Leaching of mecoprop and dichlorprop in calcareous soil. Effect of the exogen organic matter addition in this process.

Leaching studies of mecorprop (R,S)-2-(4-chloro-2-methylphenoxy)propanoic acid, and dichlorprop, (R,S)-2-(4-chloro-2,4-dichlorophenoxy) propanoic acid, under saturated conditions were conducted in unamended and amended soil columns. The purpose of the study was to investigate the leaching of these herbicides in three type of soils and the exogen organic matter effect on this process. The leaching patterns could be related to variation in the soil texture and diffusion processes of the herbicides into micropores within the walls of conducting pore. The leaching rate in the amended soil columns decreased with the addition of organic matter. The breakthrough curves (BTC) of these herbicides in the leachates of the amended soil columns were wider and more diffused than the BTC obtained for the corresponding unamended soil. The theoretical BTC overestimated the pore volume required for the displacement of these pesticides from the soil column. This may be due to the differences in the adsorption process between the bacth and soil columns methods.     

污泥施用对根际和非根际石灰性土壤中细菌多样性的影响

为研究污泥施用对石灰性土壤细菌多样性的影响,在连续2年种植夏玉米大田系统中,施用不同量的腐熟污泥,采集根际和非根际土壤进行16S rDNA-V3-V4区高通量测序,分析污泥施用对石灰性土壤细菌丰富度、多样性指数、群落结构、功能基因在代谢途径的影响,同时对细菌群落和环境因素之间的相关性进行分析。结果表明：污泥用量分别在3.5～37.5 t·hm⁻²和3.5～7.5 t·hm⁻²有利于非根际和根际土壤OTU数量增加;但污泥在75 t·hm⁻²过量施用时,根际和非根际土壤细菌的Shannon多样性指数显著降低,Simpson指数显著增加,Ace,Chao丰富度指数显著降低。主成分和门水平物种丰度分析表明：污泥施用量不同会造成根际和非根际细菌群落结构差异,并且当污泥施用量为75 t·hm⁻²时,明显降低了非根际土壤放线菌门的丰度;污泥施用量在3.75～37.5 t·hm⁻²时,非根际土壤中拟杆菌门丰度会明显增加。与对照相比,当污泥用量为75 t·hm⁻²时,根际土壤拟杆菌门有明显的增加,增加丰度达1.45倍,但酸杆菌门和放线菌门丰度降低了49.74%和80.57%。冗余分析(RDA)表明,土壤TN、Cd、Cu、TP是影响土壤细菌群落最主要的因素,其中TN、Cd、Cu和细菌Shannon、Simpson多样性指数呈现显著相关性(P< 0.05)。由此可见,连续过量施入污泥会对根际和非根际石灰性土壤中细菌多样性造成不利影响,而且上述微生物多样性变化可作为污泥合理施用的判断依据。     

Dissipation of racemic mecoprop and dichlorprop and their pure R-enantiomers in three calcareous soils with and without peat addition

Two racemic herbicides, mecoprop (R,S-MCPP) and dichlorprop (R,S-DCPP), as well as their enantiopure R-forms, were incubated in three calcareous soils at 15 degrees C and 80% of their field capacity to try to elucidate their behaviour in soil and compare the dissipation rates when racemic and enantiopure compounds are used. Quantitation of pesticides is made by HPLC and the R/S ratio by GC-MS. The inactive S-enantiomer from the racemic forms persists longer than the R-forms in silt and sandy loam soils, but for shorter time in the clay loam soil. The pure R-enantiomers, both for MCPP and DCPP, after incubation in soil, are partially converted into their S-forms. In all cases, the dissipation of racemic and pure enatiomeric forms is lower in the clay loam soil than in the silt and sandy loam soils. The R-forms' peristence, in the three soils, is approximately two times lower when they are incubated alone than when they are incubated as racemic compounds. When peat is added, the persistence of these herbicides in the silt and sandy loam soils increases, while in the clay loam soil it decreases. Besides, in the clay loam soil, the enantiomeric ratio (ER) changes from its S-preferential degradation to a preferential degradation of its R-form, so an increase in the persistence of the inactive S-form occurs.     

