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Sulfur-containing functional groups in dissolved organic matter (DOM) interact with trace metals, which in turn affects trace metal mobility and bioavailability in aquatic environments. Typical methods for identification and quantification of sulfur in DOM are costly, complex, and time intensive. Triple quadrupole inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) is capable of part per billion-level sulfur quantification in environmental samples and is a more accessible analytical technique compared with other available methods. This study is the first published investigation of ICP-MS/MS for the direct quantification of sulfur in freshwater DOM. Sulfur (32 S) detection occurs at a mass-to-charge ratio of 48 as 32 S16 O+ after removal of interferences and reaction with oxygen gas. We compare three commonly used DOM preparation methods to assess variability among replicate samples. Preparation of freshwater DOM samples by solid phase extraction followed by evaporation overnight and dissolution in 2% nitric acid results in the most accurate quantification of sulfur. Analysis of sulfur in Suwannee River Fulvic Acid standard serves as method validation, measuring a carbon-normalized sulfur concentration that is ∼20% higher than previously reported methods. We apply the ICP-MS/MS analysis method to determine sulfur concentrations in DOM from nine lakes in the northern Midwest. Carbon-normalized sulfur concentrations in the selected lakes are in general agreement with previously reported percentages of sulfur-containing formulas in DOM found by Fourier transform-ion cyclotron resonance-mass spectroscopy.

Groundwater, an important source of drinking water globally, is susceptible to contamination by naturally occurring metals and radionuclides. Regional trends in groundwater quality are useful in pr...

Manganese (Mn) oxides have been proposed for in situ treatment of organic (e.g., phenolic) contaminants, although little is known about the reactivity of reclaimed solids that might be used as alternatives to synthetic oxides. In this study, we investigate the impacts of phenol substituents and manganese oxide properties (e.g., surface area, iron substitution) on the kinetics and mechanism of this reaction. Reclaimed solids from acid mine drainage and drinking water treatment systems contain Mn(IV) and are capable of oxidizing phenolic contaminants, although their reactivity is 1–3 orders of magnitude slower than that of synthetic δ-MnO2. Both electron transfer-limited and sorption-limited mechanisms occur in 29 phenols reacted with the three manganese oxide materials. This finding contrasts with the common assumption that the first one-electron transfer from the phenol to the manganese oxide is rate-limiting. The occurrence of both mechanisms has implications for the rates and products of phenol oxidation. Interestingly, the mechanism for a given phenol changes between solids. We attribute this observed mechanism shift primarily to phenolic substituent effects, with influences from the pHpzc, surface area, and iron substitution of the manganese oxide materials. In addition, we investigate the predictive utility of quantitative structure–activity relationships, as these models have not been tested using complex reactants and non-synthetic manganese oxides. In-depth analysis and external validation measures indicate these common QSAR models are ineffective at predicting the behavior of complex contaminants or reactions with non-synthetic manganese oxides, and therefore have limited application for predicting contaminant oxidation by manganese oxides in environmental and engineered systems.

Use of recycled concrete aggregate (RCA) as highway basecourse material conserves virgin aggregate, reduces energy consumption and CO2 emissions, and may also decrease costs during construction. However, concerns remain over possible negative environmental impacts associated with high pH (>11) effluent from RCA in contact with water. This study examines the reactive transport of high-pH and high-alkalinity water, modeled on RCA leachate, through model subgrade soils. By developing an understanding of the reactions controlling effluent neutralization, this study aims to quantify the change in pH from the discharge site through surrounding subgrade soils. Four types of subgrade soils with a range of mineral composition, Atterberg limits, and cation exchange capacities (CECs) are examined. They include a clayey sand (SC10), low-plasticity clays (M14, SC25), and a high-plasticity clay (CH38). Batch reaction experiments are used to develop kinetic parameters describing the neutralization of high-pH and -alkalinity leachate by clay minerals through mineral dissolution and reprecipitation. Given this information, a reactive transport model incorporating advection, diffusion, and reaction is used to model the change in pH as a function of distance traveled through model subgrade soils and is applied to laboratory-scale column experiments. The rate at which the high pH front travels is directly related to a soil's clay mineral content. Soils with high CECs effectively delay the propagation of hydroxide front by the dissolution of clay minerals. This study demonstrates that common subgrade soils with moderate clay content will effectively neutralize high pH leachate initially produced by RCA.

