In situ sequential treatment of a mixed contaminant plume

Groundwater plumes often contain a mixture of contaminants that cannot easily be remediated in situ using a single technology. The purpose of this research was to evaluate an in situ treatment sequence for the control of a mixed organic plume (chlorinated ethenes and petroleum hydrocarbons) within a Funnel-and-Gate. A shallow plume located in the unconfined aquifer at Alameda Point, CA, was found to contain up to 218,000 μg/l of cis-1,2 dichloroethene (cDCE), 16,000 μg/l of vinyl chloride (VC) and <1000 μg/l of 1,1 dichloroethene (1,1 DCE), trans-1,2 dichloroethene (trans-1,2 DCE) and trichloroethene (TCE). Total benzene, toluene, ethylbenzene and xylenes (BTEX) concentrations were <10,000 μg/l. Contaminated groundwater was funneled into a gate, 3.0 m wide, 4.5 m long and 6.0 m deep (keyed into the underlying aquitard) where treatment occurred. The initial gate segment consisted of granular iron, for the reductive dechlorination of the higher chlorinated ethenes. The second segment, the biosparge zone, promoted aerobic biodegradation of petroleum hydrocarbons and any remaining lesser-chlorinated compounds, stimulated by dissolved oxygen (DO) and carbon dioxide (CO₂) additions via an in situ sparge system (CO₂ was used to neutralize the high pH produced from reactions in the iron wall). Groundwater was drawn through the gate by pumping two wells located at the sealed, downgradient, end. Over a 4-month period an estimated 1350 g of cDCE flowed into the treatment gate and the iron wall removed 1230 g, or 91% of the mass. The influent mass of VC was 572 g and the iron wall removed 535 g, corresponding to 94% mass removal. The other chlorinated ethenes had significantly lower influent masses (3 to 108 g) and the iron wall removed the majority of the mass resulting in >96% mass removal for any of the compounds. In spite of these high removal percentages, laboratory column tests indicated that at these levels of chlorinated contaminants, surface saturation of the iron grains likely contributed to lower than expected reaction rates. In the biosparge zone, mass removal of cDCE appeared to occur predominantly by biodegradation (65%) with volatilization (35%) being an important secondary process. The dominant removal process for VC was volatilization (70%) although significant biodegradation was also indicated (30%). Laboratory microcosm results confirmed the potential for aerobic biodegradation of cDCE and VC. When average influent field concentrations for cDCE and VC were 220,000 and 46,000 μg/l, respectively, the sequential treatment unit removed 99.6% of the total mass and when the influent concentrations decreased to 26,000 and 19,000 μg/l for cDCE and VC, respectively, >99.9% removal within the treatment gate was attained. BTEX compounds were found to be significantly retarded in the iron treatment zone. Although they did eventually break through the granular iron, and into the gravel transition zone, none of these compounds was detected in the biosparge zone. No noticeable interferences between the anaerobic (reductive) and aerobic parts of the system occurred during testing. The results of this experiment show that in situ treatment sequences are viable, although further work is needed to optimize performance.     

零价铁还原降解2,4-二硝基甲苯研究

研究了零价铁对2，4-二硝基甲苯(2，4-DNT)的还原降解情况。实验结果表明，2,4-DNT的还原降解率与溶液初始pH值、初始浓度、溶解氧含量和铁粉投加量等因素有关。2，4-DNT在还原过程中先生成2-氨基-4-硝基甲苯(2A4NT)和4-氨基-2-硝基甲苯(4A2NT)，最后被还原成2，4-二氨基甲苯(2，4-DAT)。     

