RESUMO
This study investigated chlorate reduction kinetics in multiple samples of sediments from a longitudinal profile of a wetland located downstream of the effluent discharge of a cellulose plant, including characterisation of the bacterial communities involved. The sediments were exposed to different initial chlorate concentrations in microcosm tests, with and without the addition of acetate as an external electron donor, and in a matrix of natural water or a defined medium. At a high initial chlorate concentration of 100 mg/L, in the absence of an external electron source, the degradation curves presented first-order kinetics, influenced by electron donor availability. The first-order kinetic constant varied between 0.05 and 0.17 day(-1). Subsequently, when the initial chlorate concentration was reduced to 7 mg/L, a zero-order kinetic was obtained, with the kinetic constant presenting values between 1.1 and 1.3 mg/L-day. No correlation was observed between chlorate degradation kinetics and the location of the sampling points or the previous history of exposure to chlorate. Other factors evaluated, such as the availability of organic matter or the chlorate reducing bacteria count, also proved not to have any incidence on the results. The richness of chlorate reducing bacteria species in the different samples analysed were also similar, with the greatest similarity being found between cld genes in the samples from the upstream or downstream sampling points. Additionally, cld genes most similar to those present in PCRB like Dechlorospirillum sp., Alicycliphilus denitrificans, Dechloromonas agitata, Dechloromonas sp. LT1 and Ideonella dechloratans were detected. This study showed that the anaerobic sediments of the Cruces river wetland present a high potential for chlorate natural attenuation, regardless of the previous history of exposure to chlorate. This capacity is associated with the presence of a diverse community of chlorate reducing bacteria.
Assuntos
Bactérias/metabolismo , Cloratos/metabolismo , Sedimentos Geológicos/microbiologia , Rios/microbiologia , Áreas Alagadas , Bactérias/genética , Biodegradação Ambiental , Chile , DNA Ribossômico/genética , Eletroforese em Gel de Gradiente Desnaturante , Genes Bacterianos/genética , Geografia , Cinética , Oxirredução , Oxirredutases/genética , Oxirredutases/metabolismo , Percloratos/metabolismoRESUMO
Using the biogeochemical model CCBATCH, which we expanded to include transport processes, we study a novel approach for the treatment of aquifers contaminated with toxic concentrations of metals, the diffusion-active permeable reactive barrier (DAPRB), which is based on generation of sulfide by Sulfate Reducing Bacteria (SRB) as the groundwater moves through a layered treatment zone. In the DAPRB, layers of low conductivity (low-K) containing reactive materials are intercalated between layers of high conductivity (high-K) that transport the groundwater across the barrier. Because diffusion dominates transport in the reactive layers, microbial communities can take advantage there of the chemical-gradient mechanism for protection from toxicants. The ideal sulfidic DAPRB design includes particulate organic matter (POM) and solid sulfate mineral inside the reactive (low-K) layer. This leads to sulfate reduction and the formation of sulfide ligands that complex with toxic metals, such as Zn(2+) in the high-K layer. We perform a theoretical biogeochemical analysis of the ideal configuration of a DAPRB for treatment of Zn-contaminated groundwater. Our analysis using the expanded CCBATCH confirms the gradient-resistance mechanism for bio-protection, with the ZnS bio-sink forming at the intersection of the Zn and sulfide plumes inside the high-K layers of the DAPRB. The detailed DAPRB analysis also shows that total alkalinity and pH distributions are representative footprints of the two key biogeochemical processes taking place, sulfidogenesis and Zn immobilization as sulfide mineral. This is so because these two reactions consume or produce acidic hydrogen and alkalinity. Additionally, because Zn immobilization is due to ZnS mineral precipitation, the ZnS mineral distribution is a good indicator for the bio-sink. Bio-sinks are located for the most part within the high-K layers, and their exact position depends on the relative magnitude of metal and sulfide fluxes. Finally, we conduct a practicality analysis that supports the feasibility of implementing the proposed design. For instance, the fraction of reactive material that is consumed during sulfidogenesis is relatively small (including POM and sulfate source), a total volume fraction of less than 6% over a time span of 50years.
Assuntos
Modelos Biológicos , Modelos Químicos , Sulfatos/metabolismo , Sulfetos/metabolismo , Poluentes Químicos da Água/química , Zinco/químicaRESUMO
We develop a comprehensive biogeochemical framework for understanding and quantitatively evaluating metals bio-protection in sulfidic microbial systems. We implement the biogeochemical framework in CCBATCH by expanding its chemical equilibrium and biological sub-models for surface complexation and the formation of soluble and solid products, respectively. We apply the expanded CCBATCH to understand the relative importance of the various key ligands of sulfidic systems in Zn detoxification. Our biogeochemical analysis emphasizes the relative importance of sulfide over other microbial products in Zn detoxification, because the sulfide yield is an order of magnitude higher than that of other microbial products, while its reactivity toward metals also is highest. In particular, metal-titration simulations using the expanded CCBATCH in a batch mode illustrate how sulfide detoxifies Zn, controlling its speciation as long as total sulfide is greater than added Zn. Only in the absence of sulfide does complexation of Zn to biogenic organic ligands play a role in detoxification. Our biogeochemical analysis conveys fundamental insight on the potential of the key ligands of sulfidic systems to effect Zn detoxification. Sulfide stands out for its reactivity and prevalence in sulfidic systems.
Assuntos
Metais/isolamento & purificação , Sulfetos/metabolismo , Bactérias Redutoras de Enxofre/metabolismo , Biodegradação Ambiental , Água Doce , Glucose/metabolismo , Cinética , Ligantes , Solubilidade , Titulometria , Zinco/isolamento & purificaçãoRESUMO
We expand the biogeochemical program CCBATCH to describe transport processes in 1-D ground-water systems. We use the expanded CCBATCH with our biogeochemical framework for metal detoxification in sulfidic systems to study complex bio-protection scenarios. In particular, in our numerical experiments we expose a consortium of sulfate-reducing bacteria and fermenting bacteria to a toxic concentration of Zn(2+) in a 1-D system with precipitation of zinc-sulfide solids turned off or on. Our results confirm the key role of sulfide precipitation in detoxification when coupled effects of transport and biological processes are considered. The potential of sulfide as a detoxifying agent in bio-protection is explained by its high mobility, its high affinity for metals, and its high rate of production in sulfidic systems. Thus, our numerical results offer important evidence for the gradient-resistance mechanism and validate that a metal-resistance criterion developed from an analytical solution is accurate for defining when bio-protection should succeed.