乙醇对过硫酸盐去除石灰岩含水介质中汽油组分BTEX的影响

随着乙醇汽油的推广应用,其污染岩溶地下水的环境问题受到越来越多的关注。汽油组分苯、甲苯、乙苯和二甲苯(BTEX)可以被过硫酸盐(PS)化学氧化作用有效去除。然而,乙醇的存在是否影响PS去除BTEX尚缺乏深入研究。利用石灰岩颗粒为介质,以汽油组分BTEX(总浓度为20 mg/L)和乙醇(浓度分别为500,5000 mg/L)为污染物,通过微元体(Microcosm)实验模拟污染的岩溶地下水环境,研究PS分别去除BTEX和乙醇,以及同时去除BTEX和乙醇的效果,讨论了乙醇对PS去除BTEX的影响。结果表明:前28 d,PS可以去除91%的BTEX,准一级动力学常数为0.006~0.349 d-1,其中苯最难去除,其次为甲苯。乙醇能够被PS有效去除,准一级动力学常数为0.003~0.054 d-1,去除速率小于BTEX;乙醇与BTEX共存时能够抑制BTEX的去除,但不会影响BTEX去除的优先性。PS浓度增大,有利于去除乙醇和BTEX,但会抑制微生物活性,促使pH值下降,并导致CaSO₄沉淀。该试验结果可为乙醇汽油污染岩溶地下水的原位化学氧化研究提供科学参考。     

BTEX在乙醇汽油和传统汽油污染地下水中的衰减行为对比

地下燃油储藏罐泄漏造成苯、甲苯、乙苯和二甲苯（BTEX）影响生态环境和公众健康的问题一直备受关注,随着乙醇汽油的推广使用,乙醇对BTEX修复策略的影响成为需要重视的新问题.为揭示乙醇汽油污染地下水中BTEX的衰减行为,本文通过室内两个独立砂槽投注实验和近3年的监测,对比了乙醇汽油和传统汽油中BTEX自然衰减和基于硫酸盐-硝酸盐补充的增强生物修复行为.结果表明,传统汽油BTEX自然衰减较快,乙醇汽油BTEX自然衰减较慢,一级衰减速率常数分别为0.0055~0.0329 d^-1和0.0045~0.0124 d^-1;苯衰减最快,其次为甲苯.补充硫酸盐和硝酸盐能促进生物修复,单独补充硫酸盐时其利用率为89.7%~92.9%,同时补充硝酸盐时硫酸盐利用被抑制,硝酸盐利用率为79.9%~87.2%.水位波动会促进BTEX溶解和迁移,增大质量通量.乙醇汽油不仅能消耗更多电子受体,使得BTEX衰减被抑制,而且可能会扩大水位波动引起的增溶效应.     

Anaerobic BTEX degradation in soil bioaugmented with mixed consortia under nitrate reducing conditions

Different concentrations of BTEX, including benzene, toluene, ethylbenzene, and three xylene isomers, were added into soil samples to investigate the anaerobic degradation potential by the augmented BTEX-adapted consortia under niwate reducing conditiom. All the BTEX substrates could be anaerobically biodegraded to non-detectable levels within 70 d when the initial concentrations were below 100 mg/kg in soil. Toluene was degraded faster than any other BTEX compounds, and the high-to-low order ofdegradation rates were toluene>ethylbenzene>m. xylene>o-xylene>benzene>P. xylene. Nitrite was accumulated with nitrate reduction. but the accumulation of nitrite had no inhibitory effect on the degradation of BTEX throughout the whole incubation. Indigenous bacteria in tIle soil could enhance the BTEX biodegradation ability of the enriched mixed bacteria. When the six BTEX compounds were simultaneously present in soil, there was no apparent inhibitory effect on their degradation with lower initial concentrations. Alternatively, benzene, o-xylene, and P-xylene degradation were inhibited with higher initial concentrations of 300 mg/kg. Higher BTEX biodegradation rates were observed in soil samples with the addition of sodium acetate compared to the presence of a single BTEX substrate. and the hypothesis of primary-substrate stimulation or cometabolic enhancement of BTEX biodegradation seems likely.     