赤泥添加对石灰性土壤中Pb、Cd形态分布及小麦根系的影响

通过田间种植小麦实验,研究添加不同剂量拜耳赤泥（0%、1%、2%、3%、4%和5%）对重金属污染的石灰性土壤Pb、Cd化学形态和小麦幼苗根系的影响。培养1个月,添加赤泥显著地提高了土壤pH值,提高幅度随赤泥投加量增加而增大。培养3个月,添加不同剂量的赤泥均明显降低土壤中可交换态Pb和Cd的含量,赤泥投加量为5%时效果最为显著,分别比对照下降90%和72%。添加赤泥对所种植小麦幼苗的根系也有影响。种植5个月,小麦根系总根长、总表面积和总体积等随添加赤泥的剂量增加呈现先增大后减小的趋势,赤泥投加量为3%时增幅最大,总根长、总表面积和总体积分别比对照增加88.23%、75%和90.32%。研究表明,赤泥可作为重金属污染的石灰性土壤的理想改良剂,但考虑到小剂量赤泥（即1%~3%）促进重金属污染农田中小麦根系的生长,建议在种植区采用小剂量赤泥（即3%）处理的重金属污染修复方案。     

城市污水处理过程中溶解性有机物转化特性

运用反渗透技术对城市处理厂进出水中的溶解性有机物(DOM)进行浓缩富集,利用DAX-8大孔树脂将DOM分为亲水物质(Hy I)、类富里酸(FA)和类腐殖酸(HA)3种组分。研究表明,原污水中有机物各组分经生物处理后的总量去除近90%,各组分所占总TOC的百分含量在生化反应过程中也发生了变化:出水中HA组分有降低的趋势,平均下降9.77%,而FA和Hy I两大组分所占总和呈现上升趋势,其中类FA物质升高7.94%,而Hy I组分百分比略有下降。与进水相比,出水中Hy I、FA和HA组分在Ⅲ(色氨酸)、Ⅳ(酪氨酸)区的荧光峰全部消失,而在Ⅰ(类腐殖酸)、Ⅱ(类富里酸)荧光峰变化不大。SUVA和电位滴定结果表明出水有机物的结构发生变化,各组分的芳香性比进水有机物有所增加。研究结果表明,进水中的有机物在污水处理过程中,小分子物质可以被生物利用并形成新的代谢产物释放到水中,大分子物质却较难被生物利用,但在处理过程中其分子构造在一定程度上被微生物改变,系统的生化驯养可以达到构造改变的效果,从而影响出水各组分分子量变化。     

Quantification of centimeter-scale spatial variation in PAH, glucose and benzoic acid mineralization and soil organic matter in road-side soil

The aim of the study was to determine centimeter-scale spatial variation in mineralization potential in diffusely polluted soil. To this end we employed a 96-well microplate method to measure the mineralization of ¹⁴C-labeled organic compounds in deep-well microplates and thereby compile mineralization curves for 348 soil samples of 0.2-cm³. Centimeter-scale spatial variation in organic matter and the mineralization of glucose, benzoic acid, and PAHs (phenanthrene and pyrene) was determined for urban road-side soil sampled as arrays (7 × 11 cm) of 96 subsamples. The spatial variation in mineralization was visualized by means of 2-D contour maps and quantified by means of semivariograms. The geostatistical analysis showed that the easily degradable compounds (glucose and benzoic acid) exhibited little spatial variation in mineralization potential, whereas the mineralization was highly heterogeneous for the PAH compounds that require specialized degraders. The spatial heterogeneity should be taken into account when estimating natural attenuation rates.     

土壤有机质对铊在土壤中吸附-解吸行为的影响

研究了土壤有机质对Tl＋在红壤和黄土2种土壤中的吸附-解吸行为的影响。结果表明,去除土壤有机质后红壤和黄土对Tl＋的吸附量均明显下降,下降幅度最高分别达到24.7%和28.2%,黄土的下降幅度大于红壤;黄土对Tl＋吸附率最高下降幅度约为20%,也高于红壤的15%。土壤有机质对Tl＋吸附的贡献率平均值分别是黄土39.2%、红壤32.8%。2种土壤对Tl＋的解吸量在去除有机质之后都明显增大,在初始Tl＋浓度较高的情况下,增大幅度明显;并且Tl＋的初始浓度越高,土壤在去有机质前后的解吸率相差就越大,在Tl＋最大处理浓度为20 mg/L时,红壤和黄土的解吸率增加分别达到60.8%和65.5%。     

