强化氧化后污染源浅层地下水中氯苯类污染物的自然衰减与微生物群落演化

监控自然衰减技术通常与其他地下水修复技术联用,以降低修复成本、减少环境影响,目前该技术在氯苯类污染地块的实践应用案例存在空白,其效果及作用机制尚不明确。以原位臭氧氧化和化学氧化中试后的氯苯类污染地块为研究对象,从实际工程案例的角度,监测强化氧化措施后2年内的氯苯类化合物的降解速率、细菌组成,评价不同修复措施后污染物自然衰减能力、探讨作用机制。结果显示,经过727 d的自然衰减,1,2-二氯苯和1,4-二氯苯在臭氧氧化区和化学氧化区中的降解率都超过了90%。臭氧氧化区地下水中1,2-二氯苯和1,4-二氯苯的一阶降解速率常数分别为0.005 2 d⁻¹ (R²=0.857) 和0.006 0 d⁻¹ (R²=0.967) ;化学氧化区地下水中污染物质量浓度在416 d后出现回升,不符合一阶衰减模型。细菌16S rRNA的高通量分析表明,臭氧和过硫酸钠氧化改变了地下水中细菌群落结构,在自然衰减过程中细菌群落结构逐渐恢复,环境因子S²⁻、ORP和pH值与细菌群落结构显著相关。本地块2个区域中试后416 d内都以化学氧化和微生物好氧降解为主,后向微生物厌氧降解转变。本研究可为氯苯类污染地下水修复工程的绿色高效实施提供参考。     

水动力控制强化碱活化过硫酸盐原位修复1,2-二氯乙烷污染地下水

针对某受1,2-二氯乙烷污染场地,开展水文地质实验并求解水文地质参数,采用水动力控制强化原位化学氧化技术修复了地下水含水层中受污染的地下水,探究了碱活化过硫酸盐对地下水中目标污染物去除效果,并对地下水水化学因子进行了长期监测。结果表明,实验区含水层渗透系数为7.89 m·d⁻¹,导水系数为101 m²·d⁻¹,在一维稳定流场中二维弥散条件下,含水层纵、横向弥散度α_L和α_T分别为0.89 m和0.089 m,地下水流速为3.85 m·d⁻¹,水动力条件明显优于自然状态,通过水动力控制法干扰地下水流场可有效控制修复药剂在含水层中的扩散速度和影响范围。注药后实验区污染物浓度整体呈下降趋势,在第14天,注药井4 m以内1,2-二氯乙烷浓度低于检出限,药剂修复效果在含水层中可保持28 d。碱活化过硫酸盐降解1,2-二氯乙烷的反应速率常数为0.022 d⁻¹,半衰期为29 d。实验期间地下水中硫酸盐浓度先上升后下降,140 d后恢复至原浓度水平,对实验场地二次污染影响较小。碱活化过硫酸盐在氯代烃类污染场地修复中将有广阔的应用前景。     

改性Pd/GAC粒子电极吸附-电催化去除2,4,6-三氯苯酚

以6 mol·L⁻¹硝酸和450 ℃高温共同改性后的颗粒活性炭(granular activated carbon,GAC)为载体,采用硼氢化钠还原法制备了改性Pd/GAC粒子电极,研究了电极对2,4,6-三氯苯酚(2,4,6-trichlorophenol,2,4,6-TCP)的去除能力、动力学特征及脱氯机理。结果表明,通过改性,GAC的比表面积(560.791 m²·g⁻¹)提高了1.5倍,孔容提高了36.02%,对2,4,6-TCP的最大吸附容量为199.2 mg·g⁻¹。在优化条件下,改性粒子电极4 h内对30 mg·L⁻¹的2,4,6-TCP去除率达到94.7%,反应速率常数为0.014 min⁻¹,钯的催化活性为0.3 (min·mmol)⁻¹。通过对反应过程中有机氯和无机氯变化的分析,阐明了改性Pd/GAC粒子电极强化去除2,4,6-TCP的过程。从还原途径、直接和间接还原贡献等方面探究了改性粒子电极电催化脱氯机理。     