Dissolved organic matter (DOM) varies widely across natural and engineered systems, but little is known about the influence of DOM composition on its reactivity with manganese oxides. Here, we investigate bulk and molecular transformations of 30 diverse DOM samples after reaction with acid birnessite (MnO2), a strong oxidant that may react with DOM in Mn-rich environments or engineered treatment systems. The reaction of DOM with acid birnessite reduces Mn and forms DOM that is generally more aliphatic and lower in apparent molecular weight. However, the extent of reaction depends on the water type (e.g., wastewater, rivers) and highly aromatic DOM undergoes greater changes. Despite the variability in reactivity due to the DOM composition, aqueous products attributable to the oxidation of phenolic precursors are identified in waters analyzed by high-resolution mass spectrometry. The number of matched product formulas correlates significantly with indicators of DOM aromaticity, such as double-bond equivalents (p = 2.43 × 10-4). At the molecular level, highly aromatic, lignin-like carbon reacts selectively with acid birnessite in all samples despite the variability in initial DOM composition, resulting in the formation of a wide range of aqueous products. These findings demonstrate that DOM oxidation occurs in diverse waters but also suggest that reactivity with acid birnessite and the composition of the resulting aqueous DOM pool are composition-dependent and linked to the DOM source and initial aromaticity.

Many phenolic compounds found as contaminants in natural waters are susceptible to oxidation by manganese oxides. However, there is often variability between oxidation rates reported in pristine matrices and studies using more environmentally relevant conditions. For example, the presence of cations generally results in slower phenolic oxidation rates. However, the underlying mechanism of cation interference is not well understood. In this study, cation co‐solutes inhibit the transformation of four target phenols (i.e., bisphenol A, estrone, p‐cresol, and triclosan) by acid birnessite. Oxidation rates for these compounds by acid birnessite follow the same trend, Na+ > K+ > Mg2+ > Ca2+, when cations are present as co‐solutes. We further demonstrate that the same trend applies to these cations when they are absent from solution but pre‐exchanged with the mineral. We analyze valence state, surface area, crystallinity, and zeta potential to characterize changes in oxide structure. The findings of this study show that pre‐exchanged cations have a large effect on birnessite reactivity even in the absence of cation co‐solutes, indicating that the inhibition of phenolic compound oxidation is not due to competition for surface sites, as previously suggested. Instead, the reaction inhibition is attributed to changes in aggregation and the mineral microstructure. This article is protected by copyright. All rights reserved

Bisphenol A (BPA) is an endocrine disrupting compound commonly found in natural waters at concentrations that are considered harmful for aquatic life. Manganese(III/IV) oxides are strong oxidants capable of oxidizing organic and inorganic contaminants, including BPA. Here we use δ-MnO2 in stirred flow reactors to determine if higher influent BPA concentrations, or introduction rates, lead to increased polymer production. A major BPA oxidation product, 4-hydroxycumyl alcohol (HCA), is formed through radical coupling, and was therefore used as a metric for polymer production in this study. The influent BPA concentration in stirred flow reactors did not affect HCA yield, suggesting that polymeric production is not strongly dependent on influent concentrations. However, changes in influent BPA concentration affected BPA oxidation rates and the rate of δ-MnO2 reduction. Lower aqueous Mn(II) production was observed in reactors at higher BPA introduction rates, suggesting that single-electron transfer and polymer production are favored under these conditions. However, an examination of Mn(II) sorption during these reactions indicated that the length of the reaction, rather than BPA introduction rate, caused enhanced aqueous Mn(II) production in reactors with low introduction rates and longer reaction times due to increased opportunity for disproportionation and comproportionation. This study demonstrates the importance of investigating both the organic and inorganic reactants in the aqueous and solid phases in this complex reaction.

