Fe isotopic fractionation during mineral dissolution with and without bacteria

Fe released into solution is isotopically lighter (enriched in the lighter isotope) than hornblende starting material when dissolution occurs in the presence of the siderophore desferrioxamine mesylate (DFAM). In contrast, Fe released from goethite dissolving in the presence of DFAM is isotopically unchanged. Furthermore, Δ⁵⁶Fe_{solution-hornblende} for Fe released to solution in the presence of ligands varies with the affinity of the ligand for Fe. The extent of isotopic fractionation of Fe released from hornblende also increases when experiments are agitated continuously. The Fe isotope fractionation observed during hornblende dissolution with organic ligands is attributed predominantly to retention of ⁵⁶Fe in an altered surface layer, while the lack of isotopic fractionation during goethite dissolution in DFAM is consistent with the lack of an altered layer. When a siderophore-producing soil bacterium is added to the system (without added organic ligands), Fe released to solution from both hornblende and goethite differs isotopically from Fe in the bulk mineral: Δ⁵⁶Fe_{solution-starting material} = −0.56 ± 0.19 (hornblende) and −1.44 ± 0.16 (goethite). Increased isotopic fractionation is attributed in this case to the fact that as bacterial respiration depletes the system in oxygen and aqueous Fe is reduced, equilibration between aqueous ferrous and ferric iron creates a pool of isotopically heavy ferric iron that is assimilated by bacterial cells. Adsorption of isotopically heavy ferrous iron (Fe(II) enriched in the heavier isotope) or precipitation of isotopically heavy Fe minerals may also contribute to observed fractionations.To test whether these Fe isotope signatures are recorded in natural systems, we also investigated extractions of samples of soils from which the bacteria were isolated. These extractions show variability in the isotopic signatures of exchangeable Fe and Fe oxyhydroxide fractions from one soil sample to another, but exchangeable Fe is observed to be lighter than Fe in soil Fe oxyhydroxides and hornblende. This observation is consistent with isotopically light Fe-organic complexes in soil pore water derived from the Fe-silicate starting materials in the presence of growing microorganisms, as documented in experiments reported here. The contributions from phenomena including organic ligand-promoted nonstoichiometric dissolution of Fe silicates, uptake of ferric iron by organisms, adsorption of isotopically heavy ferrous iron, and precipitation of iron minerals should create complex isotopic signatures in soils. Better understanding of these processes and the timescales over which they contribute to fractionation is needed.     

喀斯特石漠化地区土壤Fe组成及其发生学意义

土壤中氧化铁的组成反映了土壤的成土过程和环境条件。通过对西南喀斯特石漠化地区不同石漠化阶段山地自然土壤和农田土壤Fe组成的分析,研究了土壤全铁、游离氧化铁和非晶形氧化铁的分布规律,探讨了喀斯特地区石漠化土壤的发育过程和Fe的指示作用。研究表明:①喀斯特地区土壤表层全铁含量在38.9～53.9g/kg之间,游离氧化铁含量在18.0～26.7g/kg之间,铁游离度在44.1%～73.4%之间,铁活度在7.2%～11.4%之间。②随着石漠化程度的加剧,土壤游离氧化铁和铁游离度呈增加的趋势,而铁活度呈降低的趋势。③在土体分布上,自然土壤剖面随深度的增加,土壤铁游离度和铁活度呈明显降低的趋势,而农田土壤铁游离度呈增加的趋势。④喀斯特地区的土壤是石灰岩溶蚀风化的产物,人为活动干扰下的自然土壤石漠化过程是在水力作用下的表土侵蚀过程,而农田土壤受水分垂直运动的影响,是土壤丢失的过程。     

Effet de la teneur en eau d'un sol sur la réduction bactérienne d'oxydes de fer

Iron-reducing activity of autochthonous bacteria from two temporary hydromorphic soils is evaluated by the study of iron reductive dissolution, as a function of water content. The release of ferrous iron in solution is coupled to the mineralization of soil organic carbon. Water soil saturation is not necessary for iron reductive dissolution, since the highest dissolution is obtained for a wet, but not water-saturated soil (100% of water holding capacity WHC), and dissolution is also very high in a soil at 75% WHC. To cite this article: S.J. Stemmler et al., C. R. Geoscience 336 (2004).     

