吸附反应时间对潮土中除草剂阿特拉津吸附行为的影响

A batch experiment was performed to investigate nonequilibrium adsorption behavior of atrazine （2-chloro-4-ethylamino-6-isopropylamlno-1,3,5-triazlne） on a fluvo-aquic soil. The amount of atrazine sorbed increased with increasing adsorption contact periods. For a range of initial atrazlne concentrations, the percentage of atrazine sorbed within 24 h ranged from 24% to 77% of the observed total amount sorbed for the longest contact period; when adsorption contact periods were more than 72 h, the deviations in curves fitted using a nonlinear Freundllch equation gradually became less. The opposite trend was observed for the atrazine concentrations in solution. The effect of adsorption contact periods on atrazine adsorption behavior was evaluated by interpreting the temporal variations in linear and nonlinear Freundlich equation parameters obtained from the phase-distribution relationships. As the adsorption contact period increased, the nonlinear Freundlich capacity coefficient kf showed a significant linear increase （r^2 = 0.9063, P 〈 0.001）. However, a significant negative linear correlation was observed for the nonlinear coefficient n, a dimensionless parameter （r^2 = 0.5666, P 〈 0.05）. Furthermore, the linear distribution coefficient kd ranged from 0.38 to 1.44 and exhibited a significant linear correlation to the adsorption contact period （r^2 = 0.72, P 〈 0.01）. The parameters kf and n obtained from a time-dependent isotherm rather than the distribution coefficient kd estimated using the linear Freundlich equation were more appropriate to predict the herbicide residue in the field and thus more meaningful for environmental assessment.     

纳米粘土矿物对阿特拉津的吸附-解吸特性研究

采用批量平衡实验,研究了纳米粘土矿物与原粘土矿物对除草剂阿特拉津的吸附解吸特陛。结果表明,粘土矿物对阿特拉津的吸附-解吸均能用Freundlich方程很好地拟合。随着溶液中阿特拉津浓度的增加,粘土矿物对阿特拉津的吸附量增加;粘土矿物粒径越小,吸附量越大,纳米粘土矿物的吸附量显著大于原粘土矿物。粘土矿物对阿特拉津吸附量大小顺序为：纳米SiO2）纳米蒙脱石〉凹凸棒石〉蒙脱石〉SiO2。粘土矿物对阿特拉津的解吸表现出一定的滞后效应,即粘土矿物吸附的阿特拉津越多,解吸的越少。粘土矿物对阿特拉津的解吸率大小顺序为：SiO2〉凹凸棒石〉纳米蒙脱石〉纳米SiO2〉蒙脱石。     

阿特拉津除草剂对土壤微生物生态特征的影响

采用实验室培养试验研究了阿特拉津除草剂对土壤微生物生态特征的影响。结果表明：阿特拉津除草剂10mg／kg浓度处理释放的CO2与对照无明显差异,根据危害系数法的分级方法,其属于无实际危害级农药;阿特拉津除草剂10mg／kg浓度处理在初始阶段,明显降低土壤微生物生物量碳和微生物生物量氮,随培养时间推移土壤微生物生物量碳和生物量氮有所恢复,随后又有所下降,30d后土壤微生物生物量变化趋于平缓;阿特拉津除草剂对土壤微生物多样性产生一定影响．其影响随培养时间而异。在一定程度上反映出土壤微生物生态特征指标可作为除草剂污染土壤环境质量变异的参考指标。     

微生物降解阿特拉津的研究进展

除草剂阿特拉津长期使用所造成环境污染问题的日益加重,受污染土壤、水体的生物降解、生态修复等诸多问题也受到人们的广泛关注,本文综述了降解阿特拉津的微生物类群、阿特拉津降解酶以及微生物对阿特拉津的作用方式和降解途径,并对其应用前景进行了展望。     

阿特拉津降解菌ADH-2的分离、鉴定及其特性研究

从长期施用阿特拉津的玉米地中采集土样,通过富集培养的方法分离出一株能以阿特拉津为唯一碳、氮源生长的细菌ADH-2,结合生理生化特陛及16SrRNA基因的相似性分析将其初步鉴定为节杆菌属（Arthrobacter sp．）。该菌在10h内对100mg·L-1阿特拉津的降解率为99．9％。外加氮源能促进菌株的生长,但对阿特拉津的降解有轻微的抑制作用。外加蔗糖和葡萄糖能显著促进菌株的生长,但对阿特拉津的降解表现出显著的抑制。而淀粉既能促进菌株的生长又能促进阿特拉津的降解。对其降解基因的初步研究显示,该菌含有trzN、atzB和atzC3个阿特拉津降解相关基因。通过与本实验室另外两株阿特拉津降解菌比较,菌株ADH-2具有更好的应用潜力。     

