Crystalline Fe Oxides Research Articles

Suitability of urban wastes for crop production in Zaria, northern Nigeria: bioavailability and geochemical fractions of potentially toxic elements

A savannah soil amended with two urban wastes and planted with sorghum (Sorghum bicolor) in a pot experiment was evaluated for chemical forms and phytoavailability of Cr, Ni and Pb. The metals were partitioned into seven operationally defined chemical fractions: mobile (F1), easily mobilisable (F2), occluded in Mn oxides (F3), organically bound (F4), occluded in amorphous Fe oxides (FeOxam, F5), occluded in crystalline Fe oxides (FeOxc, F6), and residual (F7). Although the application of the urban wastes increased the total concentrations of the metals in the soil, there were no corresponding increases in Cr and Ni uptake by sorghum except for Pb uptake. Waste application increased mobile Ni (F1) but decreased the residual form (F7). The organically bound Pb (F4) was increased at the expense of residual Pb (F7). With respect to Cr, waste application increased Cr form occluded in non-crystalline Fe oxides (F5) in the soil. Bioassay of the test crop indicated that the uptake of Pb by sorghum (Y-Pb) correlated significantly with Pb occluded in non-crystalline and crystalline Fe oxides (F5 and F6). Since a single application of urban wastes to this savannah soil significantly increased Pb uptake by sorghum, the consequences of long-term applications under urban and peri-urban agriculture (UPA) should be of great concern; particularly with respect to children’s exposure to Pb through consumption of food and vegetables.

Speciation and spatial distribution of solid-phase iron in surface sediments of the East China Sea continental shelf

Abstract Speciation and reactivity characterization of solid-phase Fe in marine sediments are of significance to understanding its heterogeneous mineralogy and crystallinity, the diagenetic cycling of Fe and its regulating roles on many other elements in sediments. In this study, a combination of sequential and single-step extractions was used for the determination of seven Fe pools in surface sediments of the East China Sea (ECS) continental shelf: (1) carbonate associated Fe (Fe(II) carb ) plus acid volatile sulfide-Fe (Fe(II) AVS ), (2) easily reducible amorphous/poorly crystalline Fe oxides (Fe ox1 ), (3) reducible crystalline Fe oxides (Fe ox2 ), (4) magnetite (Fe mag ), (5) poorly reactive sheet silicate Fe (Fe PRS ), (6) pyrite-Fe (Fe py ), and (7) unreactive silicate Fe (Fe U ). Total Fe (Fe T ) in the sediments is largely determined by terrestrial aluminosilicate particles as indicated by a great similarity of the Fe T with that of the Yangtze River and global riverine particulates. The size of Fe PRS is found to be the largest pool, followed by Fe U , Fe ox2 , Fe mag , Fe(II) AVS+carb , Fe ox1 and Fe py . The large Fe PRS may result from neoformation of Fe-rich clay minerals via reverse weathering and subsequent ageing. The small sizes of Fe(II) AVS+carb and Fe py pools is believed to be the result of low SO 4 reduction due to generally low labile organic matter together with the oxic/suboxic, dynamic environments of the surface sediments. The occurrence of Fe ox1 , Fe ox2 and Fe PRS in the sediments is closely associated with the clay fraction as indicated by a high spatial correlation between the former and the latter. Highly reactive Fe(Fe HR ) in the sediments is comparable to that in global marine sediments, but apparently lower than in the Yangtze River and global riverine particulates due probably to sequestration in the Yangtze Estuary. The ratios of Fe HR /Fe T , Fe PR /Fe T and Fe U /Fe T in the ECS surface sediments consistently show more similarity to those in the Yangtze River particulates than in the global continental margin or deep-sea sediments. The surface sediments maintain a high level of buffering capacity toward sulfidation suggested by a large fraction of highly reactive Fe(III) oxides (Fe(III) HR ) in Fe HR .

