典型雌激素在水稻土中的吸附特征及高岭土和猪粪DOM对吸附的影响

畜禽粪污还田资源化利用的同时,带来了雌激素类物质污染风险,而吸附特性决定了雌激素的土壤环境风险和生物可利用性.为掌握雌激素在土壤中的吸附特性,采用批吸附室内模拟实验研究了典型雌激素雌酮(E1)、雌二醇(E2)和炔雌醇(EE2)在水稻土中的吸附动力学和热力学特征,以及掺杂高岭土和添加猪粪溶解性有机质(DOM)对土壤吸附雌激素的影响.结果表明,E1、E2和EE2的吸附动力学均符合拟二级反应动力学方程(R20.997),热力学特征可用Freundlich吸附等温式描述(R20.990).总体水平上,高岭土掺杂比例与3种雌激素土壤吸附能力呈显著正相关(P0.05),且随掺杂比例的增加,拟合曲线趋于线性.随猪粪DOM添加量增加,E1和EE2的吸附系数(KF)减小,而E2的KF值出现先增大后减小的现象.综合分析表明,高岭土能促进土壤对雌激素的吸附,且氢键作用和游离羟基是增强吸附的重要原因;而猪粪DOM会降低土壤对雌激素的吸附,从而增加雌激素从土壤迁移到地表水和地下水中的风险.     

吸附反应时间对除草剂阿特拉津吸附行为的影响

采用批量动态实验方法,对潮土中阿特拉津吸附特征随吸附反应时间变化进行了研究。结果表明,土壤吸附的阿特拉津量随反应时间的变化符合双曲线函数关系。在50μg·L-1～2000μg·L-1浓度系列下,在48h内,土壤颗粒对阿特拉津的吸附属于快反应,土壤吸附的阿特拉津量随吸附反应时间呈指数上升,为吸附实验结束(168h)时土壤吸附阿特拉津总量的58%到90%。当吸附反应时间超过48h后,随反应时间增加,土壤吸附阿特拉津量差异变化不显著。阿特拉津在潮土颗粒和土壤溶液中的相分配可用Freundlich方程描述。吸附容量因子Kf与吸附反应时间之间有极显著的线性正关系(r2=0.9063**,p<0.0001)。无量纲的非线性因子n与吸附反应时间之间也具有显著的线性负关系(r2=0.5666*,p=0.0192)。     

水溶性有机质对土壤吸附芘的影响

多环芳烃(PAHs)有高疏水特性,再加上土壤对PAHs的吸附作用,使得PAHs污染土壤的生物修复十分困难。水溶性有机物(Dissolved Organic Matter,DOM)虽仅占土壤有机质的很小部分,却是影响PAHs在土壤中的转化、迁移的重要因子。为了认清DOM在生物修复PAHs污染土壤中的影响作用,以四环的芘作为目标污染物,以蚯蚓粪和生猪粪作为DOM的主要来源,研究了去除内源DOM土壤和原土壤吸附PAHs的区别,探索了不同用量、不同分子量、不同来源的DOM对土壤吸附芘的影响。结果表明,(1)内源DOM抑制土壤对芘的吸附作用,去除内源DOM可促进土壤对芘的吸附。(2)不同用量DOM对土壤吸附有机污染物的作用取决于DOM的临界值质量浓度、水土比及其吸附机理。当水土比为124,DOM小于临界值时,DOM对有机物增溶起主要作用,DOM的增加抑制芘的吸附;当DOM大于临界值时,共吸附和累积吸附起主要作用,DOM促进芘的吸附。当水土比为49时,DOM质量浓度的增大能促进芘的吸附。当水土比为24时,DOM质量浓度的增大抑制芘的吸附。(3)DOM的大分子量组分质量浓度越高,对芘的增溶作用越大,更能促进芘的溶解,从而抑制土壤对芘的吸附,小分子量组分DOM的作用则相反;中分子量DOM对土壤吸附芘的影响类似于大分子量DOM。研究DOM对土壤吸附芘的影响,对于PAHs污染土壤的修复有着重要的意义。     

水溶性有机质对土壤吸附有机污染物的影响

在自然环境中,水溶性有机质(DOM)会对土壤吸附有机污染物产生影响.基于已有的成果,本文综合分析了DOM的有关因素对土壤吸附有机污染物的影响.研究表明,不同来源的DOM的亲疏水组分比例不同;随着腐解时间的增长,亲水组分减小,疏水组分增加.外源DOM的极性与亲疏水组分所含官能团的种类和数量、分子量均会影响有机污染物的吸附;DOM的临界值浓度与土壤有机质含量负相关.当DOM浓度大于临界值时抑制吸附,反之促进吸附.DOM具有酸碱缓冲作用,影响土壤溶液的pH,进而影响对有机污染物的吸附.由于土壤内源DOM对有机污染物具有增溶作用,会抑制土壤吸附有机污染物.论文最后对今后的相关研究方向提出了建议.     