纳米零价铁对衰减停滞期氯代烃污染地下水的实地修复

在处于衰减停滞期的氯代烃污染场地,进行了液相纳米零价铁(nZVI)的现场制备,并针对目标含水层完成了nZVI 的2次原位注入。监测结果表明,nZVI的原位注入可有效削减高浓度的氯乙烯(VC)且减缓其向下游的迁移。在第2次注入nZVI后期,在距注入井1 m的上游和下游监测井中,氯代乙烯整体呈现降低的趋势;而上游监测井中的氯代乙烷则发生显著反弹;在距注入井2 m的下游监测井中,各氯代烃均发生持续降解。总铁浓度变化结果表明,原位注入过程促使部分nZVI短期内向上游发生了定向迁移,导致注入初期上游监测井中氯代烃的削减程度高于下游监测井。乙烯浓度的大幅升高(由1 490 μg·L⁻¹增加至4 110 μg·L⁻¹)印证了距注入井2 m的下游监测井中脱氯反应最为显著且彻底,可推测下游适量nZVI的引入有效刺激了含水层优势微生物的协同降解。nZVI原位注入可作为以VC污染为主的衰减停滞期地下水修复的有效手段。以上研究结果可为实际场地大规模治理修复提供参考。     

4种碱基添加剂对1,2,4-三氯苯污染土壤热脱附效果的影响

含氯有机物是土壤中常见的污染物质,对人体危害大,采用热脱附修复技术去除。通过改变加热温度、加热时间及添加4种碱性物质 (NaHCO₃、NaOH、Ca(OH)₂、CaCO₃) 等条件获取TCB的去除效率及污染土壤理化性质变化情况。实验结果表明,热脱附能有效去除土壤中TCB,当温度为350 ℃加热30 min时,污染土壤中TCB去除率为83.27%;碱性物质的添加能有效强化热脱附过程,添加1%的NaHCO₃、NaOH、Ca(OH)₂和CaCO₃后,TCB去除率分别提高了28.28、26.13、20.28、18.19%。碱性物质的添加促进了TCB的脱氯和降解,相比于无碱性物质热脱附,添加1%NaHCO₃和NaOH后尾气中DCBz增加了5.4 ug·L⁻¹和3.65 ug·L⁻¹。热脱附后土壤有机碳、有效磷质量分数和阳离子交换量减少,电导率增大;碱基协同热脱附前后土壤的总有机碳质量分数变化不大,土壤中有效磷质量分数和阳离子交换量明显增大,脱附条件为250 ℃、30 min以及1%的Ca(OH)₂时,脱附前后有效磷由57.5 mg·kg⁻¹增大至80.2 mg·kg⁻¹,阳离子交换量由19.72 cmol⁺·kg⁻¹增大至24.4 cmol⁺·kg⁻¹。本研究结果可为热脱附技术修复三氯苯污染土壤提供技术参考。     

基于kintecus模型的紫外/次氯酸降解MC-LR的自由基稳态浓度及反应动力学模拟

蓝藻代谢产生的微囊藻毒素-LR(MC-LR)会污染饮用水源,并对人类健康构成威胁。紫外/次氯酸技术能产生氯自由基(Cl·)和羟基自由基(HO·)等强氧化性物质来降解MC-LR。但该技术的最优参数尚不可知,已报导的实验结果仅能提供部分参数,亟需通过数值模拟来确定更多重要参数。因此,采用kintecus化学动力模型模拟了先前报导过的实验数据并对未报导数据进行了预测。结果表明,模型预测值与实验值的变化趋势一致,误差在1.5倍以内。在pH为6时,紫外/次氯酸技术对MC-LR的降解效果最好,7 min左右降解率可达到90%。HO·和Cl·的稳态浓度分别为6.59×10⁻¹⁴ mol·L⁻¹和1.22×10⁻¹⁴ mol·L⁻¹,与原文献实验结果较为吻合(7.89×10⁻¹⁴ mol·L⁻¹,0.93×10⁻¹⁴ mol·L⁻¹)。在次氯酸添加量超过40 μmol·L⁻¹之后,降解效果提升并不明显。当紫外光波长由257.7 nm增加到301.2 nm时,MC-LR的表观降解速率常数由5.07×10⁻³ s⁻¹下降到4.69×10⁻³ s⁻¹,下降了7.5%。而在波长为257.7 nm、pH由6提升至8时,表观降解速率常数由5.07×10⁻³ s⁻¹下降到3.84×10⁻³ s⁻¹,下降了24%。因此,改变pH对降解效率的影响大于改变紫外光波长的情况。     

