Minimization of methabenzthiazuron residues in leaching water using amended soils and photocatalytic treatment with TiO2 and ZnO

In the present work, potential groundwater pollution by methabenzthiazuron （MTBU） and the effect of three different amendments （composted sheep manure, composted pine bark and spent coffee grounds） on its mobility were investigated under laboratory conditions. The efficiency of ZnO and TiO2 suspensions in the photocatalytic degradation of MTBU in leaching water was also investigated. The relative and cumulative breakthrough curves were obtained from disturbed soil columns. The presence and/or addition of organic matter drastically reduced the movement of the herbicide. On other hand, photocatalytic experiments showed that the addition of ZnO and TiO2 strongly enhances the degradation rate of this herbicide compared with the results of photolytic experiments under artificial light. ZnO appeared to be more effective in MTBU oxidation than TiO2. The results obtained point to the interest of using organic wastes and heterogeneous photocatalysis for reducing the pollution of groundwater by pesticide drainage.     

多重环境因子对氟胺磺隆在土壤中降解的影响

氟胺磺隆作为普遍使用的一种磺酰脲类除草剂,已经对土壤和作物造成了危害,其环境行为受很多物理化学或生物因素的影响.为探明不同环境因素对氟胺磺隆在土壤中降解程度的影响,通过实验室内模拟培养的方法,研究了土壤微生物、不同土壤类型、水溶性有机物（dissolved organic matter,DOM）、温度、土壤含水量等因素对氟胺磺隆在土壤中降解的影响.结果表明,各种环境因子：温度、湿度、土壤微生物和土壤类型等均在不同程度上影响了氟胺磺隆的土壤降解速率.土壤微生物量、土壤有机质和DOM的增加均有利于氟胺磺隆在土壤中的降解,并且土壤pH的降低,也会促进氟胺磺隆在土壤中的降解.其中,土壤微生物是影响氟胺磺隆土壤降解的主要因素.该研究结果将为一些生物和物理化学因子调节氟胺磺隆在土壤中消散提供初步数据.     

Adsorption of acetanilide herbicides on soil and its components. II. Adsorption and catalytic hydrolysis of diethatyl-ethyl on saturated Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite

Adsorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na⁺-, K⁺-, Ca²⁺-, and Mg²⁺-montmorillonite clays were investigated in water solution. The Freundlich adsorption coefficient, Kf, got from isotherms on clay followed the order of Na⁺ K⁺ > Mg²⁺ Ca²⁺. Analysis of FT-IR spectra of diethatyl-ethyl adsorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for adsorption, indicating that adsorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing the cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid.These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by adsorption on the clay surface.     

有机垃圾序批式厌氧消化水解动力学模型研究

在传统一级模型中引入水解有机颗粒表面积,推导并建立了片状颗粒、圆柱形颗粒和球形颗粒有机物水解修正一级模型.片状颗粒模型与传统一级模型的表达式相同.圆柱形颗粒模型和球形颗粒模型的水解速率与未水解颗粒有机物浓度并非服从一级反应动力学,而是分别与未水解颗粒有机物浓度的3/2和5/3次方成正比,且与颗粒有机物的初始浓度有关.通过试验求得有机垃圾的传统一级模型、圆柱形颗粒模型和球形颗粒模型的水解速率常数分别为0.2493、0.5378和0.6741d-1.模型预测结果与残差分析表明,有机垃圾的形状更接近于圆柱形或球形,修正一级模型比传统一级模型能更好地预测有机垃圾的水解过程.     

Sorption and cosorption of the nonionic herbicide mefenacet and heavy metals on soil and its components

Sorption and cosorption of the nonionic herbicide mefenacet and two typical metals (copper and silver) on black soil and its components (kaolinite and humic acid) were investigated. It was found that because of their different valences and properties, Cu²⁺and Ag⁺ presented different effects on the sorption of mefenacet. Due to the competition of Cu²⁺, along with the shells of dense water formed by its surface complexation, for sorption surface area with mefenacet, the addition of Cu²⁺ decreased the sorption amount of mefenacet on soil and its components, especially on humic acid. However, the addition of Ag⁺ significantly enhanced the sorption of mefenacet, which was attributed to the softness of the cation that weakened the hydrophilicity of the local region around Ag⁺-complexed functionalities, and thus mitigated the competitive sorption of water. In addition, the sorption of mefenacet on soil with or without the two metals was generally decreased with increasing pH, which was caused by the hydrolysis of carbonyl and carboxyl groups on the surface of the sorbents, π-π interaction between mefenacet and the soil organic matter, and so on. On the other hand, the presence of mefenacet seemed to have little effect on the sorption of Cu²⁺ and Ag⁺, indicating that Cu²⁺ and Ag⁺ might be sorbed strongly on the tested sorbents and the mefenacet added was too low in concentration to affect the sorption of the metals.     