铁铝土对溶解性有机质的吸附特性

采用批实验方法,结合XAD树脂分组技术研究铁铝土对3种不同亲/疏性DOM(堆肥DOM、秸秆DOM、土壤DOM)的吸附特征并分析其影响因素.结果表明:(1)铁铝土对DOM具有强吸附力,吸附量随DOM初始浓度的增加而增加,吸附动力学包括快吸附和慢吸附两个阶段,符合一级扩散方程;(2)等温吸附特征符合Freundlich方程,为物理作用主导的多层吸附过程;(3)对于同种DOM,铁铝土对DOM的吸附量表现为暗红湿润铁铝土简育铁铝土潜育水稻土,对50 mg·L~(-1)的堆肥DOM在暗红湿润铁铝土的吸附量达594.9 mg·kg~(-1),与CEC、游离氧化铁、游离氧化铝、粘粒呈极显著正相关,与砂粒呈负相关;(4)对于同种铁铝土,高疏水性DOM在铁铝土吸附量更大,表现为堆肥DOM(H-DOM)土壤DOM(M-DOM)秸秆DOM(L-DOM);(5)铁铝土对DOM各组分的吸附力表现为疏水中性组分(HON)酸不溶组分(AIM)疏水碱性组分(HOB)疏水酸性组分(HOA)亲水性组分(HIM),结合各组分的红外光谱特征,推测脂肪链状结构、高芳香性是影响吸附量的关键.(6)DOM各组分对DOM吸附量的贡献是各组分吸附能力与含量的综合作用结果.对于亲疏水性组分,HO对DOM吸附量的贡献大于HIM,达69.43%—85.08%;对于各极性-电荷特性组分,表现为H-DOM:HOA(40.24%)HON(39.1%)HIM(14.92%)AIM(3.82%)HOB(1.88%);LDOM:HOA(33.50%)HIM(30.57%)HON(24.81%)AIM(7.45%)HOB(3.68%).(7)内源DOM对铁铝土吸附外源DOM起抑制作用,且对高疏水性的DOM抑制作用更强.     

生物炭降低土壤中2,4,6-TCP有效性能力的评估

2,4,6-三氯苯酚(2,4,6-TCP)作为杀菌剂、除草剂、防腐剂被广泛应用于农业,土壤中2,4,6-TCP污染引起了人们的关注。采用批平衡实验研究了2,4,6-TCP在4种土壤(乌栅土、红壤、黑土、潮土)中的淋溶迁移性,以及在生物炭和土壤中的吸附效果。结果表明,2,4,6-TCP在土壤中淋溶迁移性大小顺序为潮土乌栅土黑土红壤。2,4,6-TCP在4种土壤中吸附等温线采用Freundlich方程拟合最佳,在乌栅土、红壤、黑土和潮土中的吸附常数Kf分别为0.775 9、75.01、100.3和0.904 7。红壤和黑土对2,4,6-TCP有很强的吸附能力,吸附曲线呈较为明显的非线性,可能为表面吸附;而乌栅土和潮土的吸附能力很差,吸附曲线呈较为明显的线性,可能为分配作用。由不同原料(稻杆、果壳、椰壳)制备的生物炭对2,4,6-TCP吸附量有明显的差异,其中椰壳生物炭吸附效果最好。添加椰壳生物炭后,土壤对2,4,6-TCP吸附能力增强,生物炭在土壤-生物炭混合体系吸附2,4,6-TCP中起主导作用,且受土壤类型的影响。并通过模型评估生物炭修复2,4,6-TCP污染土壤的可行性,其中椰壳生物炭修复效率最高,去除土壤中50%的2,4,6-TCP所需椰壳生物炭用量为2 675 kg·hm-2。研究结果为生物炭降低土壤中2,4,6-TCP有效性的评估和修复2,4,6-TCP污染土壤提供了科学依据。     