基于污水处理厂提标改造需求的难降解工业废水处理工艺改进—以湖南省某城镇污水处理厂为例

以湖南省某城镇污水处理厂一期1.0×10⁴ m³·d⁻¹提标改造工程项目为案例,针对其进水中工业废水占比高（达80%）、污染物浓度波动大、难降解有机物含量高等特点,在原“水解酸化池+AAO+高效沉淀池+纤维转盘滤池”工艺的基础上,通过现场中试实验,分析了以“臭氧催化氧化+生物活性炭滤池”(O₃-BAC)作为提标改造主要工艺的可行性,并设计了工程案例的主要构筑物参数。该项目的实施能够补齐原工艺对难降解有机物削减能力不足的短板,执行排放标准由原一级A提高至《湖南省城镇污水处理厂主要水污染物排放标准》(DB 43/T 1546-2018)二级标准。项目的建设投资为1 051.4 元·m⁻³,直接运行成本0.67 元·m⁻³,每年较原工艺可多削减以COD计的有机物36.5 t·a⁻¹,每年多削减NH₃-N排放量7.3 t·a⁻¹。该工程案例可为接纳高比例工业废水的城镇污水处理厂的提标改造项目提供参考。     

不同分子量聚乳酸的异养反硝化脱氮性能及脱氮反应机制

聚乳酸(PLA)是一种发展潜力巨大的反硝化固体碳源。为探究不同分子量PLA反硝化脱氮路径及机制,以不同分子量PLA为固体碳源研究了PLA的静态释碳性能和反硝化脱氮效果,考察了反硝化出水溶解性有机质(DOM)组分和微生物群落结构。结果表明：PLA释碳稳定,在清水和脱氮反应器中出水COD均能稳定在20 mg·L⁻¹;PLA分子量越低,脱氮效果越好,5 000 g·mol⁻¹分子量PLA的NO₃⁻-N去除率和反硝化速率达到100%和1.29 mg·L⁻¹·h⁻¹。PLA脱氮路径有2条：一是反硝化功能菌群利用水解微生物分解PLA释放的小分子碳源作为电子供体进行异养反硝化作用;一是微生物利用溶解性微生物代谢产物等有机物进行反硝化脱氮。该研究结果可为PLA固体碳源在反硝化脱氮工艺中的高效应用提供参考。     

含铁黏土矿物与电子传递体强化生物还原固定地下水中Cr(Ⅵ)的过程和机理分析

为了提高微生物还原固定Cr(Ⅵ)的速率,实现地下水Cr(Ⅵ)污染物的快速有效去除,采用添加黏土矿物与电子传递体的方法,考察了含铁黏土矿物NAu-2和电子传递体AQDS单独/共存条件下对希瓦氏菌Shewanella oneidensis MR-1还原固定地下水中不同浓度Cr(Ⅵ)(0.1~2.0 mmol·L⁻¹)的影响。结果表明：单独添加NAu-2对不同浓度Cr(Ⅵ)生物还原过程均无促进作用;单独添加AQDS对不同浓度Cr(Ⅵ)(0.2~2.0 mmol·L⁻¹)生物还原过程均产生强化作用,强化系数达到1.33~3.90;同时添加NAu-2和AQDS时,不同浓度Cr(Ⅵ)(0.2~2.0 mmol·L⁻¹)生物还原时的强化作用均得到明显提升,强化系数达到2.02~10.49。此外,对比NAu-2和AQDS共存时对MR-1还原不同浓度Cr(Ⅵ)的协同促进作用,发现在低浓度Cr(Ⅵ)(0.1~0.5 mmol·L⁻¹)体系中未产生协同作用(协同系数<1.0),中、高浓度Cr(Ⅵ)(0.8~2.0 mmol·L⁻¹)体系中产生了明显的协同作用(SF>1.0),且在Cr(Ⅵ)浓度为1.2 mmol·L⁻¹时,协同效果最为明显(协同系数为2.98),说明NAu-2和AQDS对中、高浓度Cr(Ⅵ)(0.8~2.0 mmol·L⁻¹)还原过程的协同促进作用差异较大。通过对不同Cr(Ⅵ)浓度条件下NAu-2、AQDS与MR-1共存的复杂体系中Cr(Ⅵ)迁移转化过程和机理进行研究,可为实际Cr(Ⅵ)污染场地修复提供新的修复思路及参考数据。     

