Orientador: João Carlos Dourado / Banca: Carlos Alberto Mendonça / Banca: Walter Malagutti Filho / Resumo: Este trabalho discute a aplicabilidade do método geofísico Eletromagnético Transiente (TEM) a partir de análise comparativa com o método de Eletrorresistividade, em uma área industrial contaminada por derivados de petróleo e atualmente sob processos de Atenuação Natural. Dentre os contaminantes presentes no solo e água subterrânea estão o Benzeno, Tolueno, Xileno, 1,2 Dicloroetano, Sódio, Cloreto e Sulfato. A remediação da área é realizada exclusivamente por Atenuação Natural, ou seja, ação de processos físicos, químicos e biológicos responsáveis pela degradação, dispersão e diluição dos contaminantes. Foram utilizadas as técnicas de sondagem eletromagnética de "loop" central, caminhamento eletromagnético, sondagem elétrica vertical e caminhamento elétrico. Os resultados apresentam uma anomalia de baixa resistividade adjacente aos poços de injeção, e anomalias de alta resistividade sob estes poços. A grande área abrangida pela anomalia de baixa resistividade é fruto principalmente da biodegradação dos contaminantes de fase líquida leve não aquosa - LNAPL, cujas sucessivas quebras em compostos mais simples por ação de microorganismos resulta em ácidos orgânicos que corroem grãos minerais, que são liberados ao meio sob a forma iônica. A pequena área abrangida pela anomalia de alta resistividade é produto da concentração de contaminantes pouco degradados, caracterizados por elevada resistividade em relação á água. O TEM se mostrou aplicável no estudo de áreas contaminadas e o processo de Atenuação Natural está sendo eficaz na remediação da área. / Abstract: This work discuss the applicability of the Transient Electromagnetic Method (TEM) from comparative analysis with the Electrical Method, in an industrial area contaminated by oil derived and currently under processes of Natural Attenuation. Amongst the contaminants presents in the soil and groundwater they are the Benzene, Toluene, Xylene, 1,2 Dichloroetene, Sodium, Chloride and Sulphate. A remediation of the area is carried through exclusively by Natural Attenuation, or either, action of physical, chemical and biological processes responsible for the degradation, dispersion and dilution of contaminants. The techniques of electromagnetic sounding of central loop, electromagnetic tomography, vertical electric sounding and electric tomography had been used. The results present an anomaly of low adjacent resistivity to the injection wells, and anomalies of high resistivity under these wells. The great area enclosed for the anomaly of low resistivity is fruit mainly of the biodegradation of the contaminants of light non-aqueous phase liquid - LNAPL, whose successive breakings in simpler composites for action of microorganisms result in acid organic that corrode mineral grains, that are set free to the way under the ionic form. The small area enclosed for the anomaly of high resistivity is product of the concentration of contaminants little degraded, characterized for raised resistivity in relation a water. The TEM if it showed applicable in the study of contaminated areas and the process of Natural Attenuation is being efficient in the remediation of the area. / Mestre

Development of a scientific basis for management of uranium bearing wastes and contaminants requires information from natural geologic systems. The following study of the Coles Hill uranium deposit and associated weathered zone constrains processes leading to the natural attenuation of uranium within an oxidizing, fluid rich environment typical of the eastern US. At the Coles Hill deposit fracture hosted, primary U(IV) bearing mineral assemblages formed during hydrothermal activity associated with Mesozoic faulting. The most abundant ore assemblage consists of coffinite and apatite, but uraninite-zeolite and uraninite-calcite assemblages are also present. Within the shallow bedrock there is a uranium redox transition where alteration of U(IV) minerals has produced secondary uranium minerals. Geochemical data suggests that the volume of rock containing this U(IV)/U(VI) transition is acting as a closed system with respect to uranium mass transport during oxidation. The dominant mechanism of uranium fixation within the oxidizing zone is the precipitation of Ba-U(VI) phosphates (meta-autunite group). Speciation and mineral stability calculations indicate that ground waters from the Coles Hill weathered zone are saturated with respect to Ba-meta-autunite and that this mineral is capable of buffering dissolved uranium concentrations to values lower than 20 parts per billion. U(VI) phosphates of the meta-autunite group are not stable in the vadose zone (soil pH ~ 4.5) at the Coles Hill site. In this zone uranium is associated with (Ba, Ca, Sr) aluminum phosphate of the crandallite group as well as with phosphate sorbed to iron oxy-hydroxide mineral coatings. Uranium leached from the vadose zone is reprecipitated as new meta-autunite minerals below the water table due to higher pH conditions of ~6.0 and relatively high activity ratios of dissolved phosphate to carbonate (e.g. log [H2PO4-/HCO3-] > -3). It is estimated that the U(VI) phosphates responsible for the natural attenuation of uranium at this site persist within the weathering zone for hundreds of thousands of years. Thus, the Coles Hill deposit represents an excellent natural laboratory for the study of uranium attenuation with potential applications for the design and implementation of cost effective remediation and containment strategies, such as soil amendments techniques and in-situ reactive barriers technologies. / Ph. D.