不同下垫面苯系物的挥发行为研究

结合石油化工区挥发性污染物泄漏控制的需要,选取淄博地区代表性的砂土、壤土和水3种下垫面,对苯系物的挥发行为进行试验研究,得到了不同类型下垫面中苯系物单组分及其混合物的挥发动力学曲线、最优拟合公式和挥发动力学模型.结果表明,3种下垫面中,苯系物组分及混合物的挥发速率大小依次为:苯>甲苯>BTEX>二甲苯>乙基苯;而苯系物在静水面上的挥发最快,砂土中次之,壤土中挥发最慢.另外,3种下垫面中苯系物的挥发速率常(系)数与蒸气压的关系均呈线性正相关,挥发速率系数随着组分蒸气压的增大而明显增大.下垫面对苯系物挥发的影响机制主要表现为对挥发面积和介质在挥发扩散过程中可利用孔隙通量的影响.     

基于TMVOC的地下水位波动带苯系物迁移转化模拟

为探究水位波动情况下苯系物的迁移转化规律,提高石油污染场地地下水污染治理精度,以西北某傍河石化场地为研究对象,基于TMVOC模型对特征污染物苯系物开展泄漏模拟,通过情景模拟比较水位波动对苯系物迁移转化的影响,并从污染分布、相间转化等方面,解析地下水位稳定和波动状态下苯系物迁移转化过程差异.结果表明:①TMVOC模型较好地模拟了水位波动状态下苯系物迁移转化过程.②相较于水位稳定状态下,水位波动作用下苯系物污染深度增加0.5 m,污染面积增加25%,总质量增加12 kg.③水位稳定和波动状态下苯系物"气-液-NAPL（Non-Aqueous Phase Liquids）相"占比分别为0.17%、2.03%、97.8%和0.04%、3.69%、96.27%.④NAPL相苯系物饱和度分布与苯系物质量分布呈正相关,水位波动造成NAPL相初始饱和度降低,且初始水位面以下NAPL相饱和度升高.⑤对于苯而言,水位波动状态下非饱和带中苯在液相中的质量是水位稳定状态下的1.11倍,饱和带为10.15倍.研究显示,水位波动显著地影响了苯系物的迁移转化过程,促进了苯系物的溶解,并使更多的苯系物残留在地下介质中.      

Anaerobic biodegradation of benzene series compounds by mixed cultures based on optional electronic acceptors

A series of batch experiments were performed using mixed bacterial consortia to investigate biodegradation performance of benzene, toluene, ethylbenzene and three xylene isomers （BTEX） under nitrate, sulfate and ferric iron reducing conditions. The results showed that toluene, ethylbenzene, m-xylene and o-xylene could be degraded independently by the mixed cultures coupled to nitrate, sulfate and ferric iron reduction. Under ferric iron reducing conditions the biodegradation of benzene and p-xylene could be occurred only in the presence of other alkylbenzenes. Alkylbenzenes can serve as the primary subs＇rates to stimulate the transformation of benzene and p-xylene under anaerobic conditions. Benzene and p-xylene are more toxic than toluene and ethylbenzene, under the three terminal electron acceptors conditions, the degradation rates decreased with toluene 〉 ethylbenzene 〉 m-xylene 〉 o-xylene〉 benzene 〉 p- xylene. Nitrate was a more favorable electron acceptor compared to sulfate and ferric iron. The ratio between sulfate consumed and the loss of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene was 4.44, 4.51, 4.42, 4.32, 4.37 and 4.23, respectively; the ratio between nitrate consumed and the loss of these substrates was 7.53, 6.24, 6.49, 7.28, 7.81, 7.61, respectively; the ratio between the consumption of ferric iron and the loss of toluene, ethylbenzene, o-xylene, m-xylene was 17.99, 18.04, 18.07, 17.97, respectively.     