Intermobility of barium,strontium, and lead in chloride and sulfate leach solutions

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t_50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t_50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.

     

Experimental Study on Effect of Waste Plastic Bottle Strips in Soil Improvement

With rapid advancements in technology globally, the use of plastics such as polyethylene bags, bottles etc. is also increasing. The disposal of thrown away wastes pose a serious challenge since most of the plastic wastes are non-biodegradable and unfit for incineration as they emit harmful gases. Soil stabilization improves the engineering properties of weak soils by controlled compaction or adding stabilizers like cement, lime etc. but these additives also have become expensive in recent years. This paper presents a detailed study on the behavior and use of waste plastic in soil improvement. Experimental investigation on reinforced plastic soil results showed that, plastic can be used as an effective stabilizer so as to encounter waste disposal problem as well as an economical solution for stabilizing weak soils. Plastic reinforced soil behaves like a fiber reinforced soil. This study involves the investigation of the effect of plastic bottle strips on silty sand for which a series of compaction, direct shear and California bearing ratio (CBR) tests have been performed with varying percentages of plastic strips and also with different aspect ratios in terms of size. The results reflect that there is significant increment in maximum dry unit weight, Shear Strength Parameters and CBR value with plastic reinforcement in soil. The quantum of improvement in the soil properties depends on type of soil, plastic content and size of strip. It is observed from the study that, improvement in engineering properties of silty sand is achieved at 0.4% plastic content with strip size of (15 mm?×?15 mm).     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.     

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)_(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)_(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.     

Reactive iron(III) in sediments: Chemical versus microbial extractions

The availability of particulate Fe(III) to iron reducing microbial communities in sediments and soils is generally inferred indirectly by performing chemical extractions. In this study, the bioavailability of mineral-bound Fe(III) in intertidal sediments of a eutrophic estuary is assessed directly by measuring the kinetics and extent of Fe(III) utilization by the iron reducing microorganism Shewanella putrefaciens, in the presence of excess electron donor. Microbial Fe(III) reduction is compared to chemical dissolution of iron from the same sediments in buffered ascorbate-citrate solution (pH 7.5), ascorbic acid (pH 2), and 1 M HCl. The results confirm that ascorbate at near-neutral pH selectively reduces the reactive Fe(III) pool, while the acid extractants mobilize additional Fe(II) and less reactive Fe(III) mineral phases. Furthermore, the maximum concentrations of Fe(III) reducible by S. putrefaciens correlate linearly with the iron concentrations extracted by buffered ascorbate-citrate solution, but not with those of the acid extractions. However, on average, only 65% of the Fe(III) reduced in buffered ascorbate-citrate solution can be utilized by S. putrefaciens, probably due to physical inaccessibility of the remaining fraction of reactive Fe(III) to the cells. While the microbial and abiotic reaction kinetics further indicate that reduction by ascorbate at near-neutral pH most closely resembles microbial reduction of the sediment Fe(III) pool by S. putrefaciens, the results also highlight fundamental differences between chemical reductive dissolution and microbial utilization of mineral-bound ferric iron.     

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.     

Fe(Ⅱ)/铁氧化物表面结合铁系统还原有机污染物的研究进展

在土壤和沉积物的自然厌氧环境中,铁氧化物可被铁还原菌等微生物异化还原产生Fe(Ⅱ),形成的Fe(Ⅱ)/铁氧化物表面结合铁系统具有还原活性,可使有机污染物还原转化。综述了含卤和含硝基有机污染物的非生物还原转化过程和表面结合铁系统与有机污染物之间的界面反应机理,进而揭示了污染物在环境中的赋存状态和迁移转化规律;重点分析了影响该还原过程的因素,如铁氧化物类型、pH值、Fe(Ⅱ)与铁氧化物接触时间,以及过渡金属、腐殖酸等竞争因子对反应过程的影响。强化自然界中天然的Fe(Ⅱ)/铁氧化物表面结合铁系统在有机污染治理中的作用,在受污染环境修复领域具有广阔的应用前景。 [HT5H]关 键 词:[HT5K]     