Natural Attenuation Software (NAS) was developed as a screening tool to estimate remediation timeframes for monitored natural attenuation (MNA) to lower groundwater contaminant concentrations to regulatory limits, and to assist in decision-making on the level of source zone treatment in conjunction with MNA using site-specific remediation objectives. In addition, NAS facilitates the combined use of MNA with engineered remedial actions (ERAs) so that the benefits of each technology can be maximized while minimizing costs of remediation. The primary expected benefit of NAS is to increase regulatory acceptance of MNA, thereby decreasing overall remediation costs. NAS is designed for application to ground-water systems consisting of porous, relatively homogeneous, saturated media, and assumes that groundwater flow is uniform and unidirectional. NAS consists of a combination of analytical and numerical solute transport models implemented in three main interactive modules to provide estimates for: (1) target source concentration required for a plume extent to contract to regulatory limits, (2) time required for NAPL contaminants in the source area to attenuate to a predetermined target source concentration, and (3) time required for a plume extent to contract to regulatory limits after source reduction. Natural attenuation processes that NAS models include advection, dispersion, sorption, non-aqueous phase liquid (NAPL) dissolution, and biodegradation. NAS determines redox zonation, and estimates and applies varied biodegradation rates from one redox zone to the next. Recently, NAS was enhanced to include petroleum hydrocarbons, chlorinated ethenes, chlorinated ethanes, chlorinated methanes, and chlorinated benzenes, or any user-defined contaminants (e.g., heavy metals, radioisotopes), and has included the capability to model co-mingled plumes. To enable comparison of remediation timeframe estimates between MNA and specific ERAs, NAS was modified to incorporate an estimation technique for timeframes associated with pump-and-treat remediation technology for comparison to, or in conjunction with, MNA. NAS also expanded analysis tools for improved performance assessment, as well as the assessment of sustainability of natural attenuation processes over time. A Department of Defense (DoD) Environmental Security Technology Certification Program (ESTCP) demonstration was undertaken to evaluate the capability of the NAS software to provide reasonable estimates of MNA cleanup timeframes in a variety of environments and sites throughout the United States. Overall, results suggest that NAS was satisfactory in meeting performance objectives set forth in the demonstration, and that because NAS is based on sound science, it can serve as an effective tool for decision-making and data analysis at a wide range of contaminated sites and is not limited to a small subset of “simple sites” because of its simplicity. At some sites, NAS-estimated timeframes were crucial for winning regulatory acceptance of MNA, with cost-benefit analyses providing estimates of savings associated with using MNA as a final remediation strategy. / Ph. D.

