Mathematical modeling of biologically mediated redox processes of iron and arsenic release in groundwater

A one dimensional reactive transport model was developed in order to illustrate the biogeochemical behavior of arsenic and iron reduction and release to groundwater that accounts for the reaction coupling the major redox elements under reducing environment. Mass transport equation and the method of characteristics were used considering fundamental geochemical processes to simulate transport processes of different pollutants in mobile phase. The kinetic sub-model describes the heterotrophic metabolisms of several microorganisms. To model a complete redox sequence (aerobic or denitrifiers, Fe(III)-reduction, respiration bacteria of iron and arsenic compounds, and As(V) reduction) four functional bacterial groups (X ₁, X ₂, X ₃, and X ₄) were defined. Microbial growth was assumed to follow Monod type kinetics. The exchange between the different phases (mobile, bio, and matrix) was also considered in this approach. Results from a soil column experiment were used to verify the simulation results of the model. The model depicts the utilization of oxygen, nitrate, iron oxide and arsenic as electron acceptors for oxidation of organic carbon (OC) in a column. The OC as electron donor is one of the most important factors that affect the iron and arsenic reduction bacterial activity.     

The influence of sulfides on soluble organic-Fe(III) in anoxic sediment porewaters

Solid and colloidal iron oxides are commonly involved in early diagenesis. More readily available soluble Fe(III) should accelerate the cycling of iron (Fe) and sulfur (S) in sediments. Experiments with synthetic solutions (Taillefert et al. 2000) showed that soluble Fe(III) (i.e., <50 nm diameter) reacts at a mercury voltammetric electrode at circumneutral pH if it is complexed by an organic ligand. The reactivity of soluble organic-Fe(III) with sulfide is greatly increased compared to its solid equivalent (e.g., amorphous hydrous iron oxides or goethite). We report here data from two different creeks of the Hackensack Meadowlands District (New Jersey) collected with solid state Au/Hg voltammetric microelectrodes and other conventional techniques, which confirm the existence of soluble organic-Fe(III) in sediments and its interaction with sulfide. Chemical profiles in these two anoxic sediments show the interaction between iron and sulfur during early diagenesis. Soluble organic-Fe(III) and Fe(II) are dominant in a creek where sulfide is negligible. This dominance suggests that the reductive dissolution of iron oxides goes through the dissolution of solid Fe(III), then reduction to Fe(II), or that soluble organic-Fe(III) is formed by chemical or microbial oxidation of organic-Fe(II) complexes. In a creek sediment where sulfide occurs in significant concentration, the reductive dissolution of Fe(III) is followed by formation of FeS_(aq), which further precipitates. Dissolved sulfide may influence the fate of soluble organic-Fe(III), but the pH may be the key variable behind this process. The high reactivity of soluble organic-Fe(III) and its mobility may result in the shifting of local reactions, at depths where other electron acceptors are used. These data also suggest that estuarine and coastal sediments may not always be at steady state.     

Precipitation of iron in microbial mats of the spring waters of Borra Caves,Vishakapatnam, India: some geomicrobiological aspects

The Borra caves, Vishakapatnam, India, can be described as a speleothem cave with significant amounts of unexplored microbial mats in spring waters. Here, we present the first observations and hypotheses on the possible impact of the microorganisms in these mats on the cave formation, focusing on their role on iron mineral precipitation. The spring waters (pH neutral 7.5–7.7) contained dissolved metals like iron and the organic mat sludge (pH 7.0–7.3) had a TOC content of approximately 5.4 wt%. Geochemically, the spring waters deep below the microbial mats contained Fe 369 ppb, Sr 198 ppb; and the organic mat sludge contained Mg 9 ppm, Fe 427 ppb, Zn 149 ppb, Sr 190 ppb. XRD observations displayed Fe minerals (dominantly hematite), minor amounts of zinc gallium sulfide and nitrofuryl compounds. At least four groups of bacteria identified by direct microscopy and SEM-EDX on the basis of morphology could be observed in all samples: Leptothrix-like organisms, entombed bacterial mineral sheaths, a few stalks of Gallionella-like organisms and some additional bacteria that could not be further identified. Leptothrix-like organisms contained 43.22–60.08 wt % Fe and the mineral precipitated near and around these bacteria (in the actual unaltered samples on site) contained 30.76–45.22 wt% Fe as identified and quantified by SEM-EDX. This study indicates that the precipitation of these iron-rich mats in the spring waters could be linked to the presence of abundant active communities of iron precipitating bacteria at Borra caves, Vishakapatanam.     

Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10⁻¹¹ mol Fe(II) m⁻² g⁻¹), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)_aq and bacterially-generated Fe(II)_aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.     

新疆智博铁矿火山岩中富铁岩屑地球化学特征及其地质意义

研究表明,西天山阿吾拉勒铁铜成矿带中智博铁矿区火山碎屑岩中的富铁岩屑主要由自形针状/板条状钠长石和富铁基质组成,呈辉绿/斑状结构。电子探针分析显示,富铁岩屑中钠长石端员组分变化范围为An=0.38～2.89,Ab=95.2～99.32,Or=0.17～2.79,端员组分平均值为An_(0.94)Ab_(98.01)Or_(1.06),类似于火山岩中钠长石端员组分变化范围(An=0.74～6.75,Ab=92.85～98.91,Or=0.32～1.76,端员组分平均值为An_(2.63)Ab_(96.65)Or_(0.72)),两者均为岩浆成因钠长石,而非热液交代成因钠长石。富铁基质成分变化范围较大且连续(w(SiO_2)为0.08%～50.04%,w(FeO)为24.89%～87.13%,w(Al_2O_3)为0.04%～14.83%,w(TiO_2)为0.01%～2.83%,w(Na_2O)为0～9.76%,w(MgO)为0.03%～4.88%,w(MnO)为0～0.61%),富铁基质中高Ti磁铁矿和低Ti磁铁矿同时发育,总体上成分不均一,且钠长石呈细针状,为浅成-超浅成低压下快速结晶的产物或为火山喷发作用下快速冷凝结晶所致。通过对磁铁矿-磷灰石矿物组合与安山岩中副矿物磷灰石、矿区磁铁矿的对比研究,认为智博铁矿发生磁铁矿-磷灰石岩浆不混溶作用的可能性很小。通过安山岩基质成分与安山岩成分的对比研究,得出安山岩基质比原岩w(SiO_2)、w(Al_2O_3)、w(CaO)有所降低,w(FeO)、w(Na_2O)、w(MgO)有一定升高,但是程度有限,表明岩浆结晶分异不足以使残留岩浆形成富铁矿。钠长石-磁铁矿富铁岩屑的发育是一种碱铁效应的表现,而碱铁效应对于海相火山岩型铁矿的形成具有重要意义。     

A comparison of sediment microbial communities associated with<Emphasis Type="Italic">Phragmites australis</Emphasis> and<Emphasis Type="Italic">Spartina alterniflora</Emphasis> in two brackish wetlands of New Jersey

The extensive spread ofPhragmites australis throughout brackish marshes on the East Coast of the United States is a major factor governing management and restoration decisions because it is assumed that biogeochemical functions are altered by the invasion. Microbial activity is important in providing wetland biogeochemical functions such as carbon and nitrogen cycling, but there is little known about sediment microbial communities inPhragmites marshes. Microbial populations associated with invasivePhragmites vegetation and with native salt marsh cordgrass,Spartina alterniflora, may differ in the relative abundance of microbial taxa (community structure) and in the ability of this biota to decompose organic substrates (community biogeochemical function). This study compares sediment microbial communities associated withPhragmites andSpartina vegetation in an undisturbed brackish marsh near Tuckerton, New Jersey (MUL), and in a brackish marsh in the anthropogenically affected Hackensack meadowlands (SMC). We use phospholipid fatty acid (PLFA) analysis and enzymataic activity to profile sediment microbial communities associated with both plants in each site. Sediment analyses include bulk density, total organic matter, and root biomass. PLFA profiles indicate that the microbial communities differ between sites with the undisturbed site exhibiting greater fatty acid richness (62 PLFA recovered from MUL versus 38 from SMC). Activity of the 5 enzymes analyzed (β-glucosidase, acid phosphatase, chitobiase, and 2 oxidases) was higher in the undisturbed site. Differences between vegetation species as measured by Principal Components Analysis were significantly greater at the undisturbed MUL site than at SMC, and patterns of enzyme activity and PLFAs did not correspond to patterns of root biomass. We suggest that in natural wetland sediments, macrophyte rhizosphere effects influence the community composition of sediment microbial populations. Physical and chemical site disturbances may impose limits on these rhizosphere effects, decreasing sediment microbial diversity and potentially, microbial biogeochemical functions.     