Recent studies have suggested the potential for release of iron (Fe) oxide-bound organic carbon (OC) during dissimilatory iron oxide reduction (DIR). However, the stability of Fe (hydr)oxide-bound OC in the presence of a natural microbial consortium capable of driving both OC metabolism and DIR has not been resolved. Pure ferrihydrite (Fhy) and Fhy-humic acid coprecipitates (Fhy-HA) were inoculated with a small quantity of freshwater sediment and incubated under anoxic conditions in the presence and absence of H(2) or glucose as electron donors for DIR. H(2) promoted DIR led to release of ca. 1 mM dissolved organic carbon (DOC). However, comparable amounts of DOC were released from both pure Fhy and Fhy-HA, similar to DOC levels in mineral-free, inoculum only controls. These results suggest that the observed DOC release during H(2)-promoted DIR originated from OC contained in the inoculum as opposed to the much larger pool (ca. 38 mM) of OC in the Fhy-HA. Thus, DIR preferentially released sorbed OC with low aromaticity (inoculum OC) versus highly aromatic OC (HA) coprecipitated with Fe oxide. Our findings provide new insight into the extent and mechanisms by which DIR is likely to influence aqueous/solid-phase OC partitioning in anoxic soils and sediments.

Radium (Ra) commonly occurs in groundwater obtained from the Midwestern Cambrian-Ordovician aquifer system (C-O-AS) at activities approaching and exceeding the United States Environmental Protection Agency's Maximum Contaminant Level (MCL) of 5 pCi/L for combined 226Ra and 228Ra. The occurrence of Ra(II) in groundwater is dependent on a number of factors, including the prevalence of parent radionuclides within hydrogeological strata, as well as aquifer geochemical conditions. Interbedded aquifer and aquitard sequences within the Midwestern C-O-AS are stratified with respect to Ra(II) activity and geochemical conditions, and thus the formations that serve as Ra(II) sources to groundwater remain poorly constrained. This study analyzes aqueous samples collected from short-screened wells at various depths within the Midwestern C-O-AS near Madison, WI, USA, to determine geochemical parameters including dissolved oxygen; pH; major and minor ions; and metals, including 226Ra, 228Ra, and parent isotopes 238U and 232Th. Additionally, the elemental composition of aquifer solids is determined as a function of depth. Within solid phases, 238U and 232Th occur in both fine-grained facies and as coatings on sandstone minerals. Most groundwater samples contain dissolved combined Ra(II) lower than 2.5 pCi/L; however, one well completed in the unconfined and one well completed in the confined portion of the groundwater system exceed 3.5 pCi/L. In the confined system, anoxic conditions are associated with elevated Ra(II) concentrations, while in the upper, oxic aquifer, elevated total dissolved solids are positively related to Ra(II). These results demonstrate that multiple factors impact Ra(II) sources and mobility in the regionally unconfined portion of the Midwestern C-O-AS.

Hexagonal turbostratic birnessite, with the characteristics of high contents of vacancies, varying amounts of structural and adsorbed Mn3+, and small particle size, undergoes strong adsorption reactions with trace metal (TM) contaminants. While the interactions of TM, i.e., Zn2+, with birnessite are well understood, the effect of birnessite structural characteristics on the coordination and stability of Zn2+ on the mineral surfaces under proton attack is as yet unclear. In the present study, the effects of a series of synthesized hexagonal turbostratic birnessites with different Mn average oxide states (AOSs) on the coordination geometry of adsorbed Zn2+ and its stability under acidic conditions were investigated. With decreasing Mn AOS, birnessite exhibits smaller particle sizes and thus larger specific surface area, higher amounts of layer Mn3+ and thus longer distances for the first MnO and MnMn shells, but a low quantity of available vacancies and thus low adsorption capacity for Zn2+. Zn K-edge EXAFS spectroscopy demonstrates that birnessite with low Mn AOS has smaller adsorption capacity but more tetrahedral Zn (IVZn) complexes on vacancies than octahedral (VIZn) complexes, and Zn2+ is more unstable under acidic conditions than that adsorbed on birnessite with high Mn AOS. High Zn2+ loading favors the formation of VIZn complexes over IVZn complexes, and the release of Zn2+ is faster than at low loading. These results will deepen our understanding of the interaction mechanisms of various TMs with natural birnessites, and the stability and thus the potential toxicity of heavy metal pollutants sequestered by engineered nano-sized metal oxide materials.