Effects of calcium peroxide on arsenic uptake by celery (Apium graveolens L.) grown in arsenic contaminated soil

The ability of calcium peroxide (CaO2) to immobilize As of contaminated soil was studied using pot and field experiments. In pot experiment, CaO2 applied at 2.5 and 5gkg−1 significantly increased celery shoot weight and decreased shoot As accumulation, which was ascribed to the formation of stable crystalline Fe and Al oxides bound As and the reduction of labile As fractions in the soil. The labile As fractions were pH dependent and it followed a “V” shaped profile with the change of pH. In field experiment, the dose of CaO2 application at 750kgha−1 was optimal and at which the celery was found to produce the highest biomass (63.4Mgha−1) and lowest As concentration (0.43mgkg−1). CaO2 probably has a promising potential as soil amendment to treat As contaminated soils.

Enriched Iron(III)-Reducing Bacterial Communities are Shaped by Carbon Substrate and Iron Oxide Mineralogy

Iron (Fe) oxides exist in a spectrum of structures in the environment, with ferrihydrite widely considered the most bioavailable phase. Yet, ferrihydrite is unstable and rapidly transforms to more crystalline Fe(III) oxides (e.g., goethite, hematite), which are poorly reduced by model dissimilatory Fe(III)-reducing microorganisms. This begs the question, what processes and microbial groups are responsible for reduction of crystalline Fe(III) oxides within sedimentary environments? Further, how do changes in Fe mineralogy shape oxide-hosted microbial populations? To address these questions, we conducted a large-scale cultivation effort using various Fe(III) oxides (ferrihydrite, goethite, hematite) and carbon substrates (glucose, lactate, acetate) along a dilution gradient to enrich for microbial populations capable of reducing Fe oxides spanning a wide range of crystallinities and reduction potentials. While carbon source was the most important variable shaping community composition within Fe(III)-reducing enrichments, both Fe oxide type and sediment dilution also had a substantial influence. For instance, with acetate as the carbon source, only ferrihydrite enrichments displayed a significant amount of Fe(III) reduction and the well-known dissimilatory metal reducer Geobacter sp. was the dominant organism enriched. In contrast, when glucose and lactate were provided, all three Fe oxides were reduced and reduction coincided with the presence of fermentative (e.g., Enterobacter spp.) and sulfate-reducing bacteria (e.g., Desulfovibrio spp.). Thus, changes in Fe oxide structure and resource availability may shift Fe(III)-reducing communities between dominantly metal-respiring to fermenting and/or sulfate-reducing organisms which are capable of reducing more recalcitrant Fe phases. These findings highlight the need for further targeted investigations into the composition and activity of speciation-directed metal-reducing populations within natural environments.

Transformation of phosphorus in highly calcareous soils under field capacity and waterlogged conditions

The aim of the present study was to evaluate the transformation of applied inorganic phosphorus (P) in highly calcareous soils under two moisture regimes. The experimental design was a factorial combination of two rates of P (0 and 300 mg P kg–1 as KH2PO4) and two moisture regimes (field capacity, FC; waterlogged, WL) in a completely randomised design in duplicate with 20 surface soil samples. The fractionation sequence of inorganic P included successive extraction with NaHCO3, NH4 acetate buffer (NH4OAc), MgCl2, NH4F, NaOH–Na2CO3 (HC), Na citrate–bicarbonate–dithionite (CBD), and H2SO4 carried out 80 and 160 days after incubation. Recovery of applied P in each fraction was calculated as the difference between samples treated and untreated with P. Results indicated that NaHCO3-P decreased from 80 to 160 days, and the decrement was higher under WL than FC moisture regime. The NH4OAc-P was lower under WL than FC at 160 days, while P associated with free and crystalline Fe and Al oxides (NH4F-P, HC-P, CBD-P) was higher under WL than FC for both incubation periods. Oxalate-, citrate-, and citrate–ascorbate-extractable iron under FC and in conjunction with oxalate- and CBD-extractable aluminium and quinone- and hydroxylamine–hydrochloride-extractable manganese were the most influential factors regulating all P fractions. Results of the present study revealed that transformation of applied P into Al- and Fe-P fractions is not as low as previously reported in highly calcareous soils and that Al- and Fe-P oxides may be important in P transformation of these soils, especially in waterlogged condition.