缓释氮源的固定化Rhodococcus sp.W7颗粒处理焦化废水

本研究将固定化微生物与氮源缓释相结合,以提高一般固定化微生物在氮源缺乏环境中的生物降解效率。利用尿素作为缓释氮源,通过将聚乙烯醇-海藻酸钠混合凝胶(包含尿素)在3% CaCl₂ 饱和硼酸溶液中一次交联,在0.5 mol·L⁻¹硫酸钠溶液中二次交联,最终制得的缓释尿素固定化微生物颗粒包封率高达98%以上,溶胀率在15%~25%,同时有较高的机械强度。在无氮条件下,颗粒可在4、8、12 h内分别完成对100 mg·L⁻¹苯酚、吡啶或喹啉的降解;在高碳氮比的模拟焦化废水环境下,可在6 h内完成对100 mg·L⁻¹苯酚、10 mg·L⁻¹吡啶及10 mg·L⁻¹喹啉混合底物的降解。另外,固定化微生物颗粒所包含的尿素提供的氮源能满足固定化微生物每天降解100 mg·L⁻¹苯酚并持续20 d。以上研究结果表明所制备的缓释尿素固定化微生物颗粒可应用于氮源匮乏的污水治理中并有较好的应用效果。     

Influence of root-exudates concentration on pyrene degradation and soil microbial characteristics in pyrene contaminated soil

The effect of ryegrass (Lolium perenne L.) root-exudates concentration on pyrene degradation and the microbial ecological characteristics in the pyrene contaminated soil was investigated by simulating a gradually reducing concentration of root exudates with the distance away from root surface in the rhizosphere. Results showed that, after the root-exudates were added 15 d, the pyrene residue in contaminated soil responded nonlinearly in the soils with the same pyrene contaminated level as the added root-exudates concentration increased, which decreased first and increased latter with the increase of the added root-exudates concentration. The lowest pyrene concentration appeared when the root exudates concentration of 32.75 mg kg(-1) total organic carbon (TOC) was added. At the same time, changes of microbial biomass carbon (MBC, C(mic)) and microbial quotient (C(mic)/C(org)) were opposite to the trend of pyrene degradation as the added root-exudates concentration increased. Phospholipid fatty acid (PLFA) analysis revealed that bacteria was the dominating microbial community in pyrene contaminated soil, and the changing trends of pyrene degradation and bacteria number were the same. The changing trend of endoenzyme-dehydrogenase activity was in accordance with that of soil microbe, indicating which could reflect the quantitative characteristic of detoxification to pyrene by soil microbe. The changes in the soils microbial community and corresponding microbial biochemistry characteristics were the ecological mechanism influencing pyrene degradation with increasing concentration of the added root-exudates in the pyrene contaminated soil.     

Mineralization of PAHs in coal-tar impacted aquifer sediments and associated microbial community structure investigated with FISH

The microbial community structure and mineralization of polycyclic aromatic hydrocarbons (PAHs) in a coal-tar contaminated aquifer were investigated spatially using fluorescence in situ hybridization (FISH) and in laboratory-scale incubations of the aquifer sediments. DAPI-detected microbial populations in the contaminated sediments were three orders of magnitude greater than nearby uncontaminated sediments, suggesting growth on coal-tar constituents in situ. Actinobacteria, beta- and gamma-Proteobacteria, and Flavobacteria dominated the in situ aerobic (>1 mg l(-1) dissolved oxygen) microbial community, whereas sulfate-reducing bacteria comprised 37% of the microbial community in the sulfidogenic region of the aquifer. Rapid mineralization of naphthalene and phenanthrene were observed in aerobic laboratory microcosms and resulted in significant enrichment of beta- and gamma-Proteobacteria potentially explaining their elevated presence in situ. Firmicutes, Flavobacteria, alpha-Proteobacteria, and Actinobacteria were also enriched in the mineralization assays, but to a lesser degree. Nitrate- and sulfate-limited mineralization of naphthalene in laboratory microcosms occurred to a small degree in aquifer sediments from locations where groundwater chemistry indicated nitrate- and sulfate-reduction, respectively. Some iron-limited mineralization of naphthalene and phenanthrene was also observed in sediments originating near groundwater measurements of elevated ferrous iron. The results of this study suggest that FISH may be a useful tool for providing a much needed link between laboratory microcosms and groundwater measurements made in situ necessary to better demonstrate the potential for natural attenuation at complex PAH contaminated sites.     