Laboratory microcosm experiments were conducted to assess the potential for biostimulation and bioaugmentation as source reduction measures in support of a monitored natural attenuation remedial strategy at Naval Amphibious Base (NAB) Little Creek. Previous work with laboratory microcosms conducted under simulated natural (unamended) conditions has demonstrated that indigenous dehalorespirators were capable of partial dechlorination of tetrachloroethene (PCE) to cis-dichloroethene (cis-DCE). This study attempts to achieve complete reductive dechlorination with amendments to static microcosms to test the hypotheses that nutrient-limited or microorganism-limited conditions exist in aquifer sediments obtained from the site. The enhanced bioremediation experiments were comprised of nutrient-amended microcosms receiving additions of electron donors, mineral medium, or anaerobic digester supernatant, and dechlorinating culture-amended microcosms were inoculated with a culture capable of transforming PCE to ethene. Reductive dechlorination in the nutrient-amended microcosms proceeded to cis-DCE over a 260-day study period, at slightly higher rates than in experiments conducted with aquifer sediments from the same location under natural conditions. Inoculation of aquifer sediments with a small amount of dechlorinating culture initiated rapid transformation of PCE to vinyl chloride (VC) by day 18 of the study. Zero-order rates of PCE dechlorination in unamended, propionate-, formate-, mineral medium-, digester supernatant-, and dechlorinating culture-amended microcosms were 0.24, 0.750, 1.30, 0.339, 0.177, and 1.75 µM/day, respectively. The results of this study suggest that an engineered biostimulation approach alone may not be as beneficial for PCE source reduction at NAB Little Creek, than bioaugmentation with competent dehalorespirators, along with the inclusion of supplemental nutrients which would be available to stimulate dechlorination activity of both indigenous and introduced microorganisms. / Master of Science

Contamination of soils and groundwater with nitroaromatic compounds such as 2,4,6-trinitrotoluene (TNT) and dinitrotoluenes (DNTs) has drawn considerable attention due to widely distributed contamination sites and substantial efforts for cleanup. Two isomers of DNT, specifically 2,6-dinitrotoluene (2,6-DNT) and 2,4-dinitrotoluene (2,4-DNT), occur as soil and groundwater contaminants at former TNT production sites. The discovery of bacteria that use DNT isomers as electron donors has encouraged bioremediation at contaminated sites. Current work is extending the existing engineered bioremediation to naturally occurring in situ biodegradation and focuses on the application of natural attenuation (NA) as a remediation strategy for residual DNT at contaminated sites. More specifically this research evaluated factors influencing in situ bioremediation of DNTs and TNT in surface soils, vadose zones, and saturated medium. Applications involving surface soils and vadose zones investigated the potential of water infiltration to promote in situ bioremediation. Studies in saturated media were more applicable to NA. Factors that were also considered in studies conduced included: 1) the presence and distribution of degrading microbes in field soils (Barksdale, WI); 2) the dissolution and bioavailability of contaminants in historically contaminated soils; and 3) the effect of mixtures of contaminants (i.e., DNTs and TNT) on biodegradation processes. This research provided information useful for practitioners considering an in situ bioremediation NA as a remedial solution for contaminated sites. Under the condition simulating downflow of surface waters or rainwater, the rapid rate of DNT degradation could be facilitated by the availability of oxygen in the soil gas without concern of toxicity (i.e., nitrite evolution and pH drop) and addition of nutrients. As a result, in situ bioremediation or NA should be strongly considered as a remedial option for Barksdale soils and similar sites where relatively low concentrations of DNT isomers are present as contaminants. At TNT contaminated sites TNT was not mineralized by indigenous microorganisms despite oxidative biotransformation, and mixed culture capable of growth on DNT also could not develop the mineralization of TNT during DNT degradation. This suggests that the mixtures of contamination did not improve the potential for in situ TNT bioremediation.

Factors influencing natural attenuation of dinitrotoluenes (DNT) in surface soils and the application of monitored natural attenuation (MNA) as a remediation strategy were examined using contaminated soils from Badger Army Ammunition Plant (BAAP). Based on the previous research involving contaminated media obtained from locations at BAAP, and the fact that groundwater at the site is not contaminated, it seemed likely that aerobic biodegradation of DNT is active without intervention, and that natural attenuation may be an effective strategy for managing the contamination that exists at BAAP. Microcosms showed that microbes indigenous to soils are capable of 2,4-DNT mineralization and that DNT will adsorb reversibly and become bioavailable. In column studies 2,4-DNT biodegradation was observed and the nitrite evolved during DNT degradation was presumably removed due to oxidation by nitrite oxidizers. The use of simulated rainwater as influent with no nutrient amendments suggests that nutrients do not limit the biodegradation of low concentrations of DNT in the soil tested. In the chemostat study carried out to study effect lowering of temperature (22㬠15㬠10㬠7.5㠡nd 4㩠on biodegradation of DNT at hydraulic retention time of 2.5 days, no sustained change in the DNT substrate removal was observed with change in temperature, but it had a large effect on the nitrite oxidizers. This suggests that the seasonal fluctuations in temperature will have minimal effect on the DNT removal via biodegradation at temperatures above 0㮠Nitrite oxidizers were active at 22㬠their activity decreased at 15㠡nd ceased at temperatures 10㠡nd lower. Nitrite is generally taken as a line of evidence for biodegradation of DNT. The results from the soil column study and chemostat showed that nitrite measurement should not be always taken as a conclusive indicator of DNT degradation. It should be taken into consideration that absence of nitrite does not necessarily mean absence of DNT biodegradation (probably at high temperatures).