河水入渗过程中近岸带地下水中砷的形成与影响因素研究

沈阳黄家水源地是我国北方地区典型的傍河地下水水源地,近岸带地下水中铁(Fe)、锰(Mn)、砷(As)含量严重超标。为查明地下水中As的来源与影响因素,对研究区河水、地下水以及土壤样品进行采集与测试,分析了水样常规指标与碳硫稳定同位素、土样中典型矿物、砷的含量及赋存形态。结果表明,研究区河水中As含量很低,而地下水中As含量普遍超标。河水入渗初期,氧化性河水使部分含As矿物发生氧化而释放As;随着河水入渗,地下水向还原环境转变,含As的Fe/Mn矿物发生还原性溶解,地下水中As含量逐渐升高。研究区典型矿物有黄铁矿、菱铁矿、软锰矿、赤铁矿、针铁矿、菱锰矿等,通过可交换态砷解吸、有机质结合态砷氧化、铁锰氧化物结合态砷还原性溶解等,介质中的As释放至地下水中。地下水中As含量与酸碱度(pH)、氧化还原电位(Eh)呈一定负相关,与溶解有机碳(DOC)、 {\mathrm{HCO}}_3^{-}、Fe、Mn含量呈正相关。     

Evidence in pre-2.2 Ga paleosols for the early evolution of atmospheric oxygen and terrestrial biota

The loss of Fe from some pre-2.2 Ga paleosols has been considered by previous investigators as the best evidence for a reduced atmosphere prior to 2.2 Ga. I have examined the behavior of Fe in both pre- and post-2.2 Ga paleosols from depth profiles of Fe3+/Ti, Fe2+/Ti, and sigma Fe/Ti ratios, and Fe3+/Ti vs. Fe2+/Ti plots. This new approach reveals a previously unrecognized history of paleosols. Essentially all paleosols, regardless of age, retain some characteristics of soils formed under an oxic atmosphere, such as increased Fe3+/Ti ratios from their parental rocks. The minimum oxygen pressure (PO2) for the 3.0-2.2 Ga atmosphere is calculated to be about 1.5% of the present atmospheric level, which is the same as that for the post-1.9 Ga atmosphere. The loss of sigma Fe, common in paleosol sections of all ages, was not due to a reducing atmosphere, but to reductive dissolution of ferric hydroxides formed under an oxic atmosphere. This reductive dissolution of ferric hydroxides occurred either (1) after soil formation by hydrothermal fluids or (2) during and/or after soil formation by organic acids generated from the decay of terrestrial organic matter. Terrestrial biomass on the early continents may have been more extensive than previously recognized.     

Iron and Pyritization in Wetland Soils of the Florida Coastal Everglades

We explored environmental factors influencing soil pyrite formation within different wetland regions of Everglades National Park. Within the Shark River Slough (SRS) region, soils had higher organic matter (62.65 ± 1.88 %) and lower bulk density (0.19 ± 0.01 g cm^?3) than soils within Taylor Slough (TS; 14.35 ± 0.82 % and 0.45 ± 0.01 g cm^?3, respectively), Panhandle (Ph; 15.82 ± 1.37 % and 0.34 ± 0.009 g cm^?3, respectively), and Florida Bay (FB; 5.63 ± 0.19 % and 0.73 ± 0.02 g cm^?3, respectively) regions. Total reactive sulfide and extractable iron (Fe) generally were greatest in soils from the SRS region, and the degree of pyritization (DOP) was higher in soils from both SRS (0.62 ± 0.02) and FB (0.52 ± 0.03) regions relative to TS and Ph regions (0.30 ± 0.02 and 0.31 ± 0.02, respectively). Each region, however, had different potential limits to pyrite formation, with SRS being Fe and sulfide limited and FB being Fe and organic matter limited. Due to the calcium-rich soils of TS and Ph regions, DOP was relatively suppressed. Annual water flow volume was positively correlated with soil DOP. Soil DOP also varied in relation to distance from water management features and soil percent organic matter. We demonstrate the potential use of soil DOP as a proxy for soil oxidation state, thereby facilitating comparisons of wetland soils under different flooding regimes, e.g., spatially or between wet years versus dry years. Despite its low total abundance, Fe plays an important role in sulfur dynamics and other biogeochemical cycles that characterize wetland soils of the Florida coastal Everglades.     