Kinetics of plutonium and americium sorption to natural clay

Kinetics of Pu(IV) and Am(III) sorption from natural groundwater to three types of clays were studied at trace concentrations of the elements. Higher Kd values were determined for sorption of Pu than of Am, and no clear dependence of the Kd values and the kinetic coefficients on the composition of the clays can be deduced. Kinetic data evaluated by models for six different control processes indicated a sorption mechanism controlled by Pu or Am diffusion in the inert layer on the surface of the clays. Apart from the kinetics of the elements sorption, time-dependent changes in their bonding nature were also studied using a sequential extraction. It was found that Pu(IV) was predominantly associated with amorphous and crystalline Fe oxides as well as natural organic matter sites on the clays, whereas in the case of Am(III) the exchangeable and carbonate sites played the principal role.

Sulfide Induced Mobilization of Wetland Phosphorus Depends Strongly on Redox and Iron Geochemistry

Constructed and restored wetland soils play a key role in the cycling and retention of nutrients from polluted surface waters. Elevated SO42- loading from irrigated agriculture, however, has been shown to affect both the availability and mobility of P in wetland soils. This study investigated the biogeochemical cycling of Fe, S, and P in wetland pore waters and surface soils, to determine the role of sulfides in inducing mobilization of P in a constructed wetland in the Central Valley of California (CVC). Water column, pore-water, and solid-phase soil chemistry were measured at three sites, representing a range in wetland environmental conditions (i.e., sediment and nutrient loading, redox environment, and Fe–S–P geochemistry). High SO42- concentration and active SO42- reduction in wetland pore waters contributed to elevated pore water PO43- concentration (0.42 –1.29 mg L−1) via SO42- induced P mobilization. Although high concentrations of acid volatile sulfide (AVS) were present in the surface (0–5 cm) layer (: 6.5–10.3 μmol g−1), only ∼8% of the labile Fe pool was S2- bound, leaving sufficient Fe to buffer S2−. Additionally, surface soils experienced a three- to four-fold increase in P sorption index (PSI) under anaerobic versus aerobic conditions. Results from solid-phase chemical extractions and chemical equilibrium modeling showed that this higher PSI may be due to the conversion of crystalline Fe(III) oxides to poorly crystalline forms, the preservation of Fe(III) oxides due to kinetic constraints on microbial Fe reduction, and the formation of Fe(II) oxides. This study demonstrates that mineral dominated wetlands with sufficient Fe to buffer both dissolved sulfide and PO43- concentrations, can limit the effects of high SO42- loading and SO42- reduction on the mobilization and flux of soil PO43- to the wetland water column.

Sources, spatial variation, and speciation of heavy metals in sediments of the Tamagawa River in Central Japan

Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.

Changes in Zinc Speciation with Mine Tailings Acidification in a Semiarid Weathering Environment

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semiarid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6000 to 450 mg kg(-1)) and plant-available (590 to 75 mg kg(-1)) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and microfocused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn(0.8)talc), Zn sorbed to ferrihydrite (Zn(adsFeOx)), and zinc sulfate (ZnSO(4) · 7H(2)O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Microscale analyses identified hetaerolite (ZnMn(2)O(4)), hemimorphite (Zn(4)Si(2)O(7)(OH)(2) · H(2)O) and sphalerite (ZnS) as minor phases. Bulk and microfocused spectroscopy complement the chemical extraction results and highlight the importance of using a multimethod approach to interrogate complex tailings systems.

