BTEX在河流渗滤系统中的降解行为实验模拟研究

河流渗滤是一种自然净化过程,污染河水通过该过程在河流沉积层中发生各种物理、化学和生物作用,使得污染物浓度降低,河水水质得到净化,从而达到增加地下水开采量的目的。本项研究通过淋滤实验,利用自行设计的土柱实验装置和人工配制的淋滤液,模拟了BTEX污染河水在下渗通过河流渗滤系统的过程中发生的降解行为。实验历时48 d,获得了该过程中BTEX各组分和电子受体的质量浓度变化历时曲线,得出的结论包括：污染河水中的BTEX在通过河流渗滤系统时将发生两种环境行为—吸附和降解。其中,吸附作用对于BTEX的净化效果较为有限,当吸附达到饱和之后,在存在电子受体的情况下,BTEX能够发生厌氧微生物降解,降解作用能够更有效的去除BTEX污染物。其中去除效率最高的是间二甲苯,在以NO3-为电子受体的情况下平均去除率为85.5%,在以SO42-为电子受体的情况下平均去除率为82.4%,其次是乙苯、甲苯,去除率最差的是苯,在两种电子受体的系统中平均去除率分别为68.5%和63.5%。由于吸附作用的影响,微生物降解相对于BTEX浓度变化存在一个滞后期,BTEX各组分的土壤-水吸附分配系数Kd越大,总的降解效率也就越低。通过河流渗滤系统这一自然净化过程,可以有效地去除浓度较高的BTEX混合污染,各组分平均去除效率都超过了60%,最高去除率均超过了80%。对于持续不断入渗的污染河水,当土壤吸附达到饱和、微生物活性受到抑制,去除效率会大大降低,从而使BTEX穿透河流沉积层进入含水层,对地下水产生危害。     

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%.      

天津城区夏冬季典型污染过程中BTEX变化特征及其健康风险评估

利用GC955在线气相色谱仪分别于2019年7月和2020年1月在天津市区开展苯系物（BTEX,包括苯、甲苯、乙苯、间/对-二甲苯和邻-二甲苯）实时在线观测,对典型污染过程中BTEX的浓度水平、组成及演化机制进行了研究,并运用特征物种比值法对BTEX的来源进行了定性分析,最后运用US EPA的人体暴露分析评价方法对BTEX健康风险进行评估.结果表明,臭氧和霾污染过程中BTEX体积分数平均值分别为1.32×10^-9和4.83×10^-9,其中苯的体积分数占比最大,其次是甲苯、乙苯和二甲苯占比最小.2020年1月BTEX体积分数很大程度上受到西南方向短距离传输的影响,而在2019年7月BTEX浓度受到本地排放的影响.BTEX浓度水平在2019年7月受到温度和相对湿度的共同影响,而在2020年1月当温度较低时BTEX浓度对相对湿度的变化更敏感.天津市区BTEX在霾污染过程中受生物质燃烧/化石燃料燃烧/燃煤排放的影响较大,而在臭氧污染过程中除了受到燃烧排放源影响,交通源排放在很大程度上也有影响.臭氧污染和霾污染过程中BTEX的HI分别为0.072和0.29,均处于EPA认定的安全范围内.苯的致癌风险在清洁天和污染过程中均高于EPA规定的安全阈值,需引起高度重视.     

水解酸化-缺氧生物法处理油田废水的机理

采用水解酸化-缺氧生物法对经物化预处理的油田废水进行试验研究.当进水COD为190～230mg/L,水解酸化段和缺氧段停留时间分别为10,48h时,出水COD为75～83mg/L.运用GC/MS分析油田废水有机污染物在工艺流程中相对组分变化的规律,表明水解酸化和缺氧法处理油田废水时有协同作用,可有效降解废水中酚类化合物、酮类化合物、芳烃和BTEX.运用PCR-DGGE技术,考察不同生物反应器内微生物种群及其分布特征,初步确定水解酸化和缺氧反应器内的优势菌种.     