The goal of this study was to examine the impact of simulated atmospheric aging on the oxidative potential of inorganic aerosols comprised primarily of crustal materials. Four soil samples and one coal fly ash sample were artificially aged in the laboratory through exposure to the vapor from 15.8 M nitric acid solution for 24 h at room temperature. Native and acid-aged samples were analyzed with a cellular macrophage and acellular dithionthreitol assays to determine oxidative potential. Additionally, the samples were analyzed to determine the concentration of 50 elements, both total and the water-soluble fraction of these elements by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICMS) and crystalline mineral composition using X-ray Diffraction (XRD). The results show that reactions with gaseous nitric acid increase the water-soluble fraction of many elements, including calcium, iron, magnesium, zinc, and lead. The mineral composition analysis documented that calcium-rich minerals present in the soils (e.g., calcite) are converted into different chemical forms, such as calcium nitrate (Ca(NO3)2). The nitric acid aging process, which can occur in the atmosphere, leads to a 200–600% increase in oxidative potential, as measured by cellular and acellular assays. This laboratory study demonstrates that the toxic effects of aged versus freshly emitted atmospheric dust may be quite different. In addition, the results suggest that mineralogical analysis of atmospheric dust may be useful in understanding its degree of aging.

Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethite or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 −) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially localizes on the (100) face of goethite, independent of the number of redox cycles goethite undergoes. This work demonstrates that under oxic conditions, solid Fe(II) associated with goethite resulting from rapid redox cycling is reactive and available for electron transfer to Cr(VI), suggesting Fe(III) (hydr)oxides may act as reservoirs of reactive electron density, even in oxygen saturated environments.

Bisphenol A (BPA) is an endocrine-disrupting compound widely used in the plastic industry and found in natural waters at concentrations considered harmful for aquatic life. BPA is susceptible to oxidation by Mn(III/IV) oxides, which are commonly found in near-surface environments. Here, we quantify BPA oxidation rates and the formation of its predominant product, 4-hydroxycumyl alcohol (HCA), in tandem with transformation of a synthetic, Mn(III)-rich δ-MnO2. To investigate the effect of Mn oxide structural changes on BPA oxidation rate, 12 sequential additions of 80 μM BPA are performed at pH 7. During the additions, BPA oxidation rate decreases by 3 orders of magnitude, and HCA yield decreases from 40% to 3%. This is attributed to the accumulation of interlayer Mn(II/III) produced during the reaction, as observed using X-ray absorption spectroscopy, as well as additional spectroscopic and wet chemical techniques. HCA is oxidized at a rate that is 12.6 times slower than BPA and accumulates in solution. Th...

Compliance monitoring of contaminants in public drinking water supplies results in publicly available data sets that are maintained by state agencies and useful for investigating changes in water quality. In this study, spatial and temporal trends in naturally occurring radium (combined 226Ra + 228Ra) concentrations in groundwater from the Midwestern Cambrian–Ordovician aquifer system were evaluated with a Wisconsin Department of Natural Resources compliance data set. Average combined Ra from 2000 to 2018 in the Midwestern Cambrian–Ordovician aquifer system increased from 5.5 to 7.9 pCi/L in the confined region and from 4.8 to 6.6 pCi/L in the unconfined region. On a local scale, the data demonstrate increasing radium in the communities of Sussex (n = 98) and Brookfield (n = 35), and a decreasing trend in nearby Waukesha (n = 176). This study demonstrates the utility of compliance data sets for investigating water quality trends and the importance of geographic scale in examining such data.

Natural birnessite-like minerals are commonly enriched in various transitional metals (TMs), which greatly modify the mineral structure and properties. However few studies are yet conducted systematically on the effects of TM doping on birnessite reactivity towards Cr(III) oxidation. In the present study, the transformation behaviors of Cr(III) on Co-, Ni-, V-containing birnessites were investigated. Co and Ni doping generally decrease the mineral crystalline sizes and hydrodynamic sizes (DH) while V-doping greatly decreases the crystalline sizes but not the DH, owing to particle aggregation. Co and Ni firstly decrease and then increase the mineral zeta potentials (ζ) at pH4 while V decreases ζ. Electrochemical specific capacitances for Co-containing birnessites are gradually reduced, while those for Ni-doped birnessites are slightly reduced and for V-doped birnessites increased, which have a positively linear relationship with the amounts of Cr(III) oxidized by these samples. Cr(III) removal efficiencies from solution by these Co-, Ni- and V-containing birnessites are 26–51%, ∼62–72% and ∼96–100%, respectively, compared to ∼92% by pure birnessite. Cr(III) oxidation kinetics analysis demonstrates the gradual decrease of Mn(IV) and concurrent increase of Mn(III) and the adsorption of mainly Cr(III) on mineral surfaces. A negatively linear relationship exists between birnessite lateral sizes and the proportions of Mn(IV/III) consumed to oxidize Cr(III). Apparent initial Cr(III) oxidation rate (kobs) for Co-containing birnessites are greatly reduced, while those for Ni-doped samples moderately decreased and for V-doped samples first increased and then decreased. A positively or negatively linear relationship exists between kobs or the amount of Mn(II) released and the mineral Mn(IV) content respectively. Cr(III) oxidation probably initiates from layer edge sites of Ni-doped birnessites but the vacancies of Co- and V-containing birnessites. These results provide insights into the reaction mechanisms of Cr(III) with natural birnessite-like minerals.