Molecular-scale mechanisms of distribution and isotopic fractionation of molybdenum between seawater and ferromanganese oxides

The distribution of Mo between seawater and marine ferromanganese oxides has great impacts on concentration and isotopic composition of Mo in modern oxic seawater. To reveal the adsorption chemistry of Mo to ferromanganese oxides, we performed (i) detailed structural analyses of Mo surface complexes on δ-MnO 2, ferrihydrite, and hydrogenetic ferromanganese oxides by L 3- and K-edge XAFS, and (ii) adsorption experiments of Mo to δ-MnO 2 and ferrihydrite over a wide range of pHs, ionic strengths, and Mo concentrations. XAFS analyses revealed that Mo forms distorted octahedral ( Oh) inner-sphere complexes on δ-MnO 2 whereas it forms a tetrahedral ( Td) outer-sphere complex on ferrihydrite. In the hydrogenetic ferromanganese oxides, the dominant host phase of Mo was revealed to be δ-MnO 2. These structural information are consistent with the macroscopic behaviors of Mo in adsorption experiments, and Mo concentration in modern oxic seawater can be explained by the equilibrium adsorption reaction on δ-MnO 2. In addition, the large isotopic fractionation of Mo between seawater and ferromanganese oxides detected in previous studies can be explained by the structural difference between MoO 4 2 - and adsorbed species on the δ-MnO 2 phase in ferromanganese oxides. In contrast, smaller fractionation of Mo isotopes on ferrihydrite is due to little change in the Mo local structures during its adsorption to ferrihydrite. The structures of Mo species adsorbed on crystalline Fe (oxyhydr)oxides, goethite, and hematite were also investigated at pH 8 and I = 0.70 M (NaNO 3). Our XAFS analyses revealed that Mo forms inner-sphere complexes on both minerals: Td edge-sharing (46%) and Oh double corner-sharing (54%) for goethite, and Td double corner-sharing (14%) and Oh edge-sharing (86%) for hematite. These structural information, combined with those for amorphous ferrihydrite and δ-MnO 2, show the excellent correlation with the magnitude of adsorptive isotopic fractionation of Mo reported in previous studies: the proportion of Oh species or their magnitude of distortion in Mo surface complexes become larger in the order of ferrihydrite < goethite < hematite < δ-MnO 2, a trend identical to the magnitude of isotopic fractionation. Based on the comparison with previous reports for Mo surface species on various oxides, the chemical factors that affect Mo surface complex structures were also discussed. The hydrolysis constant of cation in oxides, log K OH (or the acidity of the oxide surfaces, PZC) is well correlated with the mode of attachment (inner- or outer-sphere) of Mo surface complexes. Furthermore, the symmetric change in Mo species from Td to Oh is suggested to be driven by the formation of inner-sphere complexes on specific sites of the oxide surfaces.

Surface chemical properties and pedogenesis of tropical soils derived from basalts with different ages in Hainan, China

Abstract Limited information is available on the changes of surface chemical properties of tropical soils with time during the pedogenesis. Soil samples of three profiles derived from basalts of 10, 1330 and 2290 kilo annum (ka) in age were collected from adjacent locations in a tropical region of Hainan Province, China. The changes in soil surface chemical properties and the mineralogy of the soil clay fraction with time were investigated using ion adsorption, micro-electrophoresis, and X-ray diffraction analysis. The content of 2:1-type clay minerals decreased, while those of kaolinite and gibbsite increased with increasing basalt age and degree of soil development. The content of pedogenic free iron (Fe) oxides and the ratio of free Fe oxides/total Fe oxides increased with soil development stage, while soil poorly crystalline Fe and aluminum (Al) oxides had an opposite trend. The positive surface charge of the soils increased with increasing basalt age and degree of soil development; this was consistent with the change in their contents of free Fe/Al oxides. However, the value of negative surface charge had an opposite behavior. The soil derived from 10-ka-basalt had much more negative charge than soils derived from 1330- and 2290-ka-basalt. Soil net surface charge and zeta potential of the soil clay-fraction decreased with the increase in basalt age. Both net charge–pH curves and zeta potential–pH curves shifted to positive values with increased basalt age and degree of soil development. Increasing age also elevated the point of zero net charge of the soil and the isoelectric point of soil colloids.