Rates of trace metal and nutrient diagenesis in an intertidal creek bank

Carbon mineralization in marine sediments is a key process involved in the cycling of carbon, nutrients and trace metals. However, as marine sediments are usually diffusion dominated, the pace of element and nutrient cycling is slow, because consumption of oxidants and/or nutrients in the pore waters via microbial activity often outpaces resupply. Adding an advective flow component to such a system should change the biogeochemical dynamics considerably. Numerical simulations show that shallow coastal aquifers affected by tidal forces can establish ground water velocities of up to 7 cm h⁻¹, driving a circulation of sea water through the sediments with subsequent discharge. Although known to enhance solute exchange, the impact of advection on early diagenesis has not received much attention.To address this issue we mapped the interstitial water chemistry down to 2.5 m sediment depth along a transect on an intertidal creek bank that is subject to a periodic advective flow. Additionally a recently developed hydrogeological simulation of the creek bank was applied to calculate ages of the sampled pore waters. Sample ages obtained were used to quantify (flow path integrated) production or depletion rates for trace metals, nutrients, and sulphate.We find young sea water percolating relatively fast through sediments close to the creek showing strong signs of alteration, whereas pore waters from diffusion dominated regions are less altered. The increase in inorganic nutrients and some trace elements along the flow path requires high rates of turnover. Sulphate, molybdenum, and uranium are almost completely depleted after 200 days, while dissolved inorganic carbon (DIC), ammonia, and manganese increase. Averaged production rates for DIC appear to be three times higher when advection dominated the subsurface flow regime. Our results demonstrate that sites dominated by advection generally show signs of faster rates of diagenetic reactions.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

High-resolution monitoring of biogeochemical gradients in a tar oil-contaminated aquifer

The detailed understanding of in situ biodegradation of petroleum hydrocarbons in porous aquifers requires knowledge on biogeochemical gradients, the distribution of individual redox species and microorganisms. The generally limited spatial resolution of conventional monitoring wells, however, hampers appropriate characterization of small-scale gradients and thus localization of the relevant processes. Groundwater sampling across a BTEX plume in a sandy aquifer by means of a novel high-resolution multi-level well (HR-MLW) is presented here. The presence of distinct and steep biogeochemical gradients is demonstrated in the centimeter and decimeter scale, which could not be resolved with a conventional multi-level well. The thin BTEX plume with a vertical extension of only 80 cm exhibited a decline of contaminant concentrations by two orders of magnitude within a few centimeters in the upper and lower fringe zone. The small-scale distribution of sulfate, sulfide and Fe(II) in relation to the contaminants and elevated δ³⁴S and δ¹⁸O values of groundwater sulfate strongly indicated sulfate and iron reduction to be the dominant redox processes involved in biodegradation. High microbial activities and biomass especially at the plume fringes and the slope of chemical gradients supported the concept that the latter are regulated by microbial processes and transverse dispersion, i.e. vertical mixing of electron donors and acceptors. Transverse dispersion therefore was suggested to be a driving factor controlling biodegradation in porous aquifers, but not exclusively limiting natural attenuation processes at this site. Broad overlapping zones of electron donors and electron acceptors point towards additional factors limiting anaerobic biodegradation in situ. The identification of small-scale gradients substantially contributed to a better understanding of biodegradation processes and hence is a prerequisite for the development of reliable predictive mathematical models and future remediation strategies.     