预加入柠檬酸螯合亚铁对过硫酸盐降解土壤中农药的影响

螯合亚铁活化过硫酸盐可高效氧化降解土壤中有机污染物,但由于土壤组分的竞争效应,通常情况下修复药剂的利用效率较低. 本研究选取柠檬酸螯合亚铁(Fe2+-CA)为模型活化剂,考察了活化剂预加入对其活化过硫酸盐(PS)氧化降解不同土壤中农药、多环芳烃的影响. 结果表明:Fe2+-CA的预加入影响了柠檬酸螯合亚铁活化过硫酸盐体系(简称“Fe2+-CA/PS体系”)对土壤中莠去津的降解效果,土壤中莠去津的降解率与活化剂预加入时间的关系呈倒U型趋势线,其中在活化剂预加入约5 min时,莠去津的去除率(73.6%)达最大值,相比修复药剂直接加入体系的效果增加了17%. 相关测试表征显示,在活化剂预加入5 min的情况下硫酸根自由基的贡献增大,降低了土壤有机质对氧化剂的消耗,提高了过硫酸钠的有效利用率,促进了土壤中污染物的降解. 柠檬酸螯合亚铁预加入约5 min时促进Fe2+-CA/PS体系降解土壤中污染物的效应适用于不同过硫酸钠常用浓度、不同类型土壤和不同有机污染物(包括农药和多环芳烃),但促进效果通常与过硫酸盐用量、土壤类型、污染物种类有关. 莠去津污染土壤修复扩大规模试验证实,活化剂预加入5 min使Fe2+-CA/PS体系对含水率为饱和持水量80%的土壤中莠去津的降解效果提高了47%. 研究显示,Fe2+-CA预加入约5 min时对Fe2+-CA/PS体系降解土壤中有机污染物的促进效果最好.      

甘南尕海泥炭沼泽地退化过程土壤特征和水源涵养功能的变化

由于气候变化、过度放牧、沟蚀及修路等人为影响,尕海泥炭沼泽地出现退化现象。为了查明尕海泥炭沼泽地退化过程土壤性质和水源涵养功能的变化趋势,采用空间序列代替时间序列的方法,对该区域4 种不同退化阶段泥炭沼泽地土壤性质和水源涵养功能进行了调查研究。结果表明： 随着尕海泥炭沼泽地退化程度的加剧,0~40 cm层土壤平均容重逐渐增大,总孔隙度逐渐减小,且容重和孔隙度在土壤剖面自然分布规律发生变化;土壤有机质、全氮、速效钾和水解氮含量呈逐渐降低趋势,铵态氮呈增大趋势,全磷、全钾无明显变化规律,但均沿土壤剖面分布呈波动性变化;土壤自然含水量、最小蓄水量和毛管蓄水量均为未退化最大,中度退化最小;方差分析结果表明不同退化阶段泥炭沼泽地土壤容重、总孔隙度、有机质、氨态氮及其土壤蓄水性能均存在显著差异。土壤饱和蓄水量和毛管蓄水量与有机质之间存在显著正相关,并受植被盖度和泥炭层厚度的影响。研究结果表明地下水位、植被盖度、土壤有机质含量及泥炭层厚度的下降是导致尕海泥炭沼泽地退化过程土壤性质和水源涵养功能变化的主要原因。     

Isolation and characterization of Sporobolomyces sp. LF1 capable of degrading chlorimuron-ethyl

A yeast strain which was capable of degrading sulfonylurea herbicide chlorimuron-ethyl named as LF1 was isolated from a chlorimuron-ethyl contaminated soil near the warehouse of the factory producing chlorimuron-ethyl in Shenyang City, Northeast China. The strain was identified as Sporobolomyces sp., based on its morphological and physiological characteristics and the phylogenetic analysis of 18S rRNA gene sequence. So far, this is the only yeast strain of Sporobolomyces sp. which is able to degrade chlorimuronethyl. Incubation tests showed that when the initial concentration of chlorimuron-ethyl in culture was 5 mg/L, LF1 could degrade more than 77% of the herbicide after incubation for 4 d at 30°C. The possible mechanism of chlorimuron-ethyl degradation by LF1 could be the acidic hydrolysis caused by the acids from the metabolism of the yeast strain. Further study should be conducted to examine the pathways of chlorimuron-ethyl degradation by LF1 and to approach the feasibility of using LF1 to degrade the chlorimuron-ethyl in soil system.     