Concurrent evolution of organic and mineral components during initial soil development after retreat of the Damma glacier, Switzerland

The foreland of the Damma glacier (Switzerland) was investigated to assess the build-up of organic carbon (OC) stocks in mineral soils and organic surface layers with increasing ice-free period (ca. 15, 60–70, 71–80 and 110–140 years). Mature soils outside the proglacial area (soil ages > 700 years) served as reference for advanced soil development. All soils were sampled in triplicate per surface age to estimate the variability of soil formation. Different selective dissolution methods were applied to quantify Fe and Al pools with respect to their role for soil organic carbon (SOC) stabilization during initial pedogenesis. The chemical composition of organic matter was characterized by using solid-state CPMAS 13 C NMR spectroscopy. Leptosols and Regosols were found in the glacier foreland which showed a high variability of development ranging from morphologically undeveloped to soils forming Ah horizons within 70 years. These different stages of soil development were present at a small scale within the same surface age according to past glacier movements. Particle-size distribution varied between soils of similar age and without chronological trend. These results point to the strong impact of different glacial deposition and subsequent glaciofluvial erosion, which was indicated by buried organic surface layers, on soil formation. In general, we found a rapid accumulation of OC in the mineral soils (7.1 g m −2 year −1) and organic surface layers with increasing soil age. Similarly, the amount of poorly crystalline Fe oxides and Al phases increased reflecting the growing potential for SOC stabilization. This was indicated by the strong relationship between SOC stocks and stocks of oxalate soluble Fe and Al. In contrast to strongly increasing quantities, only small changes in the composition of organic matter as well as Fe and Al pools were detected during initial pedogenesis. Fe oxides and inorganic Al phases mainly remained poorly crystalline. Our results point to the concurrent evolution of SOC and poorly crystalline Fe oxides and Al phases with positive feedback mechanisms during initial soil formation. In the Swiss Alpine environment, soil development on silica rich parent material proceeds to Cambisols within at least 700 years as evidenced by the reference soils found outside the proglacial area. They showed indications of weak podzolization as some Fe and Al were translocated downwards. The comparison between the foreland soils and the Cambisols showed decreasing accumulation rates of SOC and pedogenic Fe and Al. This indicates that soil formation processes slow down already after some hundred years or accumulation of Fe and Al increasingly occurs at greater soil depth.

Sorption Indices to Estimate Risk of Soil Phosphorus Loss in the Rathbun Lake Watershed, Iowa

To rank and better understand the risk of P loss from potentially erodible soil materials in the Mollisol-dominated watershed of Rathbun Lake in southern Iowa, we sampled seven representative soil materials at four floodplain sites. We compared the samples by using a variety of characteristics and indices, including particle size distribution; total P, C, and N; P sorption indices; equilibrium P concentration; and degree of P saturation, as assessed by dithionite, oxalate, and Mehlich 3 extraction (M3) methods. None of the Mehlich 3 P values of samples in the present study were high enough to suggest a high risk of water impairment caused by P. Equilibrium P concentration (EPC) values ranged from 0.01 to 0.23 mg L 1 . We found that EPC values were significantly correlated with Fe extractable by oxalate or the M3, as well as with total C and total N. The oxalate and M3 provided generally consistent degree of phosphorus saturation indices, leading us to propose three general risk categories for these soil materials: low, intermediate, and high. We conclude that poorly crystalline Fe oxides and organic matter are likely to exert considerable control over the release of P to stream water from materials eroded from these sites. Moreover, risk rankings based on degree of phosphorus saturation values may not be consistent with interpretations of P mobility that are derived from EPC and sorption indices.

Moorella humiferrea sp. nov., a thermophilic, anaerobic bacterium capable of growth via electron shuttling between humic acid and Fe(III)