地下水苯系物污染原位曝气修复模拟研究

通过TMVOC软件模拟了苯系物在拟定渗流区“自然”环境条件下的污染物运移行为和原位曝气修复过程中的污染物衰减过程,确定了最佳曝气流量和所需要的曝气井数量及分布,并对修复效果进行了模拟.模拟显示,泄露过程中,在重力作用下,不饱和区的苯系物以竖直迁移为主,同时在毛细作用下横向迁移;在饱和区中以顺水流方向水平迁移为主,同时会溶解进入地下水,污染羽可到达含水层底部.从含水层底部的7个曝气孔同时以12m3/h的速率将空气注入时,只需180d即可完全修复苯系物污染区域.该条件下单井有效修复半径约5m,有效修复范围优于从含水层中部和中下部进行曝气.     

基于TMVOC的水位波动带土壤气相抽提模拟

为探究水位波动对土壤气相抽提（Soil Vapor Extraction，SVE）修复的影响，以西北某傍河石化场地为研究对象，利用TMVOC模拟苯系物的自然衰减过程及不同水位状态下SVE修复过程，从修复效果、相间转化、饱和度演变等方面比较不同条件下苯系物的衰减率.结果显示，该场地较佳的抽提井的压强为9.1×10⁴Pa，影响半径为8m；苯系物在自然衰减、水位稳定状态下SVE修复及水位波动状态下SVE修复12个月后的质量损失分别为17%、85%、96%；水位稳定和水位波动状态下SVE修复12个月后，非水相液体（Non-Aqueous Phase Liquids，NAPL）的饱和度最大可达到0.066和0.044；水位稳定状态下，苯系物在"气-液-NAPL"相去除率逐渐降低，水位波动状态下，在水位下降的阶段，更多的NAPL相苯系物转化为气相，并被抽提气流携带去除.     

北京市道路空气中挥发性有机物时空分布规律

为研究城市交通道路空气中挥发性有机化合物(VOCs)的污染状况、变化规律和不同道路类型的浓度特点,于2008年5月—2009年7月对北京市3种典型道路(街道峡谷、交叉道路和开阔道路)进行空气质量监测. 采用气相色谱法测定道路空气中非甲烷烃(NMHCs)、苯系物(苯、甲苯和二甲苯)的质量浓度. 结果表明:北京市道路空气中挥发性有机化合物污染比较严重,其中ρ(NMHCs)日均值为1.0～3.3 mg/m3,ρ(苯系物)日均值为8.8～80.0 μg/m3. 污染物浓度日变化多呈现双峰型. 选取1,4,7和10月为不同季节的代表月份,7月的ρ(NMHCs)和ρ(苯系物)均最高,10月最低. 3种典型道路中,街道峡谷的污染物质量浓度高于另外2种道路. 道路附近的挥发性有机物质量浓度主要受到机动车排放、气象条件和地形条件等的影响.      

苯系化合物在硝酸盐还原条件下的生物降解性能

运用驯化的反硝化混合菌群进行了苯系化合物(BTEX)的厌氧降解试验.结果表明,混合菌群能够在反硝化条件下有效降解苯、甲苯、乙苯、邻二甲苯、间二甲苯和对二甲苯.BTEX的降解规律符合底物抑制的Monod模型,当初始浓度小于50mg·L^-1时,6种受试基质的厌氧降解速率顺序为:甲苯>乙苯>间二甲苯>邻二甲苯>对二甲苯>苯.整个试验过程中NO₃^-的消耗与苯、甲苯、乙苯、邻二甲苯、间二甲苯及对二甲苯生物降解之间的摩尔比分别为:9.47,9.26,1     

北京大气中BTEX的观测分析与研究

采用二步深冷浓缩与气相色谱/质谱联机对北京大气中的苯类物质(BTEX) 进行了长期连续观测.最近4年观测数据表明:日变化有双峰和3峰变化,冬、春季呈现与交通高峰期吻合的双峰变化,即上午08:00至10:00和下午17:00前后各出现一个高值;秋季日变化中,夜间22:00出现第3峰值;夏季日变化呈3峰型,最大峰值在正午前后.2000～2002年BTEX月平均总浓度为(44.1±24.5) nmol/mol(碳单位),季变化峰值出现在夏季.年际变化趋势中,北京大气BTEX的总平均浓度从 1999 年到2002年大幅度下降.     