Alteration of ferrihydrite reductive dissolution and transformation by adsorbed As and structural Al: Implications for As retention

Reduction of As(V) and reductive dissolution and transformation of Fe (hydr)oxides are two dominant processes controlling As retention in soils and sediments. When developed within soils and sediments, Fe (hydr)oxides typically contain various impurities—Al being one of the most prominent—but little is known about how structural Al within Fe (hydr)oxides alters its biotransformation and subsequent As retention. Using a combination of batch and advective flow column studies with Fe(II) and Shewanella sp. ANA-3, we examined (1) the extent to which structural Al influences reductive dissolution and transformations of ferrihydrite, a highly reactive Fe hydroxide, and (2) the impact of adsorbed As on dissolution and transformation of (Al-substituted) ferrihydrite and subsequent As retention. Structural Al diminishes the extent of ferrihydrite reductive transformation; nearly three-orders of magnitude greater concentration of Fe(II) is required to induce Al-ferrihydrite transformation compared to pure two-line ferrihydrite. Structural Al decreases Fe(II) retention/incorporation on/into ferrihydrite and impedes Fe(II)-catalyzed transformation of ferrihydrite. Moreover, owing to cessation of Fe(II)-induced transformation to secondary products, Al-ferrihydrite dissolves (incongruently) to a greater extent compared to pure ferrihydrite during reaction with Shewanella sp. ANA-3. Additionally, adsorption of As(V) to Al-ferrihydrite completely arrests Fe(II)-catalyzed transformation of ferrihydrite, and it diminishes the difference in the rate and extent of ferrihydrite and Al-ferrihydrite reduction by Shewanella sp. ANA-3. Our study further shows that reductive dissolution of Al-ferrihydrite results in enrichment of Al sites, and As(V) reduction accelerates As release due to the low affinity of As(III) on these non-ferric sites.     

红壤酸化过程中铁铝氧化物矿物形态变化及其环境意义

铁铝矿物对土壤中有机质的稳定保持具有十分重要的作用。酸化作用的研究表明,随着浸泡时间的增加,红壤中铁铝总量降低,铝溶蚀较严重;红壤中铁铝氧化物的矿物形态变化表现为:游离态晶质铁铝氧化物大量溶出,而无定形和络合态变化不大。酸性条件下有机质溶出显著,说明除了可能发生水解作用外,游离态铁铝的溶出也起着关键性作用。此外,SEM观察也表明酸化作用引起了土壤团聚体结构的破坏。     

Schwertmannite stability in acidified coastal environments

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.     

Mobilization of arsenic and iron from Red River floodplain sediments, Vietnam

Sediments from the Red River and from an adjacent floodplain aquifer were investigated with respect to the speciation of Fe and As in the solid phase, to trace the diagenetic changes in the river sediment upon burial into young aquifers, and the related mechanisms of arsenic release to the groundwater. Goethite with subordinate amounts of hematite were, using Mössbauer spectroscopy, identified as the iron oxide minerals present in both types of sediment. The release kinetics of Fe, As, Mn and PO₄ from the sediment were investigated in leaching experiments with HCl and 10 mM ascorbic acid, both at pH 3. From the river sediments, most of the Fe and As was mobilized by reductive dissolution with ascorbic acid while HCl released very little Fe and As. This suggests As to be associated with an Fe-oxide phase. For oxidized aquifer sediment most Fe was mobilized by ascorbic acid but here not much As was released. However, the reduced aquifer sediments contained a large pool of Fe(II) and As that is readily leached by HCl, probably derived from an unidentified authigenic Fe(II)-containing mineral which incorporates As as well. Extraction with ascorbic acid indicates that the river sediments contain both As(V) and As(III), while the reduced aquifer sediment almost exclusively releases As(III). The difference in the amount of Fe(II) leached from river and oxidized aquifer sediments by ascorbic acid and HCl, was attributed to reductive dissolution of Fe(III). The reactivity of this pool of Fe(III) was quantified by a rate law and compared to that of synthetic iron oxides. In the river mud, Fe(III) had a reactivity close to that of ferrihydrite, while the river sand and oxidized aquifer sediment exhibited a reactivity ranging from lepidocrocite or poorly crystalline goethite to hematite. Mineralogy by itself appears to be a poor predictor of the iron oxide reactivity in natural samples using the reactivity of synthetic Fe-oxides as a reference. Sediments were incubated, both unamended and with acetate added, and monitored for up to 2 months. The river mud showed the fastest release of both Fe and As, while the effect of acetate addition was minor. This suggests that the presence of reactive organic carbon is not rate limiting. In the case of the river and aquifer sediments, the release of Fe and As was always stimulated by acetate addition and here reactive organic carbon was clearly the rate limiting factor. The reduced aquifer sediment apparently can sustain slower but prolonged microbially-driven release of As. The highly reactive pools of Fe(III) and As in the river mud could be due to reoxidation of As and Fe contained in the reducing groundwater from the floodplain aquifers that are discharging into the river. Deposition of the suspended mud on the floodplain during high river stages is proposed to be a major flux of As onto the floodplain and into the underlying aquifers.     