An anaerobic, thermophilic, spore-forming bacterium (strain 64-FGQ(T)) was isolated from a terrestrial hydrothermal spring from the Kamchatka peninsula, Russia. This strain utilized lactate as an electron donor, insoluble poorly crystalline Fe(III) oxide incorporated into alginate beads as a potential electron acceptor and 9,10-anthraquinone-2,6-disulfonate (AQDS) as an electron-shuttling compound. Vegetative cells of strain 64-FGQ(T) were Gram-stain-positive, peritrichously flagellated, motile, straight rods, 0.3-0.5 µm in diameter and 2.0-5.0 µm long, growing singly or forming short chains. Cells formed round refractive endospores in terminal swollen sporangia. The temperature range for growth was 46-70 °C, with an optimum at 65 °C. The pH range for growth was 5.5-8.5, with an optimum at pH 7.0. The substrates utilized by strain 64-FGQ(T) in the presence of AQDS as an electron acceptor included lactate, malate, succinate, glycerol and yeast extract. The strain fermented galactose, fructose, maltose, sucrose, pyruvate and peptone. Strain 64-FGQ(T) used AQDS, humic acid, thiosulfate, nitrate and perchlorate as electron acceptors for growth. Fe(III) was not directly reduced, but strain 64-FGQ(T) was able to grow and reduce Fe(III) oxide in the presence of small amounts of AQDS or humic acid as electron-shuttling compounds. The G+C content of the DNA of strain 64-FGQ(T) was 51 mol%. 16S rRNA gene sequence analysis placed the isolate in the genus Moorella, with the type strain of Moorella glycerini as its closest relative (97.2% similarity). Based on phylogenetic analysis and physiological characteristics, strain 64-FGQ(T) is considered to represent a novel species of the genus Moorella, for which the name Moorella humiferrea sp. nov. is proposed; the type strain is 64-FGQ(T) (=DSM 23265(T)=VKM B-2603(T)).

Soil Zinc Transformations as Affected by Applied Zinc and Organic Materials

Information on soil zinc (Zn) distribution is essential for understanding its chemical reactions and bioavailability. An experiment was conducted to evaluate the effect of wheat straw, cow manure, and vermicompost applied with Zn rates on Zn distribution in a calcareous soil. A sequential extraction scheme was used to fractionate Zn into soluble and exchangeable, bound to carbonate, organically bound, bound to manganese (Mn) oxide, bound to amorphous iron (Fe) oxide, bound to crystalline Fe oxide, and residual forms. In untreated soil, Zn was mainly in the residual fraction. Increasing rates of applied Zn increased all forms of Zn. Carbonate and residual forms showed the greatest increase. Organic materials application increased all fractions, except Mn-oxide form, and this increase was more pronounced for the organically bound form. Concentration of soluble, exchangeable, and organically bound forms was greatest in cow manure–amended samples as compared to other organic materials, suggesting that cow manure contained more bioavailable Zn than other organic materials.

Evolution of hillslope soils: The geomorphic theater and the geochemical play

Abstract How and how fast do hillslope soils form as the landscape’s morphology changes over time? Here results are shown from an ongoing study that simultaneously examines the morphologic and geochemical evolution of soil mantled hillslopes that have been exposed to distinctively different denudation history. In Northern Sierra Nevada, California, the authors are investigating a tributary basin to the Middle Fork Feather River. A major incision signal from the river is well marked in a knickpoint within the tributary basin which stretches from its mouth to the Feather River at an elevation of ∼700 m to the plateau at an elevation of ∼1500 m. Hillslopes are significantly steeper below the knickpoint. The area’s total denudation rates are currently being constrained using cosmogenic radio nuclides, but a previous study suggested an order of magnitude difference in total denudation rates below and above the knickpoint. When compared with topographic attributes calculated from LIDAR data, physical erosion rates can be modeled as a linear function of ridge top curvature. Surprisingly, over the wide range of total denudation rates, soil thicknesses do not vary significantly until a threshold point where soil mantled landscapes abruptly shift to bedrock dominated landscapes. Bioturbation by tree falls appear to buffer soil thickness over the wide range of physical soil erosion rates. From three hillslopes with different physical erosion rates, the concentrations of Zr, which were considered conserved during dissolution and leaching, were determined and used as a proxy for the degree of mass losses via chemical denudation. There is a general trend that colluvial soils along the hillslopes with lower physical erosion rates are enriched in fine size fractions, Zr, and pedogenic crystalline Fe oxides. Likewise, the saprolites show greater degrees of chemical denudation at the sites above the knickpoint, presumably because of the saprolites’ longer turnover time in the slowly eroding landscapes. In the two steep hillslopes below the knickpoint, no significant or systematic topgraphic trends were found for soil geochemistry. However, soils show increasing Zr enrichment in the downslope direction in the hillslope above the knickpoint, which suggests a critical denudation rate beyond which soils’ turnover time is too short to develop a geochemical catena. As detailed CRN-based soil production rates and catchment scale denudation rates are acquired, the data will be combined with a mass balance model to calculate the rates of chemical denudation and weathering in soils and saprolites along the denudation gradient.