Barite deposition resulting from phototrophic sulfide-oxidizing bacterial activity

Barite (BaSO₄) deposits generally arise from mixing of soluble barium-containing fluids with sulfate-rich fluids. While the role of biological processes in modulating barium solubility has been shown, no studies have shown that the biological oxidation of sulfide to sulfate leads to barite deposition. Here we present an example of microbially mediated barite deposition in a continental setting. A spring in the Anadarko Basin of southwestern Oklahoma produces water containing abundant barium and sulfide. As emergent water travels down a stream to a nearby creek, sulfate concentration increases from 0.06 mM to 2.2 mM while Ba²⁺ concentration drops from 0.4 mM to less than 7 μM. Stable isotope analysis, microbial activity studies, and in situ experiments provide evidence that as sulfide-rich water flows down the stream, anaerobic, anoxygenic, phototrophic bacteria play a dominant role in oxidizing sulfide to sulfate. Sulfate then precipitates with Ba²⁺ producing barite as travertine, cements, crusts, and accumulations on microbial mats. Our studies suggest that phototrophic sulfide oxidation and concomitant sulfur cycling could prove to be important processes regulating the cycling of barium in continental sulfur-containing systems.     

Flat laminated microbial mat communities

Flat laminated microbial mats are complex microbial ecosystems that inhabit a wide range of environments (e.g., caves, iron springs, thermal springs and pools, salt marshes, hypersaline ponds and lagoons, methane and petroleum seeps, sea mounts, deep sea vents, arctic dry valleys). Their community structure is defined by physical (e.g., light quantity and quality, temperature, density and pressure) and chemical (e.g., oxygen, oxidation/reduction potential, salinity, pH, available electron acceptors and donors, chemical species) parameters as well as species interactions. The main primary producers may be photoautotrophs (e.g., cyanobacteria, purple phototrophs, green phototrophs) or chemolithoautophs (e.g., colorless sulfur oxidizing bacteria). Anaerobic phototrophy may predominate in organic rich environments that support high rates of respiration. These communities are dynamic systems exhibiting both spatial and temporal heterogeneity. They are characterized by steep gradients with microenvironments on the submillimeter scale. Diel oscillations in the physical-chemical profile (e.g., oxygen, hydrogen sulfide, pH) and species distribution are typical for phototroph-dominated communities. Flat laminated microbial mats are often sites of robust biogeochemical cycling. In addition to well-established modes of metabolism for phototrophy (oxygenic and non-oxygenic), respiration (both aerobic and anaerobic), and fermentation, novel energetic pathways have been discovered (e.g., nitrate reduction couple to the oxidation of ammonia, sulfur, or arsenite). The application of culture-independent techniques (e.g., 16S rRNA clonal libraries, metagenomics), continue to expand our understanding of species composition and metabolic functions of these complex ecosystems.     

Crude oil in a shallow sand and gravel aquifer—I. Hydrogeology and inorganic geochemistry

Changes in the distribution of inorganic solutes in a shallow ground water contaminated by crude oil document a series of geochemical reactions initiated by biodegradation of the oil. Upgradient of an oil body floating on the water table, oxidation of oil to carbonic acid dissolves carbonate minerals in the aquifer matrix. In this oxidized zone pH is depressed ∼1 pH unit, and the concentrations of Ca, Mg and HCO₃⁻ increase to more than twice that of the native ground water. In the anoxic zone beneath the oil body concentrations of dissolved SiO₂, Sr, K, Fe and Mn increase significantly. Here, Fe is mobilized by microbial reduction, pH is buffered by the carbonate system, and silicates weather via hydrolysis and organic-acid-enhanced dissolution. Farther down-gradient the ground water is reoxygenated and Fe precipitates from solution, possibly as iron hydroxide or iron carbonates, while SiO₂ precipitates as amorphous silica. Other solutes, such as Mg, are transported more conservatively down-gradient where contaminated and native ground water mix.The observed changes in inorganic aqueous chemistry document changes in water-mineral interactions caused by the presence of an organic contaminant. These organic-initiated interactions are likely present in many contaminated aquifers and may be analogous to interactions occurring in other organic-rich natural waters.     