Recycled concrete aggregate (RCA) is a high-quality substitute for virgin aggregate as base or subgrade material in pavement construction. However, heavy metal leaching and/or production of...

Iron (Fe) (hydr)oxides play a key role in sediment biogeochemical cycling, particularly in dynamic environments that periodically undergo redox oscillations. The length of redox half cycles varies, depending on the environment, and is often brief in upland tropical soils, the vadose zone and at the sediment/plant root interface. One reaction that impacts Fe (hydr)oxide mineralogy in these environments is the Fe(II) catalyzed transformation of ferrihydrite. This reaction leads to the production of more crystalline phases under strictly anaerobic conditions and in cycling studies with relatively long anaerobic and/or oxic periods (e.g., 7 to 90 days). Ferrihydrite transformation has been investigated under strictly anaerobic conditions, or during a few (1–3), longer redox cycles; however, there is limited information describing the transformation of ferrihydrite, over multiple, short, sequential exposures to chemical reductants (e.g., dissolved Fe(II)) and oxidants (e.g., O2). Here, we examine the mineralogical evolution of ferrihydrite over eight redox cycles during which it reacts with dissolved Fe(II) in the absence of oxygen (anaerobic conditions) for 48 h and is subsequently exposed to air (oxic conditions) for 18 h. Using X-ray absorption spectroscopy (XAS) and 57Fe Mossbauer spectroscopy, the abundance of each mineral phase present after each anaerobic or oxic period, is quantified. Our results demonstrate that rapid redox cycling limits the extent of ferrihydrite transformation leading to disequilibrium between mineral phases. Additionally, magnetite stoichiometry increases throughout the study despite periodic exposure to oxygen. A deeper understanding of poorly crystalline Fe (hydr)oxide transformation during multiple, short redox cycles can provide insight into reactions controlling the speciation of redox active nutrients and contaminants in soils and sediments.

Selenium (Se) is an essential and crucial micronutrient for humans and animals, but excessive Se brings negativity and toxicity. The adsorption and oxidation of Se(IV) on Mn-oxide surfaces are important processes for understanding the geochemical fate of Se and developing engineered remediation strategies. In this study, the characterization of simultaneous adsorption, oxidation, and desorption of Se(IV) on δ-MnO2 mineral was carried out using stirred-flow reactors. About 9.5% to 25.3% of Se(IV) was oxidized to Se(VI) in the stirred-flow system in a continuous and slow process, with the kinetic rate constant k of 0.032 h−1, which was significantly higher than the apparent rate constant of 0.0014 h−1 obtained by the quasi-level kinetic fit of the batch method. The oxidation reaction was driven by proton concentration, and its rate also depended on the Se(IV) influent concentration, flow rate, and δ-MnO2 dosage. During the reaction of Se(IV) and δ-MnO2, Mn(II) was produced and adsorbed strongly on Mn oxide surfaces, which was evidenced by the total reflectance Fourier transform infrared (ATR-FTIR) results. The X-ray photoelectron spectroscopy (XPS) data indicated that the reaction of Se(VI) on δ-MnO2 produced Mn(III) as the main product. These results contribute to a deeper understanding of the interface chemical process of Se(IV) with δ-MnO2 in the environment.