Effects of the organic matter from swine wastewater on the adsorption and desorption of alachlor in soil

The application of swine wastewater to the soil for agricultural purposes results in the addition of total and dissolved organic matter to the soil, which may interfere with the dynamics of pesticides in the soil. The objective of this study was to evaluate the effects of the application of total and dissolved organic matter from a biodigester and a treatment lagoon of swine wastewater in the adsorption and desorption of alachlor [2-chloro-2,6-diethyl-N(methoxymethyl acetamide)]. The assay was performed by the batch equilibrium method, and the results were fitted to the Freundlich model. The curve comparison test revealed a greater adsorption of alachlor in the soil treated with swine wastewater from the biodigester. The adsorption and desorption of alachlor increased in the soils where swine wastewater was added, and hysteresis was observed in all of the treatments.     

Nonlinear binding of phenanthrene to the extracted fulvic acid fraction in soil in comparison with other organic matter fractions and to the whole soil sample

Fractions of soil organic matter in a natural soil were extracted and sorption (or binding) characteristics of phenanthrene on each fraction and to the whole sample were investigated. The organic carbon normalized single point sorption (or binding) coefficient followed lipid > humin (HM) > humic acid (HA) > fulvic acid (FA) > whole soil sample, while the nonlinear exponent exhibited lipid > FA > HA > whole soil sample > HM. FA showed nonlinear binding of phenanthrene as it often does with other fractions. HM and HA contributed the majority of organic carbon in the soil. The calculated sorption coefficients of the whole soil were about two times greater than the measured values at different equilibrium phenanthrene concentrations. As for phenanthrene, the sorption capacity and nonlinearity of the physically mixed HA-HM mixtures were stronger as compared to the chemically reconstituted HA-HM composite. This was attributed to (besides the conditioning effect of the organic solvents) interactions between HA and HM and acid-base additions during fractionation.     

Aniline and 2,4,6-trinitrotoluene associate preferentially to low molecular weight fractions of dissolved soil organic matter

Aniline and 2,4,6-trinitrotoluene (TNT) were equilibrated with particulate (POM) and dissolved organic matter (DOM) from an organic soil at different compositions of adsorbed major cations (Na, Al) and pH (aniline: 3.7–5.1, TNT: 4.8–5.0). After separation of POM, concentrations of ¹⁴C-labelled aniline and TNT* (including TNT degradation products) were determined in DOM size fractions using size-exclusion chromatography (SEC) and UV-detection. Concentrations in the <3.5 kDa size fraction were 2.8–6.0 and 8.5–9.5 times higher for aniline and TNT*, respectively, as compared to the >40 kDa fraction. Thus, both aniline and TNT* were preferentially associated to the smallest DOM size fraction. The significant binding to DOM (similar extent as to POM) and the fact that the <3.5 kDa DOM fraction was less susceptible to flocculation by major metals suggests that the mobility of aniline and TNT is highly affected by the solubility of soil organic matter.     

SBR-混凝处理渗滤液过程中有机物的变化特征

考察了SBR-混凝组合工艺对垃圾渗滤液中溶解性有机物(DOM)不同分子量区间物质及组分腐殖酸(HA)、富里酸(FA)和亲水性有机物(HyI)的去除效果,同时利用傅里叶红外光谱及三维荧光光谱对处理过程中DOM各组分变化特性进行了分析。结果表明,组合工艺对表观分子量为2 000~4 000及<2 000的DOM去除率分别为89.3%和72.1%;对渗滤液DOM组分HA、FA和HyI的去除率分别为-52.0%、73.1%和77.1%。红外光谱显示,DOM各组分都含有醇、羧酸、脂等多种有机物,SBR对糖、醇、羧酸等去除效果较好,而混凝对脂肪族及芳香族化合物去除效果较好;三维荧光光谱分析表明,经组合工艺处理,DOM各组分荧光峰强度及复杂化程度明显降低,且SBR工艺对色氨酸等类蛋白物质去除效果较好,混凝工艺对类腐殖酸、类富里酸等大分子物质的去除效果较好。     