机物料中溶解性有机质对土壤吸附除草剂的抑制作用

溶解性有机质(DOM)是陆地及水生生态系统中十分活跃的组分,对有机污染物质的环境行为 (如毒性、迁移转化及生物可降解性等)有着重要的影响,而施用有机物料会释放大量的DOM.采用批量平衡法研究了水稻秸秆腐解产生的溶解性有机质对苄嘧磺隆(BSM)在土壤中吸附行为的抑制作用.结果表明,线性方程能很好地描述BSM在土壤中的吸附行为;添加DOM降低了BSM在土壤中的分配系数即logKd值,其logKd值与对照(不加DOM)间存在极显著差异(P<0.01),秸秆腐解时间越长,logKd值越小;亲水组分和疏水组分在DOM抑制土壤吸附BSM中起着不同的作用;BSM在土壤上的吸附自由能小于40 kJ·mol-1,推测BSM在土壤上主要以物理吸附为主,吸附机理可能有范德华力、疏水键、氢键和偶极键力,不存在化学键吸附作用.     

PCB138在土壤中的吸附特征及土壤特性对其吸附的影响

为研究六氯联苯PCB138在土壤组分中的吸附特征及土壤特性对其吸附的影响,选取红壤和有机质含量较高的黑土作为供试土壤,提取土壤有机质组分中的胡敏酸和胡敏素,采用振荡平衡法研究了PCB138在原供试土壤、胡敏酸和胡敏素中的吸附特征。结果表明,PCB138在两种土壤组分中的吸附是一个快速吸附过程,240 min即可达到吸附平衡。PCB138在土壤组分中吸附速率和吸附量表现为:胡敏酸﹥原土壤﹥胡敏素,准一级动力学方程能更好地描述其吸附过程。PCB138在黑土中的吸附速率和吸附量略大于其在红壤中的相应数值。PCB138在两种土壤中的吸附过程可用Freundlich吸附等温方程描述。Pearson相关性分析结果表明,PCB138在两种土壤组分中的吸附量与土壤中有机质量分数和2μm粒径质量分数呈显著相关(P0.05)。吸附速率与土壤中有机质质量分数呈极显著相关(P0.01)。实验条件下,土壤中有机质质量分数和2μm粒径质量分数可能是影响PCB138在土壤组分中的吸附行为的主要土壤特性因素。本研究可为揭示PCBs的环境行为与污染控制提供依据。     

可溶性有机物对土壤汞向大气释放的影响

通过模拟试验,研究了浸提自稻草、腐殖土和堆肥的可溶性有机物(DOM)对紫色潮土、紫色土和黄壤三种土壤中汞向大气释放的影响.结果表明,DOM尤其是堆肥DOM能有效地抑制土壤汞向大气的释放,且土壤中DOM添加量越高,土壤汞释放量越少,即DOM对土壤汞释放的抑制作用越强;不同土壤类型,DOM的抑制作用不同,三种土壤汞释放量大小顺序均为:紫色潮土紫色土黄壤.     

三峡水库消落区土壤汞吸附解吸动力学特征

对三峡水库消落区5种土壤进行了汞的吸附-解吸试验,用不同的等温吸附方程和化学反应动力学方程进行了模拟比较,结果显示,不同土壤对汞的吸附解吸动力学规律相类似,吸附速率和解吸速率均与土壤pH值呈显著(r=0.933,p＜0.05)和极显著相关性(r=0.962,p＜0.01),但吸附量和解吸量各不相同,其中,紫色潮土对汞的吸附量最大,酸性紫色土最小;灰棕潮土对汞的解吸量最大,黄壤最小,其它类型土壤介于它们之间.     

Influence of dissolved organic matter from corn straw on Zn andCusorption to Chinese loess

The interaction of Zn and Cu with dissolved organic matter (DOM) is a significant physicochemical process affecting their sorption as well as mobility in soil. The objective of this study was to examine the influence of DOM from corn straw on the sorption of Zn and Cu by loess through batch adsorption technique. The sorption isotherms of Zn and Cu could be well described by the Freundlich equation, and the partition distribution coefficient (k) in the presence of DOM was reduced by 86% for Zn and 58% for Cu, as compared to the control receiving no DOM, suggesting that DOM had a stronger inhibitory effect on Zn sorption than that of Cu. In addition, the sorption of metal increased with an increase in pH for loess, with maximum inhibition on metal sorption observed at pH > 7.6 for Zn and pH > 5.5 for Cu in the absence ofDOM but Cu sorption of DOM was suddenly decreased with an increase of pH at pH > 7.9 in the presence of DOM. At a DOM concentration of <200 mg L^?1, sorption of Zn and Cu was reduced by 46% for Zn and 32% for Cu with an increase in DOM concentration.     