Bisphenol A (BPA) is an endocrine disrupting compound commonly found in natural waters at concentrations that are considered harmful for aquatic life. Manganese(iii/iv) oxides are strong oxidants capable of oxidizing organic and inorganic contaminants, including BPA. Here we use δ-MnO2 in stirred flow reactors to determine if higher influent BPA concentrations, or introduction rates, lead to increased polymer production. A major BPA oxidation product, 4-hydroxycumyl alcohol (HCA), is formed through radical coupling, and was therefore used as a metric for polymer production in this study. The influent BPA concentration in stirred flow reactors did not affect HCA yield, suggesting that polymeric production is not strongly dependent on influent concentrations. However, changes in influent BPA concentration affected BPA oxidation rates and the rate of δ-MnO2 reduction. Lower aqueous Mn(ii) production was observed in reactors at higher BPA introduction rates, suggesting that single-electron transfer and polymer production are favored under these conditions. However, an examination of Mn(ii) sorption during these reactions indicated that the length of the reaction, rather than BPA introduction rate, caused enhanced aqueous Mn(ii) production in reactors with low introduction rates and longer reaction times due to increased opportunity for disproportionation and comproportionation. This study demonstrates the importance of investigating both the organic and inorganic reactants in the aqueous and solid phases in this complex reaction.

Dissimilatory iron-reducing bacteria (DIRB) are known to use humic substances (HS) as electron shuttles for dissimilatory iron reduction (DIR) by transferring electrons to HS-quinone moieties, which in turn rapidly reduce Fe(III) oxides. However, the potential for HS to serve as a source of organic carbon (OC) that can donate electrons for DIR is unknown. We studied whether humic acids (HA) and humins (HM) recovered from peat soil by sodium pyrophosphate extraction could serve as both electron shuttles and electron donors for DIR by freshwater sediment microorganisms. Both HA and HM served as electron shuttles in cultures amended with glucose. However, only HA served as an electron donor for DIR. Metagenomes from HA-containing cultures had an overrepresentation of genes involved in polysaccharide and to a lesser extent aromatic compound degradation, suggesting complex OC metabolism. Genomic searches for the porin-cytochrome complex involved in DIR resulted in matches to Ignavibacterium/Melioribacter, DIRB capable of polymeric OC metabolism. These results indicate that such taxa may have played a role in both DIR and decomposition of complex OC. Our results suggest that decomposition of HS coupled to DIR and other anaerobic pathways could play an important role in soil and sediment OC metabolism.

Ferrihydrite is commonly associated with silicate (Si) and manganese (Mn) in various geological settings. Here, we examined the effects of Fe(III) hydrolysis rate and dissolved Si concentration on ferrihydrite formation, as well as the effects of aqueous Mn(II) on the transformation of two-line ferrihydrite (2LFh). Results indicate that with decreasing Fe(III) hydrolysis rate, the products transition from 2LFh to six-line ferrihydrite (6LFh) and goethite. When the hydrolysis rate is very low, lepidocrocite is formed in addition to 6LFh and goethite. This can be attributed to a decrease in the concentration of hydrolyzed Fe(III) species as the hydrolysis rate decreases. With increasing Si concentration, the products of Fe(II) oxidation transition from an assemblage of lepidocrocite and goethite to a mixture of 6LFh with minor poorly crystalline lepidocrocite and goethite, and finally to 2LFh. The strong adsorption and polymerization of Si limit the nucleation and growth of hydroxychloride green rust during Fe(II) oxidation and precipitation, thereby hindering the formation of lepidocrocite and goethite. With aging at 60 °C and various pHs, 2LFh converts into goethite and hematite within 20–140 days, with the conversion rate increasing with increasing pH. In addition, a small amount of pre-formed goethite converts into hematite at pH 7, 9 and 12. The aging of 2LFh in 8 mM Mn(II) at pH 4, 5.5, and 7 overwhelmingly favors the formation of goethite over hematite. However, the transformation of 2LFh is largely inhibited in 24 mM Mn(II) due to the limited accessibility of surface sites caused by increasing Mn(II) adsorption. These data provide evidence that the formation and secondary mineralization of ferrihydrite largely depend on pH, coexisting silicate, and Mn(II).

a Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China b Department of Ecosystem Science and Management, University of Wyoming, Laramie, WY, 82071, United States c Environmental Chemistry and Technology Program, Department of Civil and Environmental Engineering, University of Wisconsin – Madison, WI 53706, United States