Activity-dependent labeling of oxygenase enzymes in a trichloroethene-contaminated groundwater site

A variety of naturally occurring bacteria produce enzymes that cometabolically degrade trichloroethene (TCE), including organisms with aerobic oxygenases. Groundwater contaminated with TCE was collected from the aerobic region of the Test Area North site of the Idaho National Laboratory. Samples were evaluated with enzyme activity probes, and resulted in measurable detection of toluene oxygenase activity (6-79% of the total microbial cells). Wells from both inside and outside contaminated plume showed activity. Toluene oxygenase-specific PCR primers determined that toluene-degrading genes were present in all groundwater samples evaluated. In addition, bacterial isolates were obtained and possessed toluene oxygenase enzymes, demonstrated activity, and were dominated by the phylotype Pseudomonas. This study demonstrated, through the use of enzymatic probes and oxygenase gene identification, that indigenous microorganisms at a contaminated site were cometabolically active. Documentation such as this can be used to substantiate observations of natural attenuation of TCE-contaminated groundwater plumes.     

In situ sequenced bioremediation of mixed contaminants in groundwater

A mixture of chlorinated solvents (about 0.5-10 mg/l), including tetrachloroethene (PCE) and carbon tetrachloride (CT), together with a petroleum hydrocarbon, toluene (TOL), were introduced into a 24 m long x 2 m wide x 3 m deep isolated section (henceforth called a gate) of the Borden aquifer and subjected to sequential in situ treatment. An identical section of aquifer was similarly contaminated and allowed to self-remediate by natural attenuation, thus serving as a control. The control presents a rare opportunity to critically assess the performance of the treatment systems, and represents the first such study for sequenced in situ remediation. The first treatment step was anaerobic bioremediation. This was accomplished using a modified nutrient injection wall (NIW) to pulse benzoate and a nutrient solution into the aquifer, maximizing mixing by dispersion and minimizing fouling near the injection wells. In the anaerobic bioactive zone that developed, PCE, CT and chloroform (CF), a degradation product of CT, degraded with a half-lives of about 59, 5.9 and 1.7 days, respectively. The second step was aerobic bioremediation, using a biosparge system. TOL and cis-1,2 dichloroethene (cDCE), from PCE degradation, were found to degrade aerobically with half-lives of 17 and 15 days, respectively. Compared to natural attenuation, PCE and TOL removal rates were significantly better in the sequenced treatment gate. However, CT and CF were similarly and completely attenuated in both gates. It is believed that the presence of TOL helped sustain the reducing environment needed for the reduction of these two compounds.     

Microbiological analysis of multi-level borehole samples from a contaminated groundwater system

A range of bacteriological, geochemical process-related and molecular techniques have been used to assess the microbial biodegradative potential in groundwater contaminated with phenol and other tar acids. The contaminant plume has travelled 500 m from the pollutant source over several decades. Samples were obtained from the plume using a multi-level sampler (MLS) positioned in two boreholes (boreholes 59 and 60) which vertically transected two areas of the plume. Activity of the microbial community, as represented by phenol degradation potential and ability to utilise a range of substrates, was found to be influenced by the plume. Phenol degradation potential appeared to be influenced more by the concentration of the contaminants than the total bacterial cell numbers. However, in the areas of highest phenol concentration, the depression of cell numbers clearly had an effect. The types of bacteria present were assessed by culture and DNA amplification by polymerase chain reaction (PCR). Bacterial groups or processes associated with major geochemical processes, such as methanogenesis, sulphate reduction and denitrification, that have the potential to drive contaminant degradation, were detected at various borehole levels. A comparative molecular analysis of the microbial community between samples obtained from the MLS revealed the microbial community was diverse. The examination of microbial activity complemented those results obtained through chemical analysis, and when combined with hydrological data, showed that MLS samples provided a realistic profile of plume effects and could be related to the potential for natural attenuation of the site.     