Iron dissolution kinetics of mineral dust at low pH during simulated atmospheric processing

Abstract. We investigated the iron (Fe) dissolution kinetics of African (Tibesti) and Asian (Beijing) dust samples at acidic pH with the aim of reproducing the low pH conditions in atmospheric aerosols. The Beijing dust and three size fractions of the Tibesti dust (&lt;20 μm: PM20; &lt;10 μm: PM10; and &lt;2.5 μm: PM2.5) were dissolved at pH 1, 2 and/or 3 for up to 1000 h. In the first 10 min, all dust samples underwent an extremely fast Fe solubilisation. Subsequently, the Fe dissolution proceeded at a much slower rate before reaching a stable dissolution plateau. The time-dependant Fe dissolution datasets were best described by a model comprising three acid-extractable Fe pools each dissolving according to first-order kinetics. The dissolution rate constant k (h−1) of each pool was independent of the source (Saharan or Asian) and the size (PM20, PM10 or PM2.5) of the dust but highly dependent on pH. The "fast" Fe pool had a k (25 h−1 at pH = 1) of a similar magnitude to "dry" ferrihydrite nanoparticles and/or poorly crystalline Fe(III) oxyhydroxide, while the "intermediate" and "slow" Fe pools had k values respectively 50–60 times and 3000–4000 times smaller than the "fast" pool. The "slow" Fe pool was likely to consist of both crystalline Fe oxide phases (i.e., goethite and/or hematite) and Fe contained in the clay minerals. The initial mass of the "fast", "intermediate" and "slow" Fe pools represented respectively about 0.5–2%, 1–3% and 15–40% of the total Fe in the dust samples. Furthermore, we showed that in systems with low dust/liquid ratios, Fe can be dissolved from all three pools, whereas at high dust/liquid ratios (e.g., in aerosols), sufficient Fe may be solubilised from the "fast" phase to dominate the Fe dissolved and to suppress the dissolution of Fe from the other Fe pools. These data demonstrated that dust/liquid ratio and pH are fundamental parameters controlling Fe dissolution kinetics in the dust. In order to reduce errors in atmospheric and climate models, these fundamental controlling factors need to be included.

Hydrochemistry, mineralogy and chemical fractionation of mine and processing wastes associated with porphyry copper mines: A case study from the Sarcheshmeh mine, SE Iran

Abstract The Sarcheshmeh is one of the largest Oligo-Miocene porphyry Cu deposits in the world. Comparative hydrochemical, mineralogical and chemical fractionation associated with mining efflorescence salts and processing wastes of this mine are discussed. Hydrochemical results showed that rock waste dumps, reject wastes and old impoundments of tailings are the main sources of acid mine drainage waters (AMD) that contain potentially toxic metals such as Cd, Co, Cu, Mn, Ni and Zn as well as Al. Episodic fluxes of highly contaminated acidic waters were produced in a tailings dam over a short period of time. Secondary soluble minerals provide important controls on the quality of AMD produced, especially in old, dry tailings impoundments. Secondary sulfate minerals such as gypsum, magnesiocopiapite, hydronium jarosite, kornelite and coquimbite were found in rock waste drainages and in old weathered reject wastes. Highly soluble secondary minerals such as gypsum, eriochalcite, and bonattite are also observed in an evaporative layer on old tailings impoundments. Chemical fractionation patterns of potentially toxic elements showed that the geochemical behavior of metals is primarily controlled by the mineralogical composition of waste samples. Elements such as Co, Cr, Cu, Mn, Ni and Zn are readily released into the water soluble fraction from efflorescence salts associated with rock waste drainages, as well as from the evaporative layer of old tailings. Potentially toxic elements, such as As, Mo and Pb, are principally adsorbed or co-precipitated with amorphous and crystalline Fe oxides, but they may also be associated with oxidizing, primary sulfides and residual fractions. Following the development of the dammed tailings pond, the secondary minerals were dissolved, producing acidic waters contaminated by Al (154 mg L −1 ), Cu (150 mg L −1 ), Cd (0.31 m gL −1 ), Co (2.13 mg L −1 ), Mn (73.7 mg L −1 ), Ni (1.74 mg L −1 ), Zn (20.3 mg L −1 ) and Cl (1690 mg L −1 ). Therefore, the potential use of recycled water from the Sarcheshmenh dammed tailings pond is diminished by the presence of corrosive ions like Cl − in highly acidic fluids that promote corrosion of pipes and pumps in the water recycling system.