表面活性剂溶液中多氯联苯溶解的特性

对表面活性剂溶液中多氯联苯的溶解特性进行了研究.发现非离子型表面活性剂对多氯联苯增溶效果优于阴离子型表面活性剂;在浓度大于临界胶束浓度(CMC)范畴,不但表面活性剂的增溶效果远较其浓度低于CMC时为佳,而且表面活性剂浓度与多氯联苯的溶解度成正比地线性相关,此结果说明,表面活性剂主要通过形成胶束来增加多氯联苯的溶解度.多氯联苯在非离子型表面活性剂胶束溶液中与在正己烷中的紫外-可见光谱相似,进一步说明胶束内的多氯联苯分子主要分布于类似正己烷的疏水胶核区域.在十二烷基醇聚氧乙烯(10)醚溶液中,所试多氯联苯的辛醇-水分配系数(K_ow)与其胶束-水分配系数(K_m)存在很好的线性相关关系.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Impact of urbanization on hydrochemical evolution of groundwater and on unsaturated-zone gas composition in the coastal city of Tel Aviv, Israel

The coastal city of Tel Aviv was founded at the beginning of the 20th century. The number of its inhabitants and its water consumption increased rapidly. This study analyses a 15-year record (1934-1948) of pre-industrial development of groundwater chemistry in the urban area. Archive data on concentrations of major ions, dissolved gases (CO2 and O2), organic matter, and pH were available for each half-year during the period of 1934-1948. The major factors causing changes in the chemistry of groundwater flowing in three sandy sub-aquifers have been seawater encroachment due to overpumping, and infiltration of effluents from pit-latrine collectors. Influence of these factors decreases with depth. Landward-penetrating seawater passed through clayey coastal sediments, interbedded among sands and calcareous sandstones, and spread into the Kurkar Group aquifer. This has led to exchange of sodium (dominant in seawater) with calcium adsorbed on clay particles, enriching groundwater with calcium. Intensity of cation exchange decreases inland and with depth. Infiltration of pit-latrine effluents has introduced large amounts of ammonium into the unsaturated zone. Its rapid oxidation in unsaturated sediments has caused massive nitrate production, accompanied by pore-water acidification. This process induces dissolution of vadose carbonate, resulting in enrichment of groundwater recharge in calcium. Anthropogenically induced dissolution of calcite in the unsaturated zone has been the major factor for the increase of Ca2+ concentration in groundwater, accounting for about 80% of this increase. In the interface zone, an additional 20% of calcium has been supplied by cation exchange. Owing to pH increase caused by denitrification in the aquifer, Ca(2+)-rich waters supersaturated with calcite could be formed, especially in the capillary fringe of the uppermost sub-aquifer, which could induce calcite precipitation and ultimately lead to the cementation of sandy aquifers. Urban development has caused drastic changes in the gas content in the unsaturated zone and in groundwater. Carbon dioxide was intensively generated by nitrification-denitrification processes, by hydration of urea, to a lesser degree by oxidation of organic matter, and probably by anoxic biodegradation of organics. Between 1934 and 1948, concentrations of CO2 in unsaturated sediment air rose from 3.2% to 7.6%. In the unsaturated zone, oxygen consumption for oxidation of ammonium and organic matter lowered O2 concentrations in sediment air to unusually low values of 3.9-12.9%. Nitrification in the urban unsaturated zone could thus serve as a pump, sucking in atmospheric oxygen at a rate of about 0.3-0.5 g m-2 day-1. The extreme concentrations of CO2 and O2 in unsaturated sediments have been preserved due to production and consumption of gas under conditions of diminishing areas open to the atmosphere, uncovered by buildings and by roads.     

Quantifying the effects of fumarate on in situ reductive dechlorination rates

In situ methods are needed to evaluate the effectiveness of chemical amendments at enhancing reductive dechlorination rates in groundwater that is contaminated with the priority pollutant, trichloroethene (TCE). In this communication, a method that utilizes single-well, “push–pull” tests to quantify the effects of chemical amendments on in situ reductive dechlorination rates is presented and demonstrated. Five push–pull tests were conducted in each of five monitoring wells located in a TCE-contaminated aquifer at the site of a former chemical manufacturing facility. Rates for the reductive dechlorination of the fluorinated TCE-surrogate, trichlorofluoroethene (TCFE), were measured before (test 1) and after (test 5) three successive additions (tests 2–4) of fumarate. Fumarate was selected to stimulate the growth and activity of indigenous microorganisms with the metabolic capability to reduce TCFE and TCE. In three wells, first-order rate constants for the reductive dechlorination of TCFE increased by 8.2–92 times following fumarate additions. In two wells, reductive dechlorination of TCFE was observed after fumarate additions but not before. The transformation behavior of fumarate was also monitored following each fumarate addition. Correlations between the reductive dechlorination of TCFE and the reduction of fumarate to succinate were observed, indicating that these reactions were supported by similar biogeochemical conditions at this site.     