鲫鱼对除草剂阿特拉津的生物富集效应研究

采用半静态水质接触染毒法,研究鲫鱼（Carassius auratus）肝脏、肾脏和肌肉对不同质量浓度（0、0.1、0.5、1.0、5.0和10.0 mg·L^-1）阿特拉津的富集效应。结果表明,阿特拉津在鱼体中的富集速度较快;在试验所选浓度下,鲫鱼肝脏、肾脏和肌肉均在染毒后19 d即对阿特拉津达到富集稳态,但各个器官对阿特拉津的富集能力都较低。阿特拉津在肝脏、肾脏和肌肉中的富集系数均随着染毒浓度的增加而变小,呈现显著的负相关关系;其在肝脏、肾脏和肌肉中的最大和最小富集系数分别出现在最低（0.1 mg·L^-1）和最高（10.0 mg·L^-1）浓度组,最大富集系数分别为：13.08、11.00和6.02,最小富集系数分别为：5.22、4.37和2.94。而且,当阿特拉津暴露浓度相同时,鲫鱼不同组织器官对阿特拉津的富集能力存在差异,表现为：肝脏〉肾脏〉肌肉。     

土壤矿物和胡敏酸对阿特拉津的吸附-解吸作用研究

选取了6种土壤矿物(蒙脱石、高岭石、钙饱和处理蒙脱石、钙饱和处理高岭石、无定型氧化铁和无定型氧化铝),以及从土壤中提取纯化的3种胡敏酸为材料,采用批量吸附平衡法,研究土壤矿物和胡敏酸对阿特拉津的吸附特性。结果表明,各吸附剂对阿特拉津的吸附均能采用Frundlich方程进行较好地拟合(r≥0.982,p0.01)。胡敏酸对阿特拉津具有最大的吸附性能,其固-液分配系数(Kd值)随平衡浓度(Ce值)的变化基本恒定,吸附等温线呈线性(Frundlich方程常数N≈1),吸附以分配溶解作用为主,吸附可逆性较高。黏土矿物(特别是蒙脱石)对阿特拉津也具有较强的吸附能力,Kd值随Ce值增加而增加,吸附等温线呈S型(N1),吸附主要是通过表面亲水作用。无定型氧化铁铝的Kd值随Ce值增加而降低,当Ce达到一定水平后,Kd趋于恒定,吸附等温线呈L形(N1),吸附主要是通过无定型氧化物表面的羟基与阿特拉津分子间的化学键合作用,吸附可逆性最差。     

阿特拉津在土柱中的淋溶规律研究

通过室内土柱淋溶试验,对阿特拉津在2种供试土壤中淋溶规律及其影响因子进行了研究.结果表明,淋溶速度由1.8 ml/min增至4.4 ml/min,阿特拉津的土壤残留量降低,淋出量分别增加10.8%(黑土),8.2%(草甸黑土);同时,增加土壤有机质含量,适当降低淋溶液中H+离子浓度,均有利于抑制土壤中阿特拉津的迁移与流...     

离子强度对三种可变电荷土壤表面电荷和Zeta电位的影响

本文用离子活度和反号离子在土壤胶体双电层扩散层滑动面的分布解释了可变电荷土壤表面电荷与胶体Zeta电位随着离子强度增加呈相反变化趋势的原因。当p H大于土壤的盐效应零点(PZSE)时,离子强度增加导致土壤胶体双电层紧密层阴离子含量增加,土壤表面负电荷量增加,双电层滑动面上的反号离子(阳离子)数量增加,使得土壤胶体Zeta电位向正值位移。相反,当p H小于土壤PZSE,随着离子强度增加,土壤表面正电荷量增加,此时的反号离子为阴离子,双电层滑动面上的反号离子(阴离子)数量增加,导致土壤胶体Zeta电位向负值方向位移。另外,由于土壤表面对K+的吸附亲和力强于Na+,因此在相同浓度下,土壤胶体双电层滑动面上K+浓度高于Na+,导致土壤胶体在KNO3溶液中的Zeta电位高于在Na NO3溶液中的,从另一方面印证了这一解释。     