Impact of fertilizer plant effluent on water quality

The impact of National Fertilizer Company of Nigeria outfall effluent on the physicochemistry and bacteriology of Okrika creek was investigated during the sampling period from May to December, 1998. The National Fertilizer Company of Nigeria outfall effluent, the Okrika creek water and the Ikpukulubie creek (control) water samples were collected. The physico-chemical parameters analyzed for all the samples included temperature, pH, total chloride, total dissolved solids, dissolved oxygen, conductivity, free ammonia, total phosphate, urea, zinc and iron, while the bacteriological determinations were total culturable aerobic heterotrophic bacteria count and identification of representative isolates. The Okrika creek recorded higher concentrations for all the physico-chemical parameters and bacteria load than the control creek. The higher values of pH, Free NH₃, urea, TDS and the conductivity of the National Fertilizer Company of Nigeria outfall effluent above the FEPA standards reflect the poor effluent quality generated by National Fertilizer Company of Nigeria. The bacteria species isolated from the samples include Aerococcus viridans, Alcaligenes faecalis, Bacillus cereus, Citrobacter freundii, Escherichia coli, Klebsiella pneumoniae, Proteus vulgaris, Pseudomonas aeruginosa, Serratia marcescens and Staphylococcus aureus. In general, the investigation revealed that there was an extremely adverse impact on the physico-chemical and bacteriological water quality characteristics of the Okrika creek as a result of the discharge of poor quality effluent from National Fertilizer Company of Nigeria operations.     

古海洋活性铁循环研究进展及对白垩纪缺氧 富氧 沉积转变的启示

铁作为地壳中丰度最高的元素之一,广泛参与到一系列地球化学循环中。现代海洋中的铁主要来源于河流、冰川和风的铁氧化物颗粒和溶解铁的输入。陆源输入的铁氧化物在有机质埋藏、降解的早期成岩作用过程中,发生一系列转化过程而埋藏下来,该过程被称作活性铁循环。氧化 强氧化条件利于沉积物中氧化铁的持续产生或者至少保持不被溶解的状态,从而形成棕色-红色沉积物;还原条件利于沉积物中铁氧化物的溶解,形成菱铁矿、黄铁矿(铁硫化物) 等形式的埋藏,并可能造成溶解铁在海洋内的迁移。Raiswell、Canfield、Poulton等通过对现代典型海洋环境活性铁循环研究,提出了一系列用于判别古海洋氧化 还原条件的活性铁指标体系,并成功地将太古宙以来的古海洋划分成为含铁的大洋、硫化的大洋和氧化的大洋等3个演化阶段。由于活性铁的不同形态对磷具有不同的生物地球化学效应,将造成“氧化条件下磷的优先埋藏、缺氧条件下优先释放的现象”。磷是海洋生产力的限制性元素,铁和磷循环的上述耦合关系将造成“缺氧的大洋生产力越高,富氧的大洋生产力越低”现象的出现。目前已在白垩纪古海洋缺氧 富氧沉积中初步证实了上述反馈关系的存在,但是对活性铁埋藏形式对该特殊沉积的贡献还需要进一步的工作。     

Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria

Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)_aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in ⁵⁶Fe/⁵⁴Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ⁵⁶Fe_{Fe(OH)3-Fe(II)aq} fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)_aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)_aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)_aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)_aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.     

微生物参与前寒武纪条带状铁建造沉积的研究进展

地球演化早期太古代和早元古代大规模的条带状铁建造(BIF)是目前世界上最重要的铁矿资源。已有的稳定同位素组成、分子化石以及岩石磁学性质等证据支持早期微生物广泛参与了BIF的形成。本文评述了微生物参与BIF形成过程中铁搬运和沉淀及其同位素分馏、生物标志物和岩石磁学证据。深入地研究BIF成矿中的微生物矿化贡献,有助于解释BIF形成机制,反演前寒武纪大气-海洋环境演化,以及理解地球早期生命的过程。     

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric (Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic (Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine (Skeletonema costatum) and freshwater (Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ^65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria (Rhodobacter sp.), cyanobacteria (Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria (P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ⁶⁵Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ⁶⁵Cu (solid-solution) = −1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ⁶⁵Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively.Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu²⁺ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution.Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.     