Efficiency and degradation products elucidation of the photodegradation of mefenpyrdiethyl in water interface using TiO2 P-25 and Hombikat UV100

The photodegradation of mefenpyrdiethyl (MFD), an herbicide safener, was investigated in aqueous suspensions by using Degussa P-25 and Hombikat UV100 titanium oxide under simulated sunlight irradiation. The effects of initial concentration of the herbicide, pH, catalysts and hydrogen peroxide doses as well as their combinations were studied and optimized. Accordingly, the kinetic parameters were determined and the effectiveness of the processes was assessed by calculating the rate constants. A pseudo first-order kinetics was observed. Under experimental conditions, the degradation rate constants were strongly influenced using P-25 and no noticeable effect was observed for Hombikat UV100. DFT calculations with B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d,p) level of theory were performed to check whether significant conformational changes occur when the charge state of the MFD substrate changes and whether these changes could play a role in the dependency of photodegradation rate constant on the studied pH. High resolution mass spectrometry (FT-ICR/MS) was implemented to identify the main degradation products.     

Abiotic degradation of four phthalic acid esters in aqueous phase under natural sunlight irradiation

Abiotic degradability of four phthalic acid esters (PAEs) in the aquatic phase was evaluated over a wide pH range 5–9. The PAE solutions in glass test tubes were placed either in the dark and under the natural sunlight irradiation for evaluating the degradation rate via hydrolysis or photolysis plus hydrolysis, respectively, at ambient temperature for 140 d from autumn to winter in Osaka, Japan. The e ciency of abiotic degradation of the PAEs with relatively short alkyl chains, such as butylbenzyl phthalate (BBP) and di-nbutyl phthalate (DBP), at neutral pH was significantly lower than that in the acidic or alkaline condition. Photolysis was considered to contribute mainly to the total abiotic degradation at all pH. Neither hydrolysis nor photolysis of di-ethylhexyl phthalate (DEHP) proceeded significantly at any pH, especially hydrolysis at neutral pH was negligible. On the other hand, the degradation rate of diisononyl phthalate (DINP) catalyzed mainly by photolysis was much higher than those of the other PAEs, and was almost completely removed during the experimental period at pH 5 and 9. As a whole, according to the half-life (t1=2) obtained in the experiments, the abiotic degradability of the PAEs was in the sequence: DINP (32–140 d) > DBP (50–360 d), BBP (58–480 d) > DEHP (390–1600 d) under sunlight irradiation (via photolysis plus hydrolysis). Although the abiotic degradation rates for BBP, DBP, and DEHP are much lower than the biodegradation rates reported, the photolysis rate for DINP is comparable to its biodegradation rate in the acidic or alkaline condition.     

洱海沉积物有机质及其组分空间分布特征

对有机质不同组分〔TOM(总有机质)、ASOM(土壤活性有机质)、LFOM(轻组有机质)和HFOM(重组有机质)〕在洱海沉积物表层和垂向的空间分布、来源特征进行了调查研究. 结果表明:洱海表层沉积物中w(TOM)在25.7～148.9g/kg之间,w(ASOM)在4.4～62.5g/kg之间,w(LFOM)在0.2～4.2g/kg之间;w(TOM)和w(ASOM)空间分布趋势为北部湖区＞南部湖区＞中部湖区,西部湖区高于东部湖区;w(LFOM)分布趋势为南部湖区＞中部湖区＞北部湖区;洱海沉积物各组分有机质均为表层富集,而在8~30cm基本稳定,有机质组分活性越强,其富集速率越大. 湖心平台沉积物中TOM富集速率最大,北部湖湾沉积物中ASOM富集速率最大,中部湖区LFOM富集速率最大. 与长江中下游湖泊相比,洱海沉积物中有机质含量高、活性强、矿化程度低;与滇池相比,其表层富集速率较低. 北部三江和西部十八溪是洱海有机质的主要外源,退化的沉水植被是其主要内源. 水生植物残体沉积和人类活动等是影响洱海沉积物有机质空间分布及其活性的主要因素.      

餐厨垃圾厌氧保存的抑菌效果及机理分析

餐厨垃圾水分和有机物含量高,极易腐败、发臭,严重影响城市环境及其资源化利用。研究了不同保存方式对抑菌效果的影响。研究结果表明:除灭菌保存外,其他3种保存方式下样品中大肠杆菌数量顺序为直接厌氧保存组<乳酸菌厌氧保存组<自然保存组,这与样品保存期间水解酸化产物（有机羧酸和乙醇等）的浓度、乳酸+乙酸在水解产物中占比排序相反。为探究厌氧保存过程中有机酸的抑菌效果,选用大肠杆菌作为腐败菌,开展了牛津杯抑菌实验以及96孔板协同抑菌实验,结果证明,起抑菌作用的物质主要为未电离的乳酸和乙酸分子而非H+;乳酸、乙酸和乙醇的最小抑菌浓度分别为2.5,1.25,35 g/L,且乳酸+乙酸、乳酸+乙醇和乙酸+乙醇的部分抑菌浓度（FIC）指数分别为0.12、0.03和0.22,证明这3种水解产物中两两之间具有协同抑菌作用。     