阿特拉津在土表的光解行为动力学研究

研究了阿特拉津在土壤表面的光解行为的动力学,并研究了各种因素对光解的影响。实验表明,土壤粒度、湿度、pH值、有机质、腐殖酸和表面活性剂都影响阿特拉津在土壤中的降解。在太阳光辐射下,阿特拉津在土壤表面降解速率常数为0. 08~0. 17d-1,光解深度为0. 3mm以内,半衰期为4~8d。     

Adsorption of atrazine and metolachlor in three soils from Blue Creek wetlands, Waterville, Ohio

Atrazine and metolachlor are extensively used pesticides in agricultural activities in northwest Ohio. Adsorption coefficients are often used to model pesticide fate and transport. Many physical-chemical parameters, such as organic matter, clay content, pH, and ionic strength, affect pesticide adsorption. Adsorption kinetics and adsorption isotherms were studied by batch experiment. Effects of humic acid, solution pH, and ionic strength on atrazine and metolachlor adsorption were also approached. After 24 h, both atrazine and metolachlor reached adsorption equilibrium in three local soils. Adsorption isotherms were described by Freundlich equations. The Freundlich coefficient (Kf) ranged from 0.14 to 4.47 (L kg^–1) for atrazine, and 0.04 to 5.30 (L kg^–1) for metolachlor. Adsorption capacity decreased in the order Sloan loam > Del Rey loam > Ottokee fine sand. Koc values varied considerably for both pesticides: metolachlor > in Sloan loam, atrazine metolachlor in Del Rey loam, and atrazine > metolachlor in Ottokee fine sand. In addition to organic matter content, clay played a key role in adsorption in the Del Rey loam and Ottokee fine sand. Higher adsorption was observed at pH 5 for both pesticides. As pH decreased to 3 and increased to 11, adsorption decreased. Adsorption increased as ionic strength increased.     

发育程度对海南玄武岩发育土壤吸附铬酸根和磷酸根的影响

选择海南岛北部3个不同年代喷发的玄武岩发育的土壤研究了其对铬酸根(CrO42-)和磷酸根(PO43-)的吸附特征,结果表明随着母岩年龄的增加,土壤发育程度提高,土壤游离氧化铁和表面正电荷数量增加,对2种阴离子的吸附量增加。土壤CrO42-的解吸率在19.8%~39.6%之间,表明土壤对CrO42-的吸附涉及静电吸附和专性吸附2种机制,且随着土壤发育程度增加,CrO42-静电吸附所占比例增加。土壤对PO43-的吸附以非静电吸附为主,吸附的PO43-的解吸量非常低,其解吸率不超过6%。吸附PO43-在去离子水中的解吸量高于在0.1 mol/L NaNO3和KNO3中的解析量,KNO3体系中的解吸量低于NaNO3体系中的,电解质主要通过改变胶体表面离子吸附面上的静电电位影响PO43-的解吸。     

Sb(V)在三种矿物表面的吸附行为

用研究了蒙脱土、高岭土和针铁矿在不同的pH与离子强度的介质条件下对Sb(V)的吸附及解吸行为。3种矿物对Sb(V)的吸附能力差别较大,蒙脱土的吸附量远大于针铁矿和高岭土,针铁矿与高岭土的吸附能力相近。pH对Sb(V)在3种矿物表面的吸附行为影响显著。随pH的升高,Sb(V)的吸附均减弱。吸附在高岭土表面的Sb(V)易解吸,而针铁矿和蒙脱土表面的Sb(V)不易解吸。随离子强度升高,高岭土对Sb(V)的吸附减弱;离子强度对Sb(V)在针铁矿和蒙脱土表面吸附的影响较小。     

磷酸盐在水铁矿及水铁矿-胡敏酸复合体表面的吸附

The adsorption of phosphate onto ferrihydrite (FH) and two FH-humic acid (HA) complexes, obtained by co-precipitating FH with low (FH-HA1) and relatively high amounts of humic acid (FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanism of phosphate adsorption onto two soil compositions. The isoelectric point (IEP) and the specific surface area (SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower pH, and the increase in the ionic strength promoted phosphate adsorption at a higher pH. However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower pH and increased the adsorption at a higher pH.     