UV Spectroscopic Monitoring of Vaporized Monoaromatic Hydrocarbons from Petroleum-Contaminated Soils

Fast and simple systems using ultraviolet (UV) absorbance were examined for on-line monitoring of monoaromatic hydrocarbons from petroleum-contaminated soils in this research. Since soil particles hinder the UV light transmittance, the absorbance measurement of vaporized monoaromatic hydrocarbons in soil gas extracted from petroleum-contaminated soils was proposed. In the fixed system that exhibited higher sensitivity than the portable one, the absorbance intensity of benzene, toluene, ethylbenzene, and xylene increased in proportion to the concentration of the contaminants. The portable system, however, was suitable for screening purpose, while it exhibited faster response. There was no interference from water, which helps the applicability of the proposed systems to the actual fields.     

上海市文教区大气中苯系物冬季污染特征

2004年冬天对上海市文教区大气中的苯系物(BTEX-苯,甲苯,乙苯和二甲苯)浓度进行了监测.结果表明,上海市文教区冬季苯、甲苯、乙苯、对问二甲苯、邻二甲苯的平均浓度分别为13.23 μg/m3,43.66 μ g/m3,13.50μg/m3,16.49 μ g/m3,5.52μg/m3,高于国内外相似功能区的苯系物浓度,与国外大城市交通干道附近的浓度相近.所测苯系物中,甲苯的含量最高,达47.3%.白天苯系物浓度高于夜间.甲苯、乙苯、二甲苯相互间具有较好的相关性,但与苯的相关性不显著,说明苯的来源不同与其他苯系物.     

Assessing microbial degradation of o-xylene at field-scale from the reduction in mass flow rate combined with compound-specific isotope analyses

In recent years, natural attenuation (NA) has evolved into a possible remediation alternative, especially in the case of BTEX spills. In order to be approved by the regulators, biodegradation needs to be demonstrated which requires efficient site investigation and monitoring tools. Three methods--the Integral Groundwater Investigation method, the compound-specific isotope analysis (CSIA) and a newly developed combination of both--were used in this work to quantify at field scale the biodegradation of o-xylene at a former gasworks site which is heavily contaminated with BTEX and PAHs. First, the Integral Groundwater Investigation method [Schwarz, R., Ptak, T., Holder, T., Teutsch, G., 1998. Groundwater risk assessment at contaminated sites: a new investigation approach. In: Herbert, M. and Kovar, K. (Editors), GQ'98 Groundwater Quality: Remediation and Protection. IAHS Publication 250, pp. 68-71; COH 4 (2000) 170] was applied, which allows the determination of mass flow rates of o-xylene by integral pumping tests. Concentration time series obtained during pumping at two wells were used to calculate inversely contaminant mass flow rates at the two control planes that are defined by the diameter of the maximum isochrone. A reactive transport model was used within a Monte Carlo approach to identify biodegradation as the dominant process for reduction in the contaminant mass flow rate between the two consecutive control planes. Secondly, compound-specific carbon isotope analyses of o-xylene were performed on the basis of point-scale samples from the same two wells. The Rayleigh equation was used to quantify the degree of biodegradation that occurred between the wells. Thirdly, a combination of the Integral Groundwater Investigation method and the compound-specific isotope analysis was developed and applied. It comprises isotope measurements during the integral pumping tests and the evaluation of delta13C time series by an inversion algorithm to obtain spatially integrated mean isotope values at the control planes. It was shown that the Rayleigh equation is applicable to spatially integrated mean isotope values in order to obtain the mean biodegradation between the consecutive control planes. All three approaches yielded consistently a 98-99% degradation of o-xylene.     

Humic acid enhanced remediation of an emplaced diesel source in groundwater. 1. Laboratory-based pilot scale test

The enhanced solubility of petroleum-derived compounds in humic acid solutions is the basis for a new groundwater remediation technology. In this unique pilot-scale test, a stationary contaminant source consisting of diesel fuel was placed below the water table in a model sand aquifer (1.2 x 5.5 x 1.8-m deep) and flushed with water at a flow rate of 2 cm/h over 5 years. At 51 days, laboratory grade humic acid was added to the water and maintained at a level of approximately 0.8 g/l. The addition of humic acid had only a small impact on the aqueous transport of the BTEX components, which were rapidly dissolved from the diesel, but had a large effect on the flushing of PAHs, including methylated naphthalenes (MNs). Binding to aqueous humic acid enhanced the solubilization of MNs two- to tenfold. During aqueous transport, biodegradation of the BTEX and PAHs occurred, limiting the lateral and longitudinal extent of the diesel contaminant plume in the model aquifer. It appears that through enhanced solubilization, the overall biodegradation rate of the MNs was increased. As the various MNs were depleted from the diesel source, the MN plume shrank and then disappeared.     