Response of roselle (Hibiscus sabdariffa) to heavy metals contamination in soils with different organic fertilisations

The response of green roselle (Hibiscus sabdariffa) to Cu/Pb contamination and manure application in soil was investigated using pot experiments. Subsamples of a mineral soil were treated with increasing doses (0–500 mg kg^?1) of Cu/Pb only and/or amended (at 10% w/w) with poultry or swine manure. Roselle plants were grown, monitored for changes in growth rate and post-harvest aboveground dry biomass and tissue Cu/Pb concentrations were determined. The plants were typically greenish with linear growth profiles at all metal doses, indicating some level of tolerance. Dry biomass yields decreased as metal dose increased. Poultry manure enhanced roselle biomass yields better than swine manure. Tissue Cu/Pb concentrations increased linearly as metal doses increased in unamended soils; whereas nonlinear responses were observed in manure-amended soils. Soil-to-plant transfer factors, T _f (%) indicated that Cu (13≤T _f (% )≤60) was more phytoavailable to roselle than Pb (11≤T _f (% )≤20). Tissue metal concentrations were modelled from soil pH, organic matter, plant available and pseudototal metal; but the models appeared more reliable with plant available metal as a covariate than with pseudototal metal content. These observations may become useful whenever phytoextraction is the remedial option for soils moderately contaminated by toxic metals.     

Elucidation of phosphorous sorption by calcareous soils using principal component analysis

This study was conducted to understand the mechanisms governing P-sorption and desorption by calcareous soils (up to 48% CaCO ₃). Batch experiments with KCl as background were carried out by adding varying amount of P up to 100 mgP.L^?1. The desorption percentage (%DES) results show that little P was released from the adsorbed phase. Principal component analysis was applied to evaluate the combined influence of soil components on P sorption. The complex P sorption process can be related to specific soil components by the following equation: P? sorption=?2.20 (CaCO ₃% )?0.04 (Fe? oxide)+0.04 (pHe)+11.02 (sand % )+3.35 (silt)?10.73 (clay)?1.24 (EC)?0.22 (OM)?0.81 (CEC)?1.93 (P? Olsen) (R²=0.9941, SSE=380). Sand% and clay% are the most significant variables for modelling P sorption data. The derived equation could be applied to predict P sorption in other soils that have similar compositions to those investigated herein. The degree of P saturation (DPS) threshold level for all soils was less than 3% except in the soil with the lowest iron oxide. All of the studied soils have exceeded the environmentally unacceptable P concentration except the soil with the lowest iron oxide content.     

Heavy metals in soils and crops in Southeast Asia

In a reconnaissance soil geochemical and plant survey undertaken to study the heavy metal uptake by major food crops in Malaysia, 241 soils were analysed for cation exchange capacity (CEC), organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) using appropriate procedures. These soils were also analysed for arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) using aqua regia digestion, together with 180 plant samples using nitric acid digestion. Regression analysis between the edible plant part and aqua regia soluble soil As, Cd, Cr, Cu, Hg, Ni, Pb and Zn concentrations sampled throughout Peninsular Malaysia, indicated a positive relationship for Pb in all the plants sampled in the survey (R ² = 0.195, p < 0.001), for Ni in corn (R ² = 0.649, p < 0.005), for Cu in chilli (R ² = 0.344, p < 0.010) and for Zn in chilli (R ² = 0.501, p < 0.001). Principal component analysis of the soil data suggested that concentrations of Co, Ni, Pb and Zn were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. Chromium was correlated with soil pH and EC, Na, S, and Ca while Hg was not correlated with any of these components, suggesting diffuse pollution by aerial deposition. However As, Cd, Cu were strongly associated with organic matter and available and aqua regia soluble soil P, which we attribute to inputs in agricultural fertilisers and soil organic amendments (e.g. manures, composts).     

Arachis hypogaea derived activated carbon steered remediation of Benzimidazole based fungicide adsorbed soils

Sorption characteristics of the Benzimidazole fungicide Carbendazim were assessed in seven different soils using batch equilibrium method and analysed by UV-Vis spectrophotometer. The values of adsorption co-efficient K_d ranged from 14.3 to 39.8?µg/mL depending upon unique physiochemical properties of soils. Negative values for Gibbs free energy (ΔG) proposed an exothermic and low interaction between Carbendazim and soil samples leading to physiosorption. Statistical analysis showed a negative correlation of soil pH and K_d (R²= ?0.80) and a positive correlation with organic matter (R^2?=?0.77). Activated carbon prepared from Arachis hypogaea (peanut shells) by acid activation for Carbendazim removal from soils was characterised by FTIR spectrometry, indicating the change in functional groups. The highest percentage removal observed was 70% in 5?ppm initial Carbendazim concentration while 65% in 7.5?ppm concentration. This method can be implied in agricultural soils as an efficient and cheap technique for removing the hazardous pesticides from the environment.     