湖库底泥对环丙沙星吸附特性的研究

为探明环丙沙星在湖库底泥中的吸附特性,以长春市新立城水库底泥为供试样品,利用OECD guideline 106批平衡吸附试验方法,研究环丙沙星在底泥中的吸附行为,并探讨pH和Ca~(2+)强度对环丙沙星吸附过程的影响。结果表明:环丙沙星的等温吸附能较好的拟合Herry-Freundlich和Herry-Langmuir复合吸附等温方程,其中Herry-Langmuir方程的拟合效果更好,相关系数r=0.995 3,达到差异极显著水平。环丙沙星在底泥中的整个吸附过程符合准二级反应动力学方程,吸附参数k=8.76×10~(-3)kg/(min·mg)。研究发现,pH值在3~11的条件下,环丙沙星的吸附量随pH的增加呈先升高后降低的趋势。当pH=5时,吸附效果最好,可吸附环丙沙星总量的99.75%,强酸性和强碱性条件均不利于底泥对环丙沙星的吸附。随电解质中CaCl_2浓度的增加,底泥对环丙沙星的吸附能力降低,吸附量减少。当Ca~(2+)浓度增加到1.5mol/L时,Ca~(2+)和环丙沙星二者间的竞争性吸附逐渐达到平衡,底泥对环丙沙星的吸附量不会再随Ca~(2+)浓度的增加而变化,此时吸附量为总量的62.34%,由此可推断阳离子交换是环丙沙星在底泥中吸附过程的重要机制之一。     

Comparison of the surface chemical properties of four soils derived from Quaternary red earth as related to soil evolution

The surface chemical properties of soil samples i.e., surface charge and zeta potential, and the mineralogy of soil clay fraction were investigated with reference to soil weathering extent for four different soils derived from Quaternary red earth using the ion adsorption method, a micro-electrophoresis method and the X-ray diffraction analysis. Results indicated that all these soil samples contained kaolinite and gibbsite. The Ultisols from Guizhou, Hunan and Jiangxi possessed the 2:1 type clay minerals of mica and vermiculite. Hematite and magnetite were found in the Ultisols from Guangxi, Hunan and Jiangxi. Goethite was found in the Ultisols from Jiangxi, Hunan and Guizhou. The positive surface charge for these soils decreased with the order: the Ultisol from Guangxi ≅ the Ultisol from Guizhou > the Ultisols from Hunan and Jiangxi from south to north when pH < 5.0. This is consistent with the content of free Fe/Al oxides present in these soils. On the other hand, the value of negative surface charge on the Ultisol from Guangxi was found much lower than the other soils perhaps because of the intensive weathering of the soil. Both permanent and variable negative charges for the former were also lower than the latter, whereas the point of zero salt effect (PZSE) for the former was greater than that of the latter. The variability of soil negative surface charge followed the order: the Ultisol from Guangxi > the Ultisol from Guizhou > the Ultisol from Jiangxi ≅ the Ultisol from Hunan. The zeta potential and isoelectric point (IEP) of soil colloids and soil net surface charge followed the same order: the Ultisol from Guangxi > the Ultisol from Guizhou > the Ultisols from Hunan and Jiangxi. A good correlation between zeta potential and net surface charge of these soils was observed. Therefore, the magnitudes of the PZSE, IEP and zeta potential of these soils were in agreement with the weathering extent of the soils and can be employed as reference criteria for classification and evolution of soils.     

Effects of tilling no-till soil on losses of atrazine and glyphosate to runoff water under variable intensity simulated rainfall

Herbicides released through agricultural activities to surface waters and drinking water systems represent a risk to human and environmental health, as well as a cost to municipalities for removal. This study focuses on the viability of glyphosate tolerant cropping systems as an alternative to atrazine-based systems, and the impact of tilling historically no-till ground on the runoff pollution potential of these systems. Variable intensity field rainfall simulations were performed on 2 m long × 1 m wide plots within a field in first-year disk and harrow following no-till (CT), and within a long-term no-tilled (NT) field, both treated with atrazine and glyphosate according to label. Rainfall sequence was: 50 mm h⁻¹ for 50 min followed by 75 mm h⁻¹ for 15 min, 25 mm h⁻¹ for 15 min, and 100 mm h⁻¹ for 15 min. Runoff was collected at regular time intervals during two simulated rainfall events and analyzed for herbicide concentration, sediment content, and volume. Maximum glyphosate concentration in runoff was 233 μg L⁻¹ for NT and 180 μg L⁻¹ for CT (approximately 33% and 26% of the maximum contaminant limit (MCL) for glyphosate (700 μg L⁻¹), respectively, while maximum atrazine concentrations in runoff was 303 μg L⁻¹ for NT and 79 μg L⁻¹ for CT (approximately 100 times and 26 times the atrazine MCL (3 μg L⁻¹)). Atrazine concentration and loading were significantly higher in runoff from NT plots than from CT plots, whereas glyphosate concentration and loading were impacted by tillage treatment to a much lesser degree. Results suggest that glyphosate-based weed management may represent a lower drinking water risk than atrazine-based weed management, especially in NT systems.     