The entire stretch of the Ohio River is under fish consumption advisories due to contamination with polychlorinated biphenyls (PCBs). In this study, natural attenuation and biostimulation of PCBs and microbial communities responsible for PCB transformations were investigated in Ohio River sediments. Natural attenuation of PCBs was negligible in sediments, which was likely attributed to low temperature conditions during most of the year, as well as low amounts of available nitrogen, phosphorus, and organic carbon. Moreover, surface sediments were relatively oxidized, as indicated by the prevalence of aerobic bacteria such as beta- Proteobacteria, alpha-Proteobacteria, Sphingobacteria, and Nitrospira in 16S rRNA sediment clone libraries. On the other hand, several reductive dechlorinators were detected in sediments, including Dehalococcoides, Desulfitobacterium spp. which suggested that reductive dechlorination might be possible in sediments under certain biogeochemical conditions. Considerable amounts of PCBs were transformed by reductive dechlorination (80% in 177 days by pattern N) when sediments were maintained under anaerobic conditions, amended with nutrients and organic carbon, and incubated at 25 ºC in lab microcosms. Analysis of 16S rRNA clone libraries from these treatments revealed that Bacteroidetes, Chloroflexi and Firmicutes were enriched and Proteobacteria were depleted compared to clone libraries from treatment without organic amendments. Reductive dechlorination was decreased in sediments incubated at 10 and 40 ºC, and was not affected by FeSO4 amendments compared to unamended sediments incubated at 25 ºC. Transformations of PCB-153 were investigated in sediments under anaerobic, aerobic and sequential anaerobic and aerobic conditions. Transformations were only observed in treatments with an anaerobic phase, which occurred by reductive dechlorination by pattern N. Neither PCB-153 nor dechlorination products PCB-99 or PCB-47 were transformed under aerobic conditions. Analysis of 16S rRNA clone libraries revealed that Bacteoridetes, Chloroflexi, and Firmicutes were enriched under anaerobic conditions and Proteobacteria were enriched under aerobic conditions. Results from this study revealed that natural attenuation and biostimulation were not effective at removing PCBs from Ohio River sediments. Hence, other remediation methods will need to be employed to decrease PCB levels in this ecosystem.

Um estudo de caso e dois experimentos controlados de campo foram realizados, a fim de avaliar o impacto do etanol nos processos de atenuação natural que atuam em plumas de contaminação em fase dissolvida de gasolina. No estudo de caso, foi monitorada uma pluma de contaminação de E22 (gasolina com 22% de etanol em volume) em Itaguaí (RJ). Os dois experimentos controlados foram realizados no aqüífero de Borden, no Canadá, para estudar plumas de E10 e E95 (gasolinas com 10 e 95% de volume de etanol, respectivamente). Neste caso, foram realizadas injeções dos contaminantes abaixo do nível d\'água, gerando plumas que foram monitoradas. O etanol, em subsuperfície, particiona rapidamente para a água subterrânea, deixando a fase residual, e é transportado com a velocidade da água subterrânea. Os outros compostos orgânicos de gasolina migram com velocidades menores. Benzeno e tolueno apresentam velocidades mais próximas do etanol, enquanto trimetilbezenos e naftalenos são os mais retardados. Estas diferenças de migração dos compostos resultaram na separação espacial entre as plumas ao longo do período monitorado. A maior concentração de etanol detectada foi de 12.762 mg/L, que corresponde a um volume de etanol em água de 1,63%. As baixas concentrações de etanol não evidenciam que ele tenha exercido efeito cosolvente pronunciado na solubilidade dos compostos da gasolina. Os compostos orgânicos apresentaram perdas de massa ao longo do tempo de monitoramento. A biodegradação dos contaminantes foi observada pelo consumo de oxigênio dissolvido e metonogênese. O etanol apresentou a maior diminuição de massa e foi biotransformado mesmo sob condições anóxicas. O composto que apresentou a menos perda de massa foi o benzeno. A maior persistência de benzeno é atribuída à sua velocidade de migração próxima à água subterrânea associada ao efeito de consumo preferencial de receptores de elétrons pelo etanol. No estudo de caso, o desaparecimento de etanol pode estar relacionado à sua alta taxa de biodegradação, fato observado nos experimentos de campo. Entretanto, o efeito cosolvente na pluma, que explicaria o deplecionamento dos compostos mais móveis, como benzeno e tolueno, na pluma não foi comprovado nos experimentos. / A case study and two controlled field experiments were conducted to evaluate the impact of ethanol on the natural attenuation processes affecting dissolved phase of gasoline plumes. The case