Isolation and characterization of gasoline-degrading bacteria from gas station leaking-contaminated soils

The effects of culture conditions in vitro and biosurfactant detection were studied on bacterial strains capable of degrading gasoline from contaminated soils near gas station. The main results were summarized as follows. Three bacteria （strains Q10, Q14 and Q18） that were considered as efficiently degrading strains were isolated and identified as Pseudomonas sp., Flavobaeterium sp. and Rhodococcus sp., respectively. The optimal growth conditions of three bacteria including pH, temperature and the concentration of gasoline were similar. The reduction in surface tension was observed with all the three bacteria, indicating the production of biosurfactant compounds. The value of surface tension reduced by the three strains Q10, Q14 and Q18 was 32.6 mN.m, 12.4 mN. m and 21.9 mN.m, respectively. Strain Q10 could be considered as a potential biosurfactant producer. Gasoline, diesel oil, benzene, toluene, ethylbenzene and xylene （BTEX） could easily be degraded by the three isolates. The consortium was more effective than the individual cultures in degrading added gasoline, diesel oil, and BTEX. These results indicate that these strains have great potential for in situ remediation of soils contaminated by gas station leaking.     

低温条件下基于TMVOC的土壤气相抽提技术数值模拟

为研究低温条件下土壤气相抽提技术对包气带中苯系物的去除效果、解决修复技术有效性评估等难题,基于TMVOC模型模拟砂箱试验,从浓度梯度、相间转化、饱和度变化等方面分析土壤气相抽提技术对污染物空间分布规律的影响机理.结果表明,TMVOC模拟苯系物浓度的计算值与试验测量值的拟合效果较好;低温条件下,砂箱土体中苯、甲苯、乙苯、邻二甲苯的去除率分别为89.8%、71.3%、29.7%、14.4%.两次抽提过程中,苯在"气-液-NAPL（non-aqueous phase liquid）"三相中的质量均减少,减少比例近似为2:7:1,苯在液相中的质量减幅最大;在间歇期,苯由"NAPL相"以近似3:7的比例向"气、液"两相运移.在砂箱土体上部和中部NAPL相饱和度保持为0,"气-液"两相共存,间接表明苯系物在"气-液"两相间发生运移;在砂箱土体底部污染源附近"气-液-NAPL"相共存,间接表明苯系物在"气-液-NAPL"相间发生运移,抽提作用使得气相与液相饱和度升高、NAPL相饱和度降低.      

土壤中苯系物的吹扫捕集-气相色谱-质谱测定方法

采用吹扫捕集-气相色谱-质谱联用(PT-GC-MS)法,研究了污染土壤中苯系物(包括苯、甲苯、乙苯、对间二甲苯、邻二甲苯和异丙苯)的测定方法,优化了吹扫捕集作为北京潮土中苯系物预处理方法的参数. 结果表明,吹扫时间11 min,解吸温度190 ℃和解吸时间0.5 min为最佳的吹扫捕集方法参数. 采用PT-GC-MS法测定土壤中的苯系物的平均加标回收率为99.0%～103.9%,相对标准偏差为10.3%～17.5%(n=7);苯系物的检出限为1.6～2.8 μg/kg,定量限为5.4～9.6 μg/kg. 将研究结果与文献中的苯系物监测质量控制参数进行比较发现,由于采用有机质含量低、砂质壤土质地的北京潮土为研究对象,使该试验的回收率均高于文献中的结果;同时,相对标准偏差和检出限与文献中的结果也存在差异,主要是由于挥发性污染物所赋存的介质及实验仪器操作条件不同所致.      