中国南方稻田土壤汞含量及潜在危害评价

选择我国南方水稻主产区安徽、浙江、湖南、湖北以及广西5个省,采集213个稻田土壤样品,探究我国南方稻田土壤中汞的空间分布特征与土壤理化参数(如p H值和有机质)的相关关系及汞富集的潜在危害。结果表明:不同省份的稻田土壤汞含量存在显著的差异(P0.05,n=213),含量范围是0.029~0.326 mg·kg~(-1)(干重),平均值为(0.094±0.036)mg·kg~(-1),与农用地土壤环境质量标准0.30 mg·kg~(-1)(GB15618—1995)相比,除湖北省以外均有轻度汞污染。Pearson相关性分析表明,稻田土壤中的汞含量与有机质含量呈显著正相关关系(P0.01,r=0.445),说明适度偏高的有机质有利于土壤汞的富集。不同省份稻田土壤潜在危害等级除浙江省外均在轻微到中等的范围内,浙江省的为强等级。     

Kinetic,equilibrium and thermodynamic studies for the sorption of metribuzin from aqueous solution using banana peels,an agro-based biomass

Banana peels were employed for the removal of metribuzin from aqueous solution. Sorption in the batch mode was optimized regarding pH, contact time, sorbent dose, initial pesticide concentrations, and temperature. The sorption data were fitted to pseudo-first-order, pseudo-second-order, intraparticle diffusion, Elovich, and liquid film diffusion model, the pseudo-second-order exhibiting best fit (R² = 0.9803). Of the four most common sorption isotherm models (Langmuir, Freundlich, Tempkin, and Dubinin–Radushkevich), the data followed the Langmuir isotherm with highest correlation. The maximum adsorption capacity was found to be 167 mg g^?1. Gibbs free energy, enthalpy, and entropy showed that the sorption was exothermic and spontaneous.     

表面活性剂及水溶性有机物对菲生态毒性的影响

采用室内培养试验及化学试验研究了表面活性剂及水溶性有机物(DOM)对土壤中菲对小麦的生态毒性的影响.结果表明,绿肥和猪粪堆肥DOM具有具有类似表面活性剂的表面活性性质,且猪粪堆肥的表面活性较大;在本试验条件下,DOM对菲对小麦的生态毒性有减轻作用,而表面活性剂对菲生态毒性有增加的趋势;当DOM和表面活性剂共存时,菲的生态毒性则比DOM单独作用时的结果强,而弱于表面活性剂单独作用的结果.     

Adsorption of cationic and anionic surfactants onto organic polymer resin Lewatit VPOC 1064 MD PH

The adsorption of a cationic (CTAB, cetyl trimethylammonium bromide) and an anionic surfactant (SLES, sodium dodecylethersulfate) from aqueous solution onto organic polymer resin (Lewatit VPOC 1064 MD PH) was studied. A series of batch experiments were performed to determine the sorption isotherms of surfactants to organic polymer resin. The experimental studies were analyzed by Langmuir and Freundlich isotherms. Furthermore, the isotherm parameters, average percentage errors (ε) of model data, and separation factor (R _L) were calculated. Other factors influencing the adsorption capacity (contact time, adsorbent amount, and initial surfactant concentration) were also discussed. The experimental data fitted very well to the Langmuir equilibrium model in the studied concentration range. The calculated R _L values showed that the adsorption of both surfactants were favorable. Among the surfactants, CTAB showed higher adsorption capacity onto organic polymer resin compared to SLES (Q ⁰ = 250 and 34.36 mg g⁻¹, respectively).     

Sorption of heavy metals on organic and inorganic soil constituents

Sorption of heavy metals to organic matter and mineral soil constituents can hardly be separated experimentally. Here we studied the retention capacity of organic matter and minerals from soils in a long-term field experiment in which the organic carbon content had been altered, but the mineral phase had remained constant over time. The sorption of Cu, Cd and Zn showed a non-additive contribution of soil organic matter and minerals to the sorption capacity of soil. Sorption on organic matter exceeded mineral sorption from 6 to 13 times. This is the first time that sorption to soil organic matter is quantified in bulk soils.