study was conducted in Itaguaí (RJ) where an E22 (gasoline with 22 % by volume of denatured ethanol) contaminant plume was studied. The controlled field experiments were conducted at the Borden aquifer in Canada to study plumes E10 and E95. In this case, contaminants were injected below the water table and plumes were monitored down gradient. In subsurface, ethanol partitions fastly from the residual phase and is transported with the ground water velocity. The other organic compounds migrate with lower velocities. Benzene and toluene present velocities close to ethanol, while trimethylbenzenes and naphthalene are the most retarded. These transport differences resulted in the spatial separation between the plumes throughout the monitoring period. The highest ethanol concentration detected was 12,762 mg/L, which corresponds to 1.63 % of ethanol volume in water. The ethanol concentrations detected do not support the cosolvency effect on the gasoline constituents of the plumes. The organic compounds presented mass losses throughout the monitoring period. Biodegradation was also demonstrated through dissolved oxygen consumption and methanogenesis. Ethanol presented the highest mass losses and was biotransformed under anoxic conditions. Benzene presented the smallest mass loss. Benzene´s higher persistence is related to the migration close to the ground water velocity and the preferential consumption of electron acceptors by ethanol. In the case study, the disappearance of ethanol can be related to its higher biodegradation rate, which was detected through the field experiments. However, the cosolvent effect in the plume, which would explain the depletion of the most mobile compounds such as benzene and toluene was not observed during the field experiments.

Estudos recentes constataram a existência de processos que permitem a atenuação natural dos contaminantes presentes nos lixiviados. O adequado entendimento destes processos pode originar benefícios possíveis de serem aplicados em aterros antigos, novos ou naqueles que ainda serão concebidos. O presente estudo avaliou o comportamento e a atenuação de contaminantes dos líxiviados no solo, por meio de experimento desenvolvido em colunas de percolação e, para a avaliação da atenuação este teste é indicado por refletir as condições naturais e as características adsortivas do solo, propiciando uma melhor simulação da atenuação. O lixiviado e o solo utilizados neste experimento são provenientes do aterro sanitário de São Carlos - SP. O solo utilizado foi caracterizado quanto à composição física, química, biológica e mineralógica para verificar o transporte do percolado nas colunas e a interação solo-contaminante. Na área do aterro foram feitas perfurações, ensaios de condutividade hidráulica e avaliação da geologia local, para conhecimento das características físicas, químicas, biológicas, mineralógicas e geológicas do solo in situ. Este foi classificado como arenoso, apresentando características físicas e químicas que não se enquadram nos parâmetros adequados para sua utilização em áreas de disposição de resíduos sólidos urbanos, pois, a capacidade de troca de cátions, superfície específica, potencial hidrogeniônico e classe textural arenosa, evidenciam que este solo possui deficiente capacidade de retenção e imobilização de contaminantes. Além disso, pela observação in situ, constata-se que a área de disposição de resíduos sólidos de São Carlos esta situado sobre rochas da Formação Botucatu, sendo que a mineralogia do solo presente no local é composta de quartzo, caulinita, goethita, hematita, gibsita e ilita. O ensaio de condutividade hidráulica indicou que o solo presente na base do Aterro sanitário não atende a valor de permeabilidade exigida por norma, o que poderá permitir a infiltração de água da chuva, aumentando a produção do lixiviado e sua movimentação no perfil, podendo atingir as águas subterrâneas. Assim, foram traçadas curvas características do transporte de contaminantes nas amostras efluentes monitoradas durante o processo de percolação, coletadas a cada 0,25 volume de poros até atingir 10,0 volume de poros percolados. As curvas características do transporte de contaminantes traçadas apresentaram baixas concentrações de Chumbo, Cádmio, Ferro, Zinco, Manganês, Cálcio, Magnésio, Cobre, Cromo nas amostras fluentes. Já o Sódio, Potássio, Cloro, Níquel e Alumínio foram preferencialmente percolados com o lixiviado, evidenciando a variação da faixa de concentração de cada elemento no percolado. Os perfis de concentração dos metais pesados mostraram que existe uma frente de contaminação. As curvas de retenção de metais no solo mostraram que a preferência de sorção apresentada pelos solos nas colunas foi : Cobre > Cádmio > Cálcio > Zinco > Magnésio > Potássio > Manganês > Fósforo > Ferro > Níquel > Alumínio. Cujos valores retidos no solo