These results suggest that the soil solid phase influences the protein recovery and soil proteomic analysis and that distinction between protein recovery and protein expression in soil will be a challenging for soil proteomic researchers.     

The failure of using equilibrium adsorption of fosthiazate onto montmorillonite clay particles to predict their cotransport in porous media as revealed by batch and column studies

Journal of Soils and Sediments - Adsorption of fosthiazate onto montmorillonite clay particles (MPs) and cotransport of fosthiazate and MPs in sand and soil porous media were investigated for the...     

Development of a mineralogical matrix at the adsorption of polyelectrolytes on soil minerals and soils

The formation of the adsorption layers of polyelectrolytes (PEs) with the development of a mineralogical matrix on the surface of soil minerals and soils (kaolinite, montmorillonite, quartz sand, gray forest soil, and a chernozem) were established on the basis of direct measurements and IR spectroscopy. The differences in the adsorption kinetics of polyacrylamide (PAM) and polyacrylic acid (PAA) were revealed depending on the mineral nature, which were confirmed by the calculated values of the effective adsorption constants. It was found that the limit values of the PAM and PAA adsorption derived from experimental measurements for all the minerals were significantly higher than the values calculated for the formation of a monomolecular layer, which indicated adsorption on the surface of not only separate macromolecules but also secondary PE structures such as packets or fibrils. The IR spectroscopy studies confirmed the differences in the adsorption mechanism of PEs on soil minerals (from physical adsorption to chemisorption with the formation of surface compounds due to polar groups of PEs and surface groups of mineral particles). As a result, a cluster-matrix structure controlling the physicochemical properties of the modified surface was developed on the surface of natural aluminosilicates and soils.     

Electrokinetic properties of soil minerals and soils modified with polyelectrolytes

The formation features of nanoadsorption polyelectrolyte (PE) layers with the formation of a mineral-organic matrix on the surface of clay minerals and soils (kaolinite, montmorillonite, quartz sand, gray forest soil, and chernozemic soil) have been elucidated by direct adsorption measurements. It has been found that the experimental values for the limit adsorption of polyacrylamide (PAM) and polyacrylic acid (PAA) on all the minerals are significantly higher than the calculated values for the formation of a monolayer. This indicates adsorption on the surface of not only separate macromolecules but also secondary PE structures as packets or fibrils determining the cluster-matrix structure of the modified surface. The study of the electro-surface properties (electrophoretic mobility, electrokinetic potential, pH, and electroconductivity) of mineral and soil particles adsorption-modified with PEs has confirmed the differences in the adsorption mechanisms (from physical sorption to chemisorption) with the formation of surface compounds depending on the different polar groups of PEs and the mineral type.     

非均质性对保守溶质及蒙脱石胶体在饱和多孔介质中运移的影响

选取2种粒径玻璃珠构建6种不同构型的柱子(2个均质和4个非均质),研究了饱和条件下多孔介质构型对保守溶质和蒙脱石胶体运移的影响。结果表明:在2种均质介质中,保守溶质的穿透曲线相似且对称,蒙脱石胶体在大粒径玻璃珠中的移动性更强。当介质中存在大孔隙通道时,优先流现象的出现会加速保守溶质和蒙脱石胶体的迁移,大孔隙通道与周围介质交界面越大保守溶质和蒙脱石胶体的拖尾现象越明显且穿透峰较低。在大、小粒径玻璃珠均匀混合填装的柱子中,保守溶质穿透曲线形状与均质柱子相似,蒙脱石胶体的移动性介于大、小粒径玻璃珠均匀填装的柱子之间。蒙脱石胶体在玻璃珠分层填装的柱子中,大粒径与小粒径交界面区域会有更多的蒙脱石胶体滞留。研究表明非均质性对保守溶质和蒙脱石胶体在土壤和地下环境中的运移过程有重要的影响。     

Comparison of the Transport of Tetracycline-Resistant and Tetracycline-Susceptible Escherichia coli Isolated from Lake Michigan

It was recently reported that tetracycline could enhance the mobility of manure-derived Escherichia coli within saturated porous media (Walczak et al. (Water Research 45:1681-1690, 2011)). It was also shown, however, that E. coli from various sources could display marked variation in their mobility (Bolster et al. (Journal of Environmental Quality 35:1018-1025, 2009)). The focus of this research was to examine if the observed difference in the mobility of manure-derived tetracycline-resistant (tet(R)) and tetracycline-susceptible (tet(S)) E. coli strains was source-dependent. Specifically, E. coli were isolated from Lake Michigan, and the influence of tetracycline resistance on Lake Michigan-derived E. coli was investigated through column transport experiments. Additionally, a variety of cell morphology and surface properties were determined and related to the observed bacterial transport behavior. Our experimental results showed that, consistent with previous observations, the deposition rate coefficients of the tet(R)E. coli strain was ~20-100% higher than those of the tet(S)E. coli strain. The zeta potential of the tet(R)E. coli cells was ~25 mV more negative than the tet(S)E. coli cells. Because the surfaces of the E. coli cells and the quartz sands were negatively charged, the repulsive electrostatic double-layer interaction between the tet(R)E. coli cells and the quartz sands was stronger, and the mobility of the tet(R)E. coli cells in the sand packs was thus higher. The tet(R)E. coli cells were also more hydrophilic than the tet(S)E. coli cells. Results from migration to hydrocarbon phase (MATH) tests showed that about ~35% more tet(S)E. coli cells partitioned to the hydrocarbon phase. As it was previously shown that cell hydrophobicity could enhance the attachment of bacterial cells to quartz sand, the difference in cell hydrophobicity could also have contributed to the observed higher mobility of the tet(R)E. coli cells. The size of the tet(R) and tet(S)E. coli cells were similar, suggesting that the observed difference in their mobility was not size-related. Characterization of cell surface properties also showed that tet(R) and tetS E. coli cells differed slightly in cell-bound lipopolysaccharide contents and had distinct outer membrane protein profiles. Such difference could alter cell surface properties which in turn led to changes in cell mobility.     

Effect of clay colloids on the zeta potential of Fe/Al oxide-coated quartz: a streaming potential study

Purpose

This study was conducted in order to examine the effect of colloidal particles on electrochemical properties of charged larger size materials.

Materials and methods

A self-made streaming potential apparatus was used to measure the zeta potentials of Fe/Al oxide-coated quartz. The effects of colloidal particles of kaolinite and montmorillonite on the electrochemical properties of Fe/Al oxide-coated quartz were investigated through comparing the difference in zeta potential of the coated quartz in electrolyte and clay suspension.

Results and discussion

The change of zeta potentials of the coated quartz, when clay suspensions flowed through, increased with the increasing concentrations of kaolinite and montmorillonite and degree of coating with Fe/Al oxides, and decreased with increased ionic strength of the suspensions. Electrostatic attraction between clay colloids and the coated quartz was the key factor influencing the interaction between the oppositely charged particles. The deposition of colloidal particles of kaolinite and montmorillonite on coated quartz and the overlapping of the diffuse layers of electrical double layers between the oppositely charged particles were responsible for the change in zeta potential of Fe/Al oxide-coated quartz. The relative contribution of the deposition of clay particles to the change in zeta potential was greater than that of the overlapping of diffuse layers.

Conclusions

When clay suspensions flowed through the saturated sand of Fe/Al oxide-coated quartz, both overlapping of diffuse layers between charged sand and clay particles and deposition of clay particles contributed to change of zeta potential of the coated quartz.