9,10-Anthraquinone-2,6-disulfonic acid (AQDS) is commonly used as a model species to examine the influence of quinones on different biogeochemical cycles. The reduced form of this quinone, AHDS, can donate electrons to the toxic metal species Cr(VI), leading to the precipitation of less soluble Cr(III) phases. Due to the environmental abundance of Fe(III) (oxyhydr)oxides, such as goethite (α-FeOOH), it is important to study the role of these mineral phases on the electron transfer reaction between AHDS and Cr(VI). In this study, this electron transfer reaction is examined in the presence and absence of goethite at three different ratios of AHDS/Cr(VI). Ultraviolet-visible spectroscopy is used to qualitatively assess the oxidation state of AQDS during reactions with goethite. Iron K-edge and Cr K-edge X-ray absorption spectroscopy are used to examine the role of goethite in electron transfer and identify Cr(III) phases that form. Goethite inhibits the extent of Cr(VI) reduction to Cr(III), most notably at the highest ratio of AHDS/Cr(VI) investigated. Production of semiquinone radical species may limit electron transfer and decrease the yields of Fe(II) and Cr(III), both in the presence and absence of goethite. Understanding abiotic electron transfer reactions that occur in systems with multiple redox active species is important to determine the contribution of abiotic redox reactions to Fe biogeochemical cycling in natural soils.

Hydrologic exchange plays a critical role in biogeochemical cycling within the hyporheic zone (the interface between river water and groundwater) of riverine ecosystems. Such exchange may set limits on the rates of microbial metabolism and impose deterministic selection on microbial communities that adapt to dynamically changing dissolved organic carbon (DOC) sources. This study examined the response of attached microbial communities ( in situ colonized sand packs) from groundwater, hyporheic, and riverbed habitats within the Columbia River hyporheic corridor to “cross-feeding” with either groundwater, river water, or DOC-free artificial fluids. Our working hypothesis was that deterministic selection during in situ colonization would dictate the response to cross-feeding, with communities displaying maximal biomass and respiration when supplied with their native fluid source. In contrast to expectations, the major observation was that the riverbed colonized sand had much higher biomass and respiratory activity, as well as a distinct community structure, compared with those of the hyporheic and groundwater colonized sands. 16S rRNA gene amplicon sequencing revealed a much higher proportion of certain heterotrophic taxa as well as significant numbers of eukaryotic algal chloroplasts in the riverbed colonized sand. Significant quantities of DOC were released from riverbed sediment and colonized sand, and separate experiments showed that the released DOC stimulated respiration in the groundwater and piezometer colonized sand. These results suggest that the accumulation and degradation of labile particulate organic carbon (POC) within the riverbed are likely to release DOC, which may enter the hyporheic corridor during hydrologic exchange, thereby stimulating microbial activity and imposing deterministic selective pressure on the microbial community composition. IMPORTANCE The influence of river water-groundwater mixing on hyporheic zone microbial community structure and function is an important but poorly understood component of riverine biogeochemistry. This study employed an experimental approach to gain insight into how such mixing might be expected to influence the biomass, respiration, and composition of hyporheic zone microbial communities. Colonized sands from three different habitats (groundwater, river water, and hyporheic) were “cross-fed” with either groundwater, river water, or DOC-free artificial fluids. We expected that the colonization history would dictate the response to cross-feeding, with communities displaying maximal biomass and respiration when supplied with their native fluid source. By contrast, the major observation was that the riverbed communities had much higher biomass and respiration, as well as a distinct community structure compared with those of the hyporheic and groundwater colonized sands. These results highlight the importance of riverbed microbial metabolism in organic carbon processing in hyporheic corridors.

The prevalence of construction and demolition (C&D) waste and the concurrent demand for construction aggregate presents the opportunity to recycle C&D waste materials as substitutes for virgin aggregate. Commonly, recycled concrete aggregate (RCA) is used as base course in pavement construction. Environmentally responsible applications of RCA must consider the high pH leachate and trace element leaching risks reported in the literature. This review presents the methodology, results, and limitations of existing laboratory and field investigations of RCA leachate chemistry. Long-term highway field studies of RCA leachate illustrate that an initially high leachate pH approaches neutral within approximately one to two years of construction. Conversely, laboratory investigations of RCA leachate pH using batch reactor leaching tests and column leaching tests measure consistently high leachate pH (pH > 10). The discrepancies between field and laboratory measurements of RCA leachate pH suggest that the current laboratory methodology inadequately describes leachate conditions in the field. The authors recommend that future laboratory investigations consider intermittent wetting and drying cycles, eliminate particle abrasion, employ relevant contact times, and consider additional environmental processes that reduce leachate pH such as soil acidity and carbonation.