das colunas podem estar evidenciando a capacidade deste solo em reter contaminantes.O solo em questão apresentou baixo potencial para retenção dos contaminantes presentes no lixiviado, classificado como arenoso e, com características químicas que não se enquadram nos parâmetros adequados para sua utilização em áreas de disposição de resíduos sólidos urbanos. / Recent studies had found the existence of processes that allow a natural attenuation of the leachates\'s cotaminants. An adequate understanding of these processes may originate benefits, that may be applied in ancient, new or to be created landfills. This work evaluated the contaminant\'s behavior and attenuation, contaminants existing in soil\'s leaching, throughout an experiment developed in percolation columns. This is the indicated examination for evaluate the attenuation, because it reflects soil\'s natural conditions and adsorptive characteristics, providing a better simulation of it\'s attenuation. The leachate and the soil used in this experiment came from Sao Carlos-SP landfill. The used soil has been characterized as its mineralogical\'s and physical chemical-biological\'s composition, looking for the percolated\'s transportation inside the columns, and for the interaction soil-contaminant. The landfill\'s area has been several times drilled, tested as it\'s hydraulic conductivity and assessment of local geology, in order to know the physical, chemical, biological, mineralogical and geological in situ soil\'s characteristics. This, has been classified as sandy, and, by presenting chemical characteristics that does not reach the adequated value for utilization on solid urban wastes, due to the values of CTC, SE, pH, and the textural sandy class, what shows a deficient buffering capacity in retaining and immobilisating contaminants. By observation in situ, has been found that Sao Carlos\'s solids disposal waste is located over rocks from the Botucatu formation, and the mineralogy of it is composed of quartz, caulinith, goethith, hematith, gibsith an ilith. The hydraulic conductivity test has indicated that the soil in the base of the sanitary landfill does not reaches the permeability values required by the standards, what may allow rain water\'s infiltration, and raises the amount of leachate and it\'s movement onto the ground, and even the leachete to reach the underground waters. So, has been drawn the characteristics curves of the contaminant\'s transportation in the effluents samples found during the percolation process, collected by every 0,25 VP until it reaches 10,0 VP percolated. The characteristical curves of the contaminant\'s transportation drawn showed low concentrations in the effluent samples of Lead, Cadmium, Iron, Zinc, Manganese, Calcium, Magnesium, Cooper, Chromium. Also, Sodium, Potassium, Chlorine, Nickel and Aluminium had been preferencially percolated within the leachate, what evidentiates the variation in the range of concentrations of every percolated element. The concentration profiles from heavy metal\'s had shown that there is a front of contamination. The retention curves from the soil\'s retaining metal showed that the preferency for the sorption was: Cooper > Cadmium > Calcium > Zinc > Magnesium > Potassium > Manganese > Phosphorus > Iron > Nickel > Aluminium, whose values may point the soil\'s ability in retaining contaminants. The studied soil has presented low potential in retain contaminants from the leachete, and is characterized as sandy, and it\'s chemical features shall not be framed according the standards parameters to be utilized in solid urban waste\'s disposal.

For this study, we revisited whether the common iron Fe mineral, magnetite Fe3O4 (s), can reduce tetrachloroethylene (PCE) and trichloroethylene (TCE) as discrepancies exist in the literature regarding rates and extent of reduction. We measured PCE and TCE reduction in batch reactors as a function of magnetite stoichiometry (x = Fe2+/Fe3+ ratio), solids loading, pH, and Fe(II) concentration. Our results show that magnetite reacts only slowly with TCE (t1/2 = 7.6 years) and is not reactive with PCE over 150 days. The addition of aqueous Fe(II) to magnetite suspensions, however, results in slow, but measurable PCE and TCE reduction under some conditions. The solubility of ferrous hydroxide, Fe(OH)2(s), appears to play an important role in whether magnetite reduces PCE and TCE. In addition, we found that Fe(OH)2(s) reduces PCE and TCE at high Fe(II) concentrations as well. At certain conditions degradation of the PCE and TCE is enhanced by an unexplored synergistic response from magnetite and ferrous hydroxide iron phases. Our work suggests that measuring dissolved Fe(II) concentration and pH may be used as indicators to predict whether PCE and TCE will be abiotically degraded by groundwater aquifer solids containing magnetite.