古元古代末浅海赤铁矿化微生物席: 标识与意义*

微生物活动导致铁氧化被认为是前寒武纪铁建造和红层形成的重要机制之一,但是地质记录中却鲜有相关证据。针对这一问题,本研究选择华北古元古代末的大红峪组微生物席成因构造(MISS)为研究对象,通过沉积学和矿物学的综合研究,揭示微生物活动在前寒武纪铁循环中的关键作用。研究表明:华北井陉大红峪组发育大量以砂裂为代表的MISS,指示当时潮间带至潮上带广泛发育微生物席;非微生物席层发育大量原位和近距离搬运的海绿石,指示低氧富铁的浅海和孔隙水化学条件,而相邻微生物席层则发生了显著的赤铁矿化,指示相对更氧化的沉积环境。考虑到微生物席层与相邻(厘米级)非微生物席层间微生物活动与矿物组成的明显差异,笔者提出微生物活动可能是导致当时低氧铁化浅海环境局部铁氧化的重要机制。本研究提供了微生物参与Fe²⁺离子氧化的重要证据,对揭示前寒武纪红层和大规模铁建造形成机制具有启示意义。     

By design: The architecture of microbial redox cycling

The authors’ work on mine systems, combines field and laboratory integrated microbial geochemical investigation with high-resolution techniques enabling characterization and visualization at the bacterium scale (i.e. STXM). The results indicate a repeated motif of socially organized microbial cooperation occurring within microbial consortial macrostructures (pods). The pod structure directly enables the specific geochemical processes linked to the metabolic function of the consortial members. These microbially linked geochemical processes have important ramifications for bulk system geochemistry that were previously unknown. Results from two examples: (1) microbial metal interactions within AMD biofilms and (2) sulfur redox cycling by a novel consortia within mine waters, illustrate how the ecology of the pod consortia is linked to pod biogeochemical macrostructure as well as to the resulting geochemistry associated with pod metabolism. In both instances the pod structures enabled the associated consortia to carry out reactions not predicted by classic geochemical understanding of these systems. Investigation of AMD biofilm biogeochemical architecture capturing the micro-scale linkages amongst geochemical gradients, metal dynamics and depth resolved micro-organism community structure, illustrated a novel biomineralization process driven by biofilm associated pods controlling biofilm metal capture. Similarly, the groups’ recent discovery of an environmental S redox cycling, pod-forming, consortium revealed ecologically driven S cycling with previously unknown implications for both AMD mitigation and AMD carbon flux modeling. These results highlight how microbes cooperatively orchestrate their geochemical environment, underscoring the need to consider syntrophic community activity in environmental processes and the requirement for integrated, high-resolution techniques spanning geochemistry, molecular microbiology and imaging to reveal the biogeochemistry involved.     

Electrochemical interaction of Shewanella oneidensis MR-1 and its outer membrane cytochromes OmcA and MtrC with hematite electrodes

Bacterial metal reduction is an important biogeochemical process in anaerobic environments. An understanding of electron transfer pathways from dissimilatory metal-reducing bacteria (DMRB) to solid phase metal (hydr)oxides is important for understanding metal redox cycling in soils and sediments, for utilizing DMRB in bioremedation, and for developing technologies such as microbial fuel cells. Here we hypothesize that the outer membrane cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 are the only terminal reductases capable of direct electron transfer to a hematite working electrode. Cyclic voltammetry (CV) was used to study electron transfer between hematite electrodes and protein films, S. oneidensis MR-1 wild-type cell suspensions, and cytochrome deletion mutants. After controlling for hematite electrode dissolution at negative potential, the midpoint potentials of adsorbed OmcA and MtrC were measured (−201 mV and −163 mV vs. Ag/AgCl, respectively). Cell suspensions of wild-type MR-1, deletion mutants deficient in OmcA (ΔomcA), MtrC (ΔmtrC), and both OmcA and MtrC (ΔmtrC–ΔomcA) were also studied; voltammograms for ΔmtrC–ΔomcA were indistinguishable from the control. When the control was subtracted from the single deletion mutant voltammograms, redox peaks were consistent with the present cytochrome (i.e., ΔomcA consistent with MtrC and ΔmtrC consistent with OmcA). The results indicate that OmcA and MtrC are capable of direct electron exchange with hematite electrodes, consistent with a role as terminal reductases in the S. oneidensis MR-1 anaerobic respiratory pathway involving ferric minerals. There was no evidence for other terminal reductases operating under the conditions investigated. A Marcus-based approach to electron transfer kinetics indicated that the rate constant for electron transfer k_et varies from 0.025 s⁻¹ in the absence of a barrier to 63.5 s⁻¹ with a 0.2 eV barrier.