土壤中苯氧羧酸类除草剂的降解动态

在室内模拟条件下研究了 2甲 4氯、2,4-D和除草醚在土壤中的降解动态 .将它们放在 3种不同有机质含量的土壤中培养 ,隔一段时间取出测定它们在土壤中的含量 ,发现随着时间的延长 ,它们的含量在逐渐减少 .在未考虑土壤中微生物的作用时 ,上述 3种农药在土壤中的稳定性与土壤中的有机质含量及 pH值似乎存在一定的相关性 .除草剂在有机质含量高的土壤中降解较快 ,2甲 4氯 ,2 ,4-D和除草醚在黑土中的降解半衰期分别为 28.6d,27.3d,71.5d;而在红土中的降解半衰期分别为223.6d,301.4d,97.6d,苯氧羧酸类除草剂在酸性土壤中表现得更为稳定 .     

蔬菜类废物两相厌氧消化水解酸化相颗粒降解规律

研究蔬菜类废物两相厌氧消化过程中水解酸化液物化性质随水解时间的变化情况,结合总有机碳(TOC)、溶解性有机碳(DOC)、颗粒粒径和溶解性有机物(DOM)分子量的分析,探讨了蔬菜类废物水解酸化过程中TOC溶出和颗粒降解之间的关系,分析了水解酸化相颗粒物降解规律.实验结果表明,蔬菜类废物水解过程可以分成两个阶段:易水解的颗粒物在前5d迅速水解,TOC浓度迅速升高,在第5d达到最大值4920mg/L,水解产生颗粒态物质的二次平均直径从第1d的58.38μm降至第5d的4.64μm,有机物快速溶出,DOC/TOC比值在第4d达到最大值85%,该水解过程可用Contois模型模拟;第5d后,难水解颗粒物质的缓慢水解起主导作用,颗粒态物质的二次平均直径从4.64μm开始逐渐增大,并稳定在8.97~10.68μm范围内,TOC和DOC溶出率逐渐降低,且DOC溶出率小于TOC溶出率.大分子溶解性有机物的降解也主要集中在水解过程的前5d,水解第1d产生的大分子DOM(1.6×109~1.9×109Da)到第5d已经全部降解成分子量在5×104~4×106Da的DOM;第5d过后,DOM的分子量分布情况并未发生较大变化.表明蔬菜类废物两相厌氧消化工艺过程中水解时间可缩短为5d.     

灭草松在土壤中吸附的支配因素

通过振荡平衡法测定了灭草松在6种土壤中的吸附等温线,计算了灭草松在吸附过程中平均偏摩尔自由能的变化值.结果表明灭草松在其中5种土壤上的吸附等温线为直线,分配常数Kd 0.14～0.31mL·g^-;土壤吸附灭草松的强弱次序为:德清水稻土＞安吉水稻土(pH4.79)＞余杭水稻土＞临安红壤＞安吉水稻土(pH7.36)＞德清黄壤.土壤性质与分配常数的相关分析,发现支配灭草松在土壤上吸附的主要因素是pH值和土壤有机质含量.灭草松在土壤上的吸附主要是中性灭草松及其阴离子在土壤有机质中的分配,与有机质性质关系不大.     

土壤污染对植物根系生长影响的研究进展

人类活动所产生的污染物通过各种途径进入土壤,其数量和速度超过了土壤的容纳和净化能力,致使土壤的自然功能失调、土壤质量恶化,从而严重影响植物的正常生长发育,造成有害物质在植物体内累积。土壤污染物进入植物体内最先进入根系,污染物在根系积累最大,浓度最高,根部受害最严重。本文以重金属砷、镉、铬和有机物农药、除草剂为例,结合相关资料探讨了土壤污染对植物根系生长的影响,植物根系对重金属的吸收与重金属的理化性质及不同植物的特性有关,对有机物的吸收与有机物的结构特性和土壤性质有关,并且讨论了该研究仍需解决的一些问题。     

Metabolism of carbaryl and carbofuran in soil planted to rice

In greenhouse experiments carbaryl and carbofuran disappeared more rapidly from a soil planted to rice than from an unplanted soil under both flooded and non-flooded (60% water-holding capacity) conditions. The rate of degradation was little affected by the moisture regime. The degradation of both carbamate insecticides proceeded essentially by hydrolysis. Further degradation of the hydrolysis products, 1-naphthol from carbaryl and 2,3-dihydro-2,2-dimethylbenzofuran-7-ol from carbofuran was slow in both planted and unplanted systems. A significant portion (20–38%) of the ring ¹⁴C in carbaryl and carbofuran accumulated in the soil as the respective hydrolysis products + soil-bound residues. Evolution of ¹⁴CO₂ from the ¹⁴C (from both side chain and ring labels) in carbaryl and carbofuran was negligible even in soil planted to rice.