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.     

自硬性玻璃基生物水泥的结构研究

利用X射线衍射和扫描电镜研究了玻璃基生物水泥在生理模拟液中羟基磷灰石（HAP）晶相的形成和长大，应用溶解－析晶理论，阐述了玻璃粉末与调和液及表面活性剂反应，形成HAP的动力学观点，实验结果表明，玻璃基生物水泥在调和液作用下，会形成HAP晶相，在生理模拟液中，随着时间的延长，晶体逐渐长大，图3表1参5     

草酸盐介导下含As(V)黄钾铁矾的相转化过程与As(V)的再分配行为

黄钾铁矾能够通过吸附和共沉淀作用固定酸性矿山废水（AMD）中的重（类）金属（如砷）,降低其迁移性和生物可利用性.草酸盐广泛存在于天然水环境中,其具有的羧酸官能团能改变铁矿物的稳定性,进而影响吸持的重（类）金属的再分配行为.利用水热法合成含As（V）黄钾铁矾,探究其在不同草酸盐浓度与pH条件下的溶解、重结晶和共沉淀As（V）的行为.研究结果表明,草酸盐与含As（V）黄钾铁矾表面Fe（III）活性位点配位形成的可溶性强络合物是促进矿物溶解的第一步和关键;在pH 2.5时,含As（V）黄钾铁矾的溶解速率随草酸盐浓度增加而增加,伴随大量As（V）释放到溶液,反应过程中只有少量As（V）重新吸附到固相上,这是由于草酸盐与As（V）竞争矿物表面的同一活性位点;在pH 6.5条件下,草酸盐促进含As（V）黄钾铁矾的重结晶,经X射线衍射分析表明针铁矿和纤铁矿为主要产物,能有效地吸附释放的As（V）.研究结果有助于揭示在AMD环境下黄钾铁矾沉积物与含羧酸官能团有机酸共存时对As（V）的释放和固定机理,对AMD环境中As（V）污染控制有重要意义.     

小球藻对土壤-水稻系统砷化学形态转化的影响

为揭示绿藻对土壤-水稻系统砷形态转化的影响特征,系统分析了不同浓度小球藻共存条件下水稻土砷氧化还原与溶解释放行为的变化,并结合水稻培育试验,对小球藻影响水稻砷吸收与体内砷形态的发生机制进行探讨.试验设置对照组及小球藻浓度（以体积分数计）分别为1%、5%、10%的处理,研究了小球藻对溶液体系、淹水土壤体系和淹水土壤-水稻体系中砷的化学形态转化的作用.结果表明:加藻组使As（Ⅲ）溶液和淹水土壤E_h（氧化还原电位）与pH均普遍高于对照组.在As（Ⅲ）溶液体系中,加藻组As（Ⅲ）氧化转化率较对照组升高2.38%~4.95%,该作用在淹水土壤中得到印证,小球藻的共存使土壤孔隙水ρ[As（Ⅴ）]较对照组升高129.22%~221.41%,而ρ（甲基砷）出现显著下降（5.25%~53.31%）.水稻栽培试验进一步发现,小球藻明显促进土壤中晶体态铁铝氧化物向弱结晶与无定形铁铝氧化物结合态砷等的转化,导致水稻幼苗对砷的吸收积累量增加-3.4%~23.11%,推测这与小球藻作用下土壤孔隙水ρ（DOC）的增加密切相关.研究显示,尽管小球藻有利于提高淹水土壤体系E_h并加速As（Ⅲ）的氧化转化,但小球藻可能通过有机酸等分泌物的竞争吸附作用促进铁铝氧化物结合态砷的溶解释放,从而增加水稻砷吸收;淡水藻类对土壤-水稻体系砷吸收积累的风险值得引起高度关注,并需要在大田试验中进一步加以验证.