Adsorption of atrazine, hydroxyatrazine, deethylatrazine, and deisopropylatrazine onto Fe(III) polyhydroxy cations intercalated vermiculite and montmorillonite

This paper describes the modification of the clay minerals vermiculite (VT) and montmorillonite (MT) by intercalating Fe(III) polymers of different [OH(-)]:[Fe(III)] ratios with the aim of removing atrazine (AT) and its metabolites deethylatrazine (DEA), deisopropylatrazine (DIA), and hydroxyatrazine (ATOH) from aqueous solution. An enhancement of adsorption capacity was observed for both intercalated clay minerals in comparison to the potassium-saturated materials (KVT or KMT). The results showed that different [OH(-)]:[Fe(III)] molar ratios had a small influence on the adsorption capacity, as well as in the basal spacing, BET surface area, and porosity. For the lowest initial concentrations of AT, DIA, and ATOH (0.050 mg L(-)(1)) studied, the modified VT adsorbed almost 80% of AT and DIA, while ATOH was removed at concentration levels below the detection limit of the technique, implying in at least 99.5% of sorption. Weak interaction between intercalated VT and DEA was observed, although a significant adsorption enhancement occurred in comparison to KVT. Within a 24 h interval, desorption of AT and DIA in aqueous medium reached levels close to 20% of the amount initially adsorbed, while for ATOH only 3% of the adsorbed compound was desorbed. The adsorption capacity of the Fe(III)-intercalated VT decreased after the first adsorption/desorption cycle, implying that the material is not suitable for reutilization. The intercalated MT was a powerful sorbent for AT, DEA, DIA, and ATOH, removing all of these chemicals from solution almost quantitatively (sorption greater than 99.5%), even at initial concentrations as high as 1.0 mg L(-)(1). Additionally, desorption of AT, ATOH, and DIA in water was not measurable up to the tube corresponding to the initial concentration of 1.0 mg L(-)(1), suggesting strong irreversible binding of these compounds to the intercalated MT materials. Desorption of DEA from the intercalated MT was between 5 and 30%. Unlike what was observed for VT, the intercalated MT materials were recyclable, keeping an excellent performance when reutilized.     

不同pH/离子强度时Cu/Cd复合污染土壤解吸和迁移特征

重金属污染土壤在用固化/稳定化技术修复后,若外部环境发生变化,失去活性的重金属会否再次释放出来并在土壤中迁移,造成污染风险,是一个值得探讨的重要科学问题。为揭示不同化学因素对污染土壤中重金属活化及迁移过程的影响,通过室内土柱实验,研究了不同离子强度、pH及阳离子类型（Ca2+、Na+）下Cu2+、Cd2+在土壤中的解吸及迁移行为。结果表明：总体而言,离子强度增大,Cu2+、Cd2+淋出浓度峰值也随之增大;此外,在CaCl2淋溶阶段,0.005、0.01、0.05、0.1 mol·L-1 CaCl2时,Cu2+、Cd2+解吸量依次增加,且Cd2+的解吸量高于Cu2+,而0.5 mol·L-1 CaCl2时抑制了Cd2+的解吸,且Cu2+的解吸量高于Cd2+。pH减小时,Cu2+、Cd2+解吸量增大,即偏酸性的环境有利于Cu2+、Cd2+的解吸;但从Cu2+、Cd2+浓度峰值来看,pH为3时的Cu2+、Cd2+浓度峰值反而小于pH为4、5时。Ca2+较Na+更有利于Cu2+、Cd2+的解吸,但在0.005 mol·L-1时,NaCl溶液更有利于Cu2+的解吸,并且去离子水淋溶阶段Cu2+浓度要高于CaCl2淋溶阶段;此外,离子强度为0.005、0.05和0.5 mol·L-1 NaCl的三种情况下均出现了土壤颗粒的出流,且0.05和0.5 mol·L-1 NaCl时,存在流速下降的现象。