Natural hexagonal birnessites are enriched in various transition metals (TMs). Many studies have examined the effects of single metal doping on the structures and properties of birnessites, but none focused on the simultaneous interaction mechanism of coprecipitation of two different TMs with birnessite. In this work Co and Ni co-doped hexagonal birnessites were synthesized and characterized by powder X-ray diffraction (XRD), elemental analysis, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy to investigate the effects of co-doping on the structure and reactivity of birnessite and the crystal chemistry of Co and Ni. These co-doped birnessites have lower crystallinity, i.e., fewer manganese layers stacking in the c* direction, larger specific surface areas (SSAs) and increased Mn average oxidation states (AOSs) than the undoped birnessite, and Co exists in a valence of + 3. Co, Ni and Mn K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) spectra demonstrate an increase in edge-sharing Ni–Me (Me = Ni, Co and Mn) distances in birnessite layers with the increase of the contents of dopants while Mn–Me distances first decrease and then increase while those of Co–Me pairs are nearly constant, coupled with first a decrease and then increase of the in-plane unit-cell parameter b. The effect of co-doping on the amounts of structural Mn and K+, numbers of [MnO6] layers stacked in c* axis, and SSAs, is larger than the effects of doping with Co alone, but less than singly Ni doping. In birnessites doped with both Co and Ni, ~ 74–79% of the total Co and ~ 23–39% of the total Ni are present within the manganese layers. Compared with the spatial distribution of TM in singly doped birnessites, the coexistence of Ni hinders the incorporation of Co into the layers during birnessite crystallization; however, coprecipitation with Co has little effects, neither hindrance nor promotion, on the insertion of Ni into the layers. These results provide insight into the interaction mechanism between coexisting Co, Ni within layered Mn oxides. It further helps us to interpret the geochemical characteristics of multi-metal incorporation into natural Mn oxides and their effects on the structures and physicochemical properties of these minerals.

Geochemical behaviors of heavy metal contaminants, such as Cu 2 + , are strongly controlled by natural birnessite-like minerals in both marine and terrestrial environments. However, the mechanisms of the interaction of Cu 2 + with birnessite are not fully understood yet. In the present study, Cu 2 + was coprecipitated with Mn 2 + to produce hexagonal turbostratic birnessite, which is analogous to natural birnessite. The obtained Cu-doped birnessite was characterized by powder X-ray diffraction, field-emission scanning electron microscopy, and X-ray absorption spectroscopy (XANES + EXAFS). The stability of Cu(II) in the birnessite structure was investigated by acid treatment. Increasing the dopant content reduces the mineral crystallinity in the [001] direction and the unit cell parameter b from the hexagonal layers. It also shortens the bond length of Mn O in the [MnO 6 ] unit and the edge-sharing Mn Mn distance in the layers, and increases the average oxidation state (AOS) of Mn and the specific surface area. Analysis of Cu K-edge XANES and EXAFS data indicates that, only a small part of Cu(II) is inserted into the birnessite layers, while most of it is adsorbed on the vacancies. When the Cu/Mn molar ratio is increased from 0.08 to 0.23, an increasing part of Cu(II) is present as polynuclear clusters on the birnessite edge sites in the pH range of ~ 3.3–5.3. Reaction with H 2 SO 4 solution is found to easily dissolve the polynuclear Cu clusters and the highly distorted Cu octahedra in innersphere complexes on the birnessite-water interface, with ~ 53% of the Cu 2 + released into the solution. On the other hand, the reaction with HCl solution leads to reductive dissolution of the mineral matrix, the release of Mn 2 + into solutions, the decrease in the first Mn O and edge-sharing Mn Mn distances and Mn AOS, in addition to the release of Cu 2 + . The release rate of Cu 2 + is much faster than that of Ni 2 + in Ni-doped birnessites, owing to the lower stability of distorted [CuO 6 ] octahedron upon proton attack. These results indicate the formation of multinuclear Cu complexes on birnessite surfaces under the investigated conditions. The results also suggest the lower stability of Cu 2 + in these minerals and thus higher potential toxicity in acidic conditions, in comparison with other metal pollutants, such as Ni 2 + . This study provides new insights into the interaction mechanisms between Cu 2 + and birnessite-like minerals, and help to clarify the structural stability and geochemical behaviors of Cu 2 + associated with birnessite-like minerals in natural environments.

Hexagonal turbostratic birnessite, with the characteristics of high contents of vacancies, varying amounts of structural and adsorbed Mn