Differential sorption of herbicides as related to soil topography and organic matter 1

Abstract

The sorption of bromacil and simazine by the surface soil (0–15 cm) sampled at various positions along an 8% slope citrus grove (Candler fine sand; Typic Quartzipsamment) and at various depths (0–200 cm) at upper, middle, and lower positions along the slope were investigated. The sorption of both herbicides by the top 15 cm soil decreased considerably from the upper to mid position along the slope and increased at the lower position. The organic matter content and concentrations of Ca, Mg, K, P, and Cu in the soil showed evidence of transport of organic matter and mineral nutrients from the mid position on the slope and accumulation in the lower position. The differential sorption of herbicides by the soil samples taken at various positions along the slope was closely related to changes in organic matter content. Although sorption of bromacil and simazine varied considerably at various positions along the slope, the sorption of bromacil was very similar at depths below 30 cm regardless of positions along the slope. In the case of simazine, however, the sorption was much greater at all depths in the lower than in the upper and mid position of the slope. The sorption of both herbicides decreased considerably at depths below 30 cm at all positions along the slope, thus, indicating the potential for rapid leaching of the herbicides down the soil profile.     

pH和有机质对铬渣污染土壤中Cr赋存形态的影响

选用3种不同的铬渣污染土壤作为试验样,通过调节其pH和有机质含量,并采用碱消解-共沉淀法和改良BCR顺序提取法,研究了pH和有机质含量对土壤中铬的价态及形态的影响。结果表明,总体上Cr(Ⅵ)含量随pH降低和有机质投加量增大而减小,Cr(Ⅲ)则增加,但土1各水平间差异均显著(F8.89),土2和土3只有部分水平间差异显著。同时,随pH降低和有机质投加量增大,酸可提取态Cr含量减小,可氧化态Cr增加,可还原态略有增加,表明酸性条件和有机质有利于Cr(Ⅵ)的还原和酸可提取态Cr向可还原态和可氧化态Cr的转化。     

Influence of organic amendments on diuron leaching through an acidic and a calcareous vineyard soil using undisturbed lysimeters

The influence of different organic amendments on diuron leaching was studied through undisturbed vineyard soil columns. Two composts (A and D), the second at two stages of maturity, and two soils (VR and Bj) were sampled. After 1 year, the amount of residues (diuron + metabolites) in the leachates of the VR soil (0.19-0.71%) was lower than in the Bj soil (4.27-8.23%), which could be explained by stronger diuron adsorption on VR. An increase in the amount of diuron leached through the amended soil columns, compared to the blank, was observed for the Bj soil only. This result may be explained by the formation of mobile complexes between diuron and water-extractable organic matter (WEOM) through the Bj soil, or by competition between diuron and WEOM for the adsorption sites in the soil. For both soils, the nature of the composts and their degree of maturity did not significantly influence diuron leaching.     

Impact of soil organic matter on the distribution of polycyclic aromatic hydrocarbons (PAHs) in soils

The knowledge on the distribution of hydrophobic organic contaminants in soils can provide better understanding for their fate in the environment. In the present study, the n-butanol extraction and humic fractionation were applied to investigate the impact of SOM on the distribution of polycyclic aromatic hydrocarbons (PAHs). The results indicated that 80.5%-94.8% of the target PAHs could be extracted by n-butanol and 63.1%-94.6% of PAHs were associated with fulvic acid (FA). Concentrations of un-extracted PAHs increased significantly with the increasing soil organic matter (SOM), however, such an association was absent for the extractable fractions. The results suggested that the sequestration played a critical role in the accumulation of PAHs in soils. SOM also retarded the diffusion of PAHs into the humin fractions. It implied that sequestration in SOM was critical for PAH distribution in soils, while the properties of PAH compounds also had great influences.     

