Characteristics of MnO2 catalytic ozonation of sulfosalicylic acid and propionic acid in water

The characteristics of different types of MnO₂ catalytic ozonation of sulfosalicylic acid (SSal) and propionic acid (PPA) have been investigated in this paper. The experimental results show the dependence of catalytic activity of MnO₂ on organic compounds and the pH of solutions, but it is independent on the type of MnO₂. For example, three types of MnO₂ have not any catalytic activity when ozonation of PPA under the condition of this experiment. All MnO₂ catalytic ozonation of SSal at pH=1.0 have a greater total organic carbon removal than ozonation alone has, however, at pH=6.8 and 8.5, catalytic efficiency is not observed. Furthermore, the batch experimental results indicate that there are no direct relationship between the activity of metal oxide catalytic decomposition of ozone and that of its catalytic degradation of organic compounds.     

垃圾渗滤液有机物特征及臭氧对其结构的影响

为分析不同填埋龄的垃圾渗滤液中有机物的组分特征及臭氧氧化对其结构的影响,选取成熟和年轻的垃圾渗滤液,利用液相色谱-有机碳-有机氮-紫外吸收(LC-OCD-OND-UVD)、紫外可见光谱、三维荧光光谱和树脂分离技术表征了不同填埋龄垃圾渗滤液中有机物的组分特征。结果表明：在2种垃圾渗滤液有机物中,主要组分为以类富里酸为代表的憎水性腐殖质类和亲水的中性小分子有机化合物,且其组分比例随着填埋龄增加可分别提高至60%和28%。年轻渗滤液中的高含量生物多聚物组分(BP)是其最显著特征。臭氧氧化可快速分解BP并最终生成类腐殖质的分解产物,但TOC去除率<10%。对于含量低于4%的腐殖质类小分子酸,因其含氮杂环结构成为最难矿化的有机物,故较低臭氧投加量无法将其氧化分解。LC-OCD-OND-UVD结合其他表征方法印证分析是获取有机物信息的有效手段,可为深入了解有机物的氧化分解过程提供参考。     

Modeling in situ ozonation for the remediation of nonvolatile PAH-contaminated unsaturated soils

Mathematical models were developed to investigate the characteristics of gaseous ozone transport under various soil conditions and the feasibility of in situ ozone venting for the remediation of unsaturated soils contaminated with phenanthrene. On the basis of assumptions for the mass transfer and reactions of ozone, three approaches were considered: equilibrium, kinetic, and lump models. Water-saturation-dependent reactions of gaseous ozone with soil organic matter (SOM) and phenanthrene were employed. The models were solved numerically by using the finite-difference method, and the model parameters were determined by using the experimental data of Hsu [The use of gaseous ozone to remediate the organic contaminants in the unsaturated soils, PhD Thesis, Michigan State Univ., East Lansing, MI, 1995]. The transport of gas-phase ozone is significantly retarded by ozone consumption due to reactions with SOM and phenanthrene, in addition to dissolution. An operation time of 156 h was required to completely remove phenanthrene in a 5-m natural soil column. In actual situations, however, the operation time is likely to be longer than the ideal time because of unknown factors including heterogeneity of the porous medium and the distribution of SOM and contaminant. The ozone transport front length was found to be very limited (< 1 m). The sensitivity analysis indicated that SOM is the single most important factor affecting in situ ozonation for the remediation of unsaturated soil contaminated with phenanthrene. Models were found to be insensitive to the reaction mechanisms of phenathrene with either gas-phase ozone or dissolved ozone. More study is required to quantify the effect of OH* formation on the removal of contaminant and on ozone transport in the subsurface.     