Bio-removal of mixture of benzene, toluene, ethylbenzene, and xylenes/total petroleum hydrocarbons/trichloroethylene from contaminated water

Four pure cultures were isolated from soil samples potentially contaminated with gasoline compounds either at a construction site near a gas station in Fai Chi Kei, Macau SAR or in the northern parts of China (Beijing, and Hebei and Shandong). The e ects of di erent concentrations of benzene, toluene, ethylbenzene, and three isomers (ortho-, meta-, and para-) of xylene (BTEX), total petroleum hydrocarbons (TPH), and trichloroethylene (TCE), when they were present in mixtures, on the bio-removal e ciencies of microbial isolates were investigated, together with their interactions during the bio-removal process. When the isolates were tested for the BTEX (50–350 mg/L)/TPH (2000 mg/L) mixture, BTEoX in BTEoX/TPH mixture was shown with higher bio-removal e ciencies, while BTEmX in BTEmX/TPH mixture was shown with the lowest, regardless of isolates. The TPH in BTEmX/TPH mixture, on the other hand, were generally shown with higher bio-removal e ciencies compared to when TPH mixed with BTEoX and BTEpX. When these BTEX mixtures (at 350 mg/L) were present with TCE (5–50 mg/L), the stimulatory e ect of TCE toward BTEoX bio-removal was observed for BTEoX/TCE mixture, while the inhibitory e ect of TCE toward BTEmX for BTEmX/TCE mixture. The bio-removal e ciency for TPH was shown lower in TPH (2000 mg/L)/TCE (5–50 mg/L) mixtures compared to TPH present alone, implying the inhibitory e ect of TCE toward TPH bio-removal. For the mixture of BTEX (417 mg/L), TPH (2000 mg/L) along with TCE (5– 50 mg/L), TCE was shown co-metabolically removed more e ciently at 15 mg/L, probably utilizing BTEX and/or TPH as primary substrates.     

污水处理过程中苯系物和氯代烃三相分布规律

为研究污水处理过程中曝气对苯系物中苯、甲苯和二甲苯以及氯代烃中三氯甲烷、四氯化碳、三氯乙烯和四氯乙烯去除的影响,设计了2个反应器,模拟污水处理过程,一个为活性污泥反应器,另一个为没有活性污泥的对照反应器.结果表明,在液相中,30.6%的TOC未经微生物降解而直接因曝气逸散到气相.苯系物的逸散比例达到了100%;三氯甲烷、四氯化碳、三氯乙烯和四氯乙烯的逸散比例分别为27.5%、39.0%、42.4%和38.5%.同时利用密闭水箱研究了生物处理单元中苯系物和氯代烃三相分布规律.在厌氧阶段,固相中苯、甲苯、二甲苯、三氯甲烷、四氯化碳、三氯乙烯和四氯乙烯占总量比例分别为38.7%、43.6%、38.0%、28.8%、24.3%、15.3%和20.5%.在曝气阶段,苯系物全部被去除,氯代烃总量略有下降.二沉池阶段,固相中三氯甲烷、四氯化碳、三氯乙烯、四氯乙烯占总质量的比例分别为5.2%、20.1%、6.8%和0%.      

某染料化工厂地块苯系物分布特征分析

为掌握长江中游某染料化工污染地块土壤中苯系物分布特征,对地块17个地下水样品和343个土壤样品进行了测定。结果表明:地下水和土壤苯系物分布区域一致,污染具有同源性;地块地势平坦,土壤水平渗透性差,污染物扩散范围有限。受土壤防污性能影响,苯,间、对-二甲苯及邻-二甲苯主要在7.2 m深度以上土壤中检出;3种物质在土壤中主要以轻质非水相液体（LNAPL）存在,在地下水水位附近出现聚集,在饱和带以溶解态继续向下迁移扩散。土壤中氯苯主要以重质非水相液体（DNAPL）存在,其浓度大,迁移深度深,与氯苯在土壤中存在形态、迁移时间以及地质条件有关。后续修复工程中,建议浅部污染土采用异位常温解吸和化学氧化联合修复技术,深部污染土和受污染地下水一同采用原位化学氧化修复技术。     

Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation

In the first phase of this study, the e ectiveness of intrinsic bioremediation on the containment of petroleum hydrocarbons was evaluated at a gasoline spill site. Evidences of the occurrence of intrinsic bioremediation within the BTEX (benzene, toluene, ethylbenzene, and xylenes) plume included (1) decreased BTEX concentrations; (2) depletion of dissolved oxygen (DO), nitrate, and sulfate; (3) production of dissolved ferrous iron, methane, and CO2; (4) deceased pH and redox potential; and (5) increased methanogens, total heterotrophs, and total anaerobes, especially within the highly contaminated areas. In the second phase of this study, enhanced aerobic bioremediation process was applied at site to enhance the BTEX decay rates. Air was injected into the subsurface near the mid-plume area to biostimulate the naturally occurring microorganisms for BTEX biodegradation. Field results showed that enhanced bioremediation process caused the change of BTEX removal mechanisms from anaerobic biodegradation inside the plume to aerobic biodegradation. This variation could be confirmed by the following field observations inside the plume due to the enhanced aerobic bioremediation process: (1) increased in DO, CO2, redox potential, nitrate, and sulfate, (2) decreased in dissolved ferrous iron, sulfide, and methane, (3) increased total heterotrophs and decreased total anaerobes. Field results also showed that the percentage of total BTEX removal increased from 92% to 99%, and the calculated total BTEX first-order natural attenuation rates increased from 0.0092% to 0.0188% per day, respectively, after the application of enhanced bioremediation system from the spill area to the downgradient area (located approximately 300 m from the source area).     

Co-adsorption of gaseous benzene, toluene, ethylbenzene, m-xylene (BTEX) and SO2 on recyclable Fe3O4 nanoparticles at 0-101% relative humidities

We herein used Fe3O4 nanoparticles(NPs) as an adsorption interface for the concurrent removal of gaseous benzene, toluene, ethylbenzene and m-xylene(BTEX) and sulfur dioxide(SO2), at different relative humidities(RH). X-ray diffraction, Brunauer–Emmett–Teller, and transmission electron microscopy were deployed for nanoparticle surface characterization.Mono-dispersed Fe3O4(Fe2O3·Fe O) NPs synthesized with oleic acid(OA) as surfactant, and uncoated poly-dispersed Fe3O4 NPs demonstrated comparable removal efficiencies.Adsorption experiments of BTEX on NPs were measured using gas chromatography equipped with flame ionization detection, which indicated high removal efficiencies(up to(95 ± 2)%) under dry conditions. The humidity effect and competitive adsorption were investigated using toluene as a model compound. It was observed that the removal efficiencies decreased as a function of the increase in RH, yet, under our experimental conditions, we observed(40 ± 4)% toluene removal at supersaturation for Fe3O4 NPs, and toluene removal of(83 ± 4)% to(59 ± 6)%, for OA-Fe3O4 NPs. In the presence of SO2, the toluene uptake was reduced under dry conditions to(89 ± 2)% and(75 ± 1)% for the uncoated and coated NPs, respectively, depicting competitive adsorption. At RH 100%,competitive adsorption reduced the removal efficiency to(27 ± 1)% for uncoated NPs whereas OA-Fe3O4 NPs exhibited moderate efficiency loss of(55 ± 2)% at supersaturation.Results point to heterogeneous water coverage on the NP surface. The magnetic property of magnetite facilitated the recovery of both types of NPs, without the loss in efficiency when recycled and reused.     

北京市BTEX的污染现状及变化规律分析

2008年10～2009年10月,利用前级浓缩-气相色谱/质谱法,对北京市大气中5种苯系物BTEX（苯、甲苯、乙苯、间、对二甲苯、邻二甲苯）的组成及浓度变化进行了采样分析研究.结果表明,北京市大气BTEX平均浓度为13.9～44.0μg.cm-3,其中甲苯的含量最高,苯次之,邻二甲苯含量最低,与国外城市和地区相比北京大气中BTEX浓度较低,研究发现北京市BTEX主要来自机动车排放,城市燃煤和工业溶剂挥发也是BTEX的重要来源.一年的观测结果表明,BTEX春、夏季节浓度较高,秋季浓度较低,季节性排放源的变化是BTEX季节变化的主要原因,同时也不能忽视温度和大风等天气因素对BTEX浓度的影响.受交通排放和边界层高度的影响,BTEX类化合物的日变化形式为夜晚高于白天,呈双峰形,日最低浓度出现在14：00前后.