Inverse modeling of BTEX dissolution and biodegradation at the Bemidji, MN crude-oil spill site

The U.S. Geological Survey (USGS) solute transport and biodegradation code BIOMOC was used in conjunction with the USGS universal inverse modeling code UCODE to quantify field-scale hydrocarbon dissolution and biodegradation at the USGS Toxic Substances Hydrology Program crude-oil spill research site located near Bemidji, MN. This inverse modeling effort used the extensive historical data compiled at the Bemidji site from 1986 to 1997 and incorporated a multicomponent transport and biodegradation model. Inverse modeling was successful when coupled transport and degradation processes were incorporated into the model and a single dissolution rate coefficient was used for all BTEX components. Assuming a stationary oil body, we simulated benzene, toluene, ethylbenzene, m,p-xylene, and o-xylene (BTEX) concentrations in the oil and ground water, respectively, as well as dissolved oxygen. Dissolution from the oil phase and aerobic and anaerobic degradation processes were represented. The parameters estimated were the recharge rate, hydraulic conductivity, dissolution rate coefficient, individual first-order BTEX anaerobic degradation rates, and transverse dispersivity. Results were similar for simulations obtained using several alternative conceptual models of the hydrologic system and biodegradation processes. The dissolved BTEX concentration data were not sufficient to discriminate between these conceptual models. The calibrated simulations reproduced the general large-scale evolution of the plume, but did not reproduce the observed small-scale spatial and temporal variability in concentrations. The estimated anaerobic biodegradation rates for toluene and o-xylene were greater than the dissolution rate coefficient. However, the estimated anaerobic biodegradation rates for benzene, ethylbenzene, and m,p-xylene were less than the dissolution rate coefficient. The calibrated model was used to determine the BTEX mass balance in the oil body and groundwater plume. Dissolution from the oil body was greatest for compounds with large effective solubilities (benzene) and with large degradation rates (toluene and o-xylene). Anaerobic degradation removed 77% of the BTEX that dissolved into the water phase and aerobic degradation removed 17%. Although goodness-of-fit measures for the alternative conceptual models were not significantly different, predictions made with the models were quite variable.     

Is it possible to remediate a BTEX contaminated chalky aquifer by in situ chemical oxidation?

An industrial coating site in activity located on a chalky plateau, contaminated by BTEX (mainly xylenes, no benzene), is currently remediated by in situ chemical oxidation (ISCO). We present the bench scale study that was conducted to select the most appropriate oxidant. Ozone and catalyzed hydrogen peroxide (Fenton’s reaction) were discarded since they were incompatible with plant activity. Permanganate, activated percarbonate and activated persulfate were tested. Batch experiments were run with groundwater and groundwater-chalk slurries with these three oxidants. Total BTEX degradation in groundwater was reached with all the oxidants. The molar ratios [oxidant]:[Fe²⁺]:[BTEX] were 100:0:1 with permanganate, 100:100:1 with persulfate and 25:100:1 with percarbonate. Precipitation of either manganese dioxide or iron carbonate (siderite) occurred. The best results with chalk slurries were obtained with permanganate at the molar ratio 110:0:1 and activated persulfate at the molar ratio 110:110:1. To avoid precipitation, persulfate was also used without activation at the molar ratio 140:1. Natural Oxidant Demand measured with both oxidants was lower than 5% of initial oxidant contents. Activated percarbonate was not appropriate because of radical scavenging by carbonated media. Permanganate and persulfate were both effective at oxidant concentrations of ca 1 g kg⁻¹ with permanganate and 1.8 g kg⁻¹ with persulfate and adapted to site conditions. Activation of persulfate was not mandatory. This bench scale study proved that ISCO remediation of a chalky aquifer contaminated by mainly xylenes was possible with permanganate and activated or unactivated persulfate.