微气泡催化臭氧化深度处理制药废水的效果及DOM组分特性的变化

采用镁铝层状双氢氧化物(MAL)微气泡催化臭氧化(MAL/MB/O₃)体系深度处理实际制药废水,考察了该体系对溶解性有机物(DOM)的深度去除性能及DOM组分的变化特性,并与普通气泡臭氧化(CB/O₃)、普通气泡催化臭氧化(MAL/CB/O₃)、微气泡臭氧化(MB/O₃)工艺进行了比较。结果表明,MAL/MB/O₃处理性能优于CB/O₃、MAL/CB/O₃和MB/O₃,在臭氧投加总量与处理废水初始COD值之比为0.6、气流量0.5 L·min⁻¹、催化剂投加量0.5 mg·L⁻¹的条件下,整体COD去除率可达49.79%,COD去除量与臭氧消耗量的比值为0.83,废水的可生化性得到了一定改善,生物毒性显著下降。废水DOM中疏水性组分氧化去除率高于亲水性组分。臭氧直接氧化可去除疏水性组分,而亲水性组分去除主要依赖HO·氧化。MAL/MB/O₃对DOM的去除效率最高,可达到52.51%,其中疏水性组分整体去除率56.67%,亲水性组分整体去除率46.93%。废水DOM在氧化处理中存在官能团向酸性基团转化、类腐殖质向类富里酸和类胡敏酸转化、其他组分向亲水性酸(HIA)组分转化的趋势。MAL/MB/O₃强氧化能力对于DOM组分不饱和结构和荧光结构的破坏作用最为显著。以上研究结果可为制药废水深度处理提供参考。     

臭氧氧化对二级出水有机物(EfOM)特性机制的影响

开展了臭氧氧化对二级出水有机物(effluent organic matter,EfOM)的去除效能研究,并进一步采用超滤分离、三维荧光光谱等方法,系统研究了不同臭氧投加量下,EfOM的分子量分布、亲疏水特性以及荧光特性的变化规律。结果表明,臭氧化去除EfOM的效果有限,但能够有效分解二级出水中具有强烈紫外吸收的有机物。此外,臭氧能优先氧化分解二级出水中大分子有机物,有效提高二级出水的可生化性。臭氧氧化过程中,分子质量(molecular weight,MW)>100 kDa的有机物组分被完全氧化分解,10 kDa< MW< 100 kDa和1 kDa< MW< 10 kD的有机物组分含量总体呈下降趋势,而MW<1 kDa的有机物组分随臭氧投加时间的延长含量不断上升。臭氧化后,EfOM中疏水组分减少,亲水组分升高;酸性组分减少。随着臭氧投量的增加,蛋白质与腐殖酸类物质的荧光吸收强度迅速下降。     

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.     

Electro-migration of heavy metals in an aged electroplating contaminated soil affected by the coexisting hexavalent chromium

Cr(VI) was often reported to oxidize soil organic matter at acidic environments due to its high ORP, probably thus changing cationic metal species bound to soil organic matter, and influencing their electro-migration patterns. However, such an effect on the electro-migration was not confirmed in most previous studies. Therefore, this study applied a fixed voltage direct current field on an aged electroplating contaminated clayed soil, with a special interest in the direct or indirect influence of Cr(VI) on the electro-migration of other coexisting metals. After 353 h electrokinetic process, 81% of Zn, 53% of Ni and 22% of Cu in the original soil were electro-migrated into the electrolyte, and most of the remaining concentrated near the cathode. The Cr(VI) oxidized some soil organic matter along its migration pathway, with a pronounced reaction occurred near the anode at low pHs. The resulting Cr(III) reversed its original movement, and migrated towards the cathode, leading to the occurrence of a second Cr concentration peak in the soil. Metal species analyses showed that the amount of metals bound to soil organic matter significantly decreased, while a substantial increase in the Cr species bound to Fe/Mn (hydro-)oxides was observed, suggesting an enhancement of cationic metal electro-migration by the reduction of Cr(VI) into Cr(III). However, the Cr(VI) may form some stable lead chromate precipitates, and in turn demobilize Pb in the soil, as the results showed a low Pb removal and an increase in its acid-extractable and residual fractions after electrokinetic remediation.     