Soil temperature effect in calculating attenuation and retardation factors

The effect of annual variation of daily average soil temperature, at different depths, in calculating pesticides ranking indexes retardation factor and attenuation factor is presented. The retardation factor and attenuation factor are two site-specific pesticide numbers, frequently used as screening indicator indexes for pesticide groundwater contamination potential. Generally, in the calculation of these two factors are not included the soil temperature effect on the parameters involved in its calculation. It is well known that the soil temperature affects the pesticide degradation rate, water-air partition coefficient and water-soil partition coefficient. These three parameters are components of the retardation factor and attenuation factor and contribute to determine the pesticide behavior in the environment. The Arrhenius equation, van't Hoff equation and Clausius-Clapeyron equation are used in this work for estimating the soil temperature effect on the pesticide degradation rate, water-air partition coefficient and soil-water partition coefficient, respectively. These dependence relationships, between results of calculating attenuation and retardation factors and the soil temperature at different depths, can aid to understand the potential pesticide groundwater contamination on different weather conditions. Numerical results will be presented with pesticides atrazine and lindane in a soil profile with 20 degrees C constant temperature, minimum and maximum surface temperatures varying and spreading in the soil profile between -5 and 30 degrees C and between 15 and 45 degrees C.     

柴油降解菌的筛选、菌群构建及其对柴油和十五烷的降解机理

针对柴油污染土壤生物修复技术效率低的问题,通过构建高效降解菌群修复柴油污染的土壤,采用组合优化和正交实验构建最佳组合与接种比例的菌群,并研究其柴油降解特性。结果表明,通过筛选、鉴定并命名的4株柴油降解菌为Bacillus sp. VOC18-L1、Enterococcus faecalis-L2、Lysinibacillus-L3、Rhodococcus equi-L4;当4株菌接种比例为3∶1∶3∶4,pH = 7.0,30 ℃,转速150 r·min⁻¹时,柴油降解的效果最佳,14 d对7.0 mL·L⁻¹的柴油降解率达到89.0%。通过气相色谱质谱联用仪(GC-MS)检测柴油降解产物,发现该混合菌株能将柴油中的烷烃降解为短链烷烃,最终转化为小分子物质。同时利用KEGG数据库获得代谢丰度图并初步预测每种菌的功能,根据微生物多样性测试结果,进一步证明了混合菌对柴油完全降解的效果优于单种菌种。通过人工构建的微生物菌群可以有效地应用于柴油污染土壤的修复。     

Evaluation of soil temperature effect on herbicide leaching potential into groundwater in the Brazilian Cerrado

The effect of annual variations in the daily average soil temperatures, at different depths, on the calculation of pesticide leaching potential indices is presented. This index can be applied to assess the risk of groundwater contamination by a pesticide. It considers the effects of water table depth, daily recharge net rate, pesticide sorption coefficient, and degradation rate of the pesticide in the soil. The leaching potential index is frequently used as a screening indicator in pesticide groundwater contamination studies, and the temperature effect involved in its calculation is usually not considered. It is well known that soil temperature affects pesticide degradation rates, air-water partition coefficient, and water-soil partition coefficient. These three parameters are components of the attenuation and retardation factors, as well as the leaching potential index, and contribute to determine pesticide behavior in the environment. The Arrhenius, van't Hoff, and Clausius-Clapeyron equations were used in this work to estimate the soil temperature effect on pesticide degradation rate, air-water partition coefficient, and water-soil partition coefficient, respectively. The relationship between leaching potential index and soil temperature at different depths is presented and aids in the understanding of how potential pesticide groundwater contamination varies on different climatic conditions. Numerical results will be presented for 31 herbicides known to be used in corn and soybean crops grown on the municipality of S?o Gabriel do Oeste, Mato Grosso do Sul State, Brazil.