光催化氧化降解垃圾渗滤液中溶解性有机物

研究了UV-TiO2光催化氧化降解垃圾渗滤液过程中溶解性有机物(DOM)的变化特征。结果表明:在适宜条件下,UV-TiO2光催化氧化降解垃圾渗滤液的色度、COD和DOC的去除率分别可达97%、72%和60%;紫外光谱分析说明渗滤液DOM中包括多种含有共轭双键、羰基的大分子有机物及多环芳香类化合物,不同光催化处理液中DOM具有基本一致的结构单元和官能团;红外光谱分析说明渗滤液DOM中含有大量包括羟基、羧基、氨基和苯环的芳香族化合物,在光催化处理液中这几种官能团都能被有效降解;GC/MS分析结果表明,渗滤液DOM中含有72种有机污染物,醇类、羧酸和酮类分别为25、14和12种;在光催化72 h处理液中,有机物减少为44种;酯类和醇类较多,分别为12种和16种;酮类8种,羧酸没有检出。     

有机酸对成都平原镉污染土壤的淋洗效果

以成都平原某化工厂附近受Cd污染的2种土壤为对象,采用振荡淋洗技术,研究了有机酸在不同浓度、固液比、振荡时间和复合淋洗条件下对重金属Cd的去除效果。实验结果表明：柠檬酸和酒石酸对Cd含量为22.78 mg·kg-1的SLT-01土壤具有更好的去除效果,分别达到73%和62%,而乙酸和草酸的去除能力较低;随着固液比的降低,有机酸对Cd的去除率逐步提高;随着时间的增加,Cd的去除率波动增加;柠檬酸和酒石酸复合淋洗并没有提高Cd的去除率;振荡淋洗前后土壤结构未发生明显变化。综合考虑土壤中Cd的去除效果和成本,选择柠檬酸作为最佳淋洗剂;最佳实验条件：溶液浓度为0.10 mol·L-1,固液比为1∶20,淋洗时间为8 h。     

改良型AO法组合工艺中有机物的三维荧光分析

采用三维荧光(EEM)光谱技术,对上海竹园第二污水处理厂改良型AO法组合工艺运行过程中的各种溶解性有机物(DOM)进行分析,并对比研究传统好氧活性污泥法曝气池出水和A/O脱氮工艺硝化池出水DOM的EEM光谱的迁移变化特性.结果表明,各种DOM中主要的荧光物质有类蛋白质(荧光峰A和B)及类腐殖质(荧光峰C),经改良型AO法组合工艺处理后,荧光峰的强度降低了14％～60％,同时类蛋白质和腐殖质的结构也发生了变化;腐殖酸溯源表明DOM中的腐殖酸以微生物代谢产生的带有荧光基团的腐殖酸类为主.     

Effect of catchment land use and soil type on the concentration,quality, and bacterial degradation of riverine dissolved organic matter

We studied the effects of catchment characteristics (soil type and land use) on the concentration and quality of dissolved organic matter (DOM) in river water and on the bacterial degradation of terrestrial DOM. The share of organic soil was the strongest predictor of high concentrations of dissolved organic carbon, nitrogen, and phosphorus (DOC, DON, and DOP, respectively), and was linked to DOM quality. Soil type was more important than land use in determining the concentration and quality of riverine DOM. On average, 5–9 % of the DOC and 45 % of the DON were degraded by the bacterial communities within 2–3 months. Simultaneously, the proportion of humic-like compounds in the DOM pool increased. Bioavailable DON accounted for approximately one-third of the total bioavailable dissolved nitrogen, and thus, terrestrial DON can markedly contribute to the coastal plankton dynamics and support the heterotrophic food web.     

厌氧-跌水充氧接触氧化工艺有机物降解数学模型

厌氧-跌水充氧接触氧化-人工湿地组合工艺是一种新型的污水处理工艺,为优化该工艺在实际工程应用中的参数设计,通过分析研究其工艺流程及有机物降解机理,在借鉴和参考污水处理领域数学模型相关研究的基础上,构建了有机物降解数学模型。结果表明,有机物在不同条件下进行降解时,水温、DO浓度等各种影响因素互相干扰,降解机理复杂。基于人工神经网络的反向传播算法,以COD的初始浓度、DO、温度为输入层,以有机物降解速率常数为输出层,建立确定有机物降解速率常数的神经网络模型,并仿真多因素同时变化时降解速率常数的动力学趋势。验证结果表明,建立的有机物降解模型能够对该工艺的污水处理效果即出水水质进行较好的模拟预测。