微波催化氧化修复技术处理有机氯污染土壤

采用微波催化氧化修复技术处理常州某农药厂有机氯农药污染场地和南通某化工厂有机氯污染场地土壤,考察不同参数条件下实验装置对污染土壤的处理效能。结果表明,在微波功率18kW、微波辐射时间20min、土壤处理量400kg/h、土壤含水率15%、活性炭添加量0.03kg/kg的最佳条件下,实验装置运行稳定,有机氯农药污染土壤中氯丹去除率可达70%左右;有机氯污染土壤中邻二氯苯、石油烃总量、1,2-二氯乙烷、苯酚去除率分别可达到99.98%、91.29%、98.52%、74.74%。研发的污染土壤微波催化氧化修复技术及实验装置对有机氯污染土壤的修复具有一定的普适性。     

Elevated carbon dioxide does not offset loss of soil carbon from a corn-soybean agroecosystem

The potential for storing additional C in U.S. Corn Belt soils - to offset rising atmospheric [CO₂] - is large. Long-term cultivation has depleted substantial soil organic matter (SOM) stocks that once existed in the region's native ecosystems. In central Illinois, free-air CO₂ enrichment technology was used to investigate the effects of elevated [CO₂] on SOM pools in a conservation tilled corn-soybean rotation. After 5 and 6 y of CO₂ enrichment, we investigated the distribution of C and N among soil fractions with varying ability to protect SOM from rapid decomposition. None of the isolated C or N pools, or bulk-soil C or N, was affected by CO₂ treatment. However, the site has lost soil C and N, largely from unprotected pools, regardless of CO₂ treatment since the experiment began. These findings suggest management practices have affected soil C and N stocks and dynamics more than the increased inputs from CO₂-stimulated photosynthesis.     

微气泡催化臭氧化酸性大红3R的性能及机理

以活性炭为催化剂,采用微气泡催化臭氧化处理酸性大红3R,考察其处理性能和机理,并与微气泡以及传统气泡臭氧化处理性能进行了比较。结果表明：微气泡催化臭氧化可加速液相臭氧分解,其分解系数为0.093 min⁻¹;同时氧化能力明显增强,其脱色速率和TOC去除速率常数分别为0.342 min⁻¹和0.024 2 min⁻¹,均显著高于微气泡和传统气泡臭氧化。微气泡催化臭氧化处理中,臭氧微气泡收缩破裂和活性炭催化的协同效应可强化·OH氧化反应,其对TOC去除的贡献率可达到75%。·OH捕获剂的存在使得微气泡催化臭氧化TOC去除率下降,其中Na₂CO₃的抑制作用最为显著。微气泡催化臭氧化中,臭氧利用效率和反应效率亦得到强化,平均臭氧利用率为98.3%,累积TOC去除量和臭氧消耗量比值R可达0.128 mg·mg⁻¹。GC-MS分析结果表明,微气泡催化臭氧化酸性大红3R降解途径包括偶氮键断裂、萘环/苯环开环、小分子有机酸矿化等过程。     

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.     

微气泡臭氧化强化吸收-氧化处理高浓度乙酸乙酯气体

采用微气泡臭氧化处理模拟高浓度乙酸乙酯气体,考察了强化吸收与氧化去除体系的性能、反应动力学及氧化反应的过程。结果表明,微气泡臭氧化能明显提高易溶性乙酸乙酯气体吸收-氧化处理的效率,乙酸乙酯气体整体平均去除率高于96%,氧化矿化率可达到90.22%,高于普通气泡臭氧化过程的63.25%和47.15%。微气泡臭氧化可提高臭氧利用效率,累积臭氧利用率可达到85.5%,高于普通气泡中的58.6%;同时,还可强化·OH氧化反应,提高臭氧化反应效率,反应中臭氧消耗量与乙酸乙酯TOC去除量比值(R)仅为1.04 mg∙mg⁻¹,明显低于普通气泡臭氧化过程的1.53 mg∙mg⁻¹。微气泡臭氧化处理中,乙酸乙酯传质吸收和氧化矿化反应均符合表观零级动力学方程,氧化矿化速率与传质速率基本平衡。以上结果表明,微气泡臭氧化处理可实现长期稳定高效处理乙酸乙酯气体。     

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.     