Formation and Transformation of Iron Oxide–Kaolinite Associations in the Presence of Iron(II)

Iron oxide–kaolinite associations are important components of tropical and subtropical soils and have significant influence on the physical and chemical properties of soils. In this study, the formation and transformation of Fe oxide–kaolinite associations as a function of pH, temperature, and time were investigated at different Fe(II)/Fe(III) molar ratios (R). Results show that the formation of crystalline Fe oxides was significantly inhibited due to the presence of kaolinite, while accelerated by Fe(II). The formation of lepidocrocite– and goethite–kaolinite associations were accelerated by Fe(II) at R = 0.04 to 0.06, an initial pH (pHi) of 5 to 8, and a temperature (T) of 50 to 70°C; the formation of hematite–kaolinite association was accelerated by Fe(II) at R = 0.06, pHi 7 to 8, and T = 60 to 80°C; magnetite–kaolinite association was obtained at R = 0.06, pHi 9, and T = 60°C or at R = 0.1 to 0.5, pHi 7, and T = 60°C. The pH as a function of time (pHt) decreased sharply when crystalline Fe oxides were formed in the presence of Fe(II), Fe(III), and kaolinite. The decrease in pHt was slow, however, in the system with Fe(III) and kaolinite but without Fe(II) and in the system with Fe(II) and kaolinite but without Fe(III). The morphologies of lepidocrocite, goethite, hematite, and magnetite in associations are strip shaped, nanorod like, pseudo‐cubic shaped, and nanosphere like, respectively. In a system with Fe(II), Fe(III), and kaolinite, Fe(II) weakened the inhibition of the formation of crystalline Fe oxides by kaolinite; the presence of kaolinite decreased the acceleration by Fe(II); and the morphologies of Fe oxides were influenced by both Fe(II) and kaolinite.

Reduction of iron oxides by Klebsiella pneumoniae L17: Kinetics and surface properties

The kinetics of the reduction dissolution of iron oxides was studied by using Klebsiella pneumoniae L17 in a pH 7.0 bicarbonate buffer. The microbial reduction of various iron oxides was measured in the absence and presence of AQDS (9,10-anthraquinone-2,6-disulfonic acid), and the results of their rates vs. the surface areas of iron oxides suggested that the iron oxide reduction rate by L17 was obviously affected by the surface area but did not completely depend on it especially for hydrous ferric oxide. Increasing the crystalline degree of hematite decreased the rate of iron reduction, indicating that a higher crystalline degree inhibited microbial iron reduction. Increasing the AQDS concentration significantly increased the rate of HFO reduction, which suggested that the addition of AQDS significantly accelerated the microbial reduction of crystalline Fe(III) oxides. From the increased production of AH 2DS (2,6-anthrahydroquinone disulfonate) and cell numbers, it can be concluded that the enhancement may be because of the growth in cells and abiotic Fe(III) reduction by AH 2DS. X-ray diffraction, Fourier transform infrared spectra and scanning electron microscopy all indicated that secondary minerals (e.g., vivianite (Fe 3(PO 4) 2) and siderite (FeCO 3)) were the biogenic Fe(II) solids formed upon the bioreduction of iron oxides.