我国有机物污染场地土壤修复技术的专利计量分析

以我国公开的691项有机物污染场地土壤修复技术专利为依据,分析研究了有机物污染场地土壤修复技术的发展趋势和进展,同时对化学氧化修复技术、生物修复技术、热脱附技术、淋洗技术等的研究进展进行分析,总结了目前国内有机物污染场地修复专利技术发展现状,并提出了今后的发展方向,以期为我国今后开展相关修复技术的研究与应用提供参考。结果显示：我国有机物污染场地土壤修复技术相关专利于2010年后开始快速发展,研究创新点基本集中于高效技术的开发、节能以及二次污染的防治;热脱附技术在该领域应用广泛;氧化修复技术的开发是2017年的技术发展特点,具有一定的研究前景;而联合多种修复技术更能灵活地适用于实际场地修复的需要,其已成为重要的研究趋势。     

On spurious water flow during numerical simulation of steam injection into water-saturated soil

Numerical simulation of steam injection into a water-saturated porous medium may be hindered by unphysical behavior causing the model to slow down. We show how spurious water flow may arise on the boundary between a steam zone and a saturated zone, giving rise to dramatic pressure drops. This is caused by the discretization of the temperature gradient coupled with the direct relation between pressure and temperature in the steam zone. The problem may be a severe limitation to numerical modeling. A solution is presented where the spurious water flow is blocked and this widely enhances the performance of the model. This new method is applied to a previously reported example exhibiting numerical problems. Furthermore, it is applied to the simulation of 2-D sandbox experiments where LNAPL is remediated from a smearing zone by steam injection. These experiments would have been difficult to analyze numerically without the adjustment to prevent spurious flow.     

Investigating roles of organic and inorganic soil components in sorption of polar and nonpolar aromatic compounds

The main objective of the present study was to assess the roles of various soil components in sorption of organic compounds differing in polarity. Removal of the whole soil organic matter decreased sorption by approximately 86% for nonpolar 1,3,5-trichlorobenzene (TCB), but only 34-54% for highly polar 1,3,5-trinitrobenzene (TNB); however, removal of the extractable humic/fulvic acids did not much affect sorption of the two sorbates. With normalization of solute hydrophobicity, TNB exhibits several orders of magnitude stronger sorption compared with TCB to maize burn residue (black carbon), extracted humic acid and Na⁺-saturated montmorillonite clay, suggesting specific sorptive interactions for TNB with the individual model soil components. It was proposed that sorption of TCB to the bulk soil was dominated by hydrophobic partition to the condensed, non-extractable fraction of organic matters (humin/kerogen and black carbon), while interactions with soil clay minerals were an important additional factor for sorption of TNB.     

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.     

回填材料对土壤原位热传导修复的影响及数值模拟

原位热传导修复技术是一种有机污染土壤高效修复手段。由于施工过程中加热井与土壤间会存在一定空隙,关于是否使用回填材料以及回填材料的选取原则,尚未有明确的指导意见。利用实验和数值模拟方法,对原位热传导修复过程中回填材料的影响进行了研究,分析了不同加热温度(200、400 、600 、800 ℃)、回填材料(空气、原土)、回填厚度(40、100、150 mm)对传热的影响。结果表明,基于实验数据所建立的原位热传导数值预测模型是可靠的,模拟计算值与实测值最小平均相对误差为6.69%;当加热温度高于450 ℃时,无回填料时传热效果更好;当加热温度小于300 ℃时,用土壤回填较好;在300~450 ℃时,有无回填料传热效果相差不明显;原位热传导修复技术工程在应用过程中,回填材料厚度100 mm时传热效果最佳。本研究结果可为污染土壤原位热传导修复的工程实践提供参考。     

Effects of soil organic matter on the development of the microbial polycyclic aromatic hydrocarbons (PAHs) degradation potentials

The microbial activity in soils was a critical factor governing the degradation of organic micro-pollutants. The present study was conducted to analyze the effects of soil organic matter on the development of degradation potentials for polycyclic aromatic hydrocarbons (PAHs). Most of the degradation kinetics for PAHs by the indigenous microorganisms developed in soils can be fitted with the Logistic growth models. The microbial activities were relatively lower in the soils with the lowest and highest organic matter content, which were likely due to the nutrition limit and PAH sequestration. The microbial activities developed in humic acid (HA) were much higher than those developed in humin, which was demonstrated to be able to sequester organic pollutants stronger. The results suggested that the nutrition support and sequestration were the two major mechanisms, that soil organic matter influenced the development of microbial PAHs degradation potentials.