Release of arsenic associated with the reduction and transformation of iron oxides

The behaviour of trace amounts of arsenate coprecipitated with ferrihydrite, lepidocrocite and goethite was studied during reductive dissolution and phase transformation of the iron oxides using [⁵⁵Fe]- and [⁷³As]-labelled iron oxides. The As/Fe molar ratio ranged from 0 to 0.005 for ferrihydrite and lepidocrocite and from 0 to 0.001 for goethite. For ferrihydrite and lepidocrocite, all the arsenate remained associated with the surface, whereas for goethite only 30% of the arsenate was desorbable. The rate of reductive dissolution in 10 mM ascorbic acid was unaffected by the presence of arsenate for any of the iron oxides and the arsenate was not reduced to arsenite by ascorbic acid. During reductive dissolution of the iron oxides, arsenate was released incongruently with Fe²⁺ for all the iron oxides. For ferrihydrite and goethite, the arsenate remained adsorbed to the surface and was not released until the surface area became too small to adsorb all the arsenate. In contrast, arsenate preferentially desorbs from the surface of lepidocrocite. During Fe²⁺ catalysed transformation of ferrihydrite and lepidocrocite, arsenate became bound more strongly to the product phases. X-ray diffractograms showed that ferrihydrite was transformed into lepidocrocite, goethite and magnetite whereas lepidocrocite either remained untransformed or was transformed into magnetite. The rate of recrystallization of ferrihydrite was not affected by the presence of arsenate. The results presented here imply that during reductive dissolution of iron oxides in natural sediments there will be no simple correlation between the release of arsenate and Fe²⁺. Recrystallization of the more reactive iron oxides into more crystalline phases, induced by the appearance of Fe²⁺ in anoxic aquifers, may be an important trapping mechanism for arsenic.     

广东省普宁市土壤硒的分布特征及影响因素研究

开展了广东省普宁市区域土壤硒调查研究,采集了413个表层土壤样品(0～20 cm)和103个深层土壤样品(> 150 cm),测定了土壤全硒含量,据此研究土壤硒分布特征及其影响因素。结果表明,普宁市土壤全硒含量变化于0. 16～2. 01 mg/kg,平均值为0. 63 mg/kg,总体上处于中硒及高硒水平,不存在缺硒和硒过剩土壤。砂页岩风化形成的赤红壤全硒含量较高,平均值达0. 86 mg/kg,以侏罗系页岩母质发育的土壤全硒含量最高,平均值达0. 89 mg/kg;三角洲第四系沉积物发育形成的水稻土全硒含量最低,平均值为0. 41 mg/kg。回归分析表明,土壤全硒含量与铁铝含量、有机碳含量具有极显著正相关,与p H呈极显著负相关。影响普宁市土壤硒含量的主要因素是成土母质,土壤p H、有机碳和铁铝含量及土地利用方式对土壤全硒含量分布与富集也有一定的影响。     

Dissolution of hausmannite (Mn3O4) in the presence of the trihydroxamate siderophore desferrioxamine B

That microbial siderophores may be mediators of Mn(III) biogeochemistry is suggested by recent studies showing that these well known Fe(III)-chelating ligands form very stable Mn(III) aqueous complexes. In this study, we examine the influence of desferrioxamine B (DFOB), a trihydroxamate siderophore, on the dissolution of hausmannite, a mixed valence Mn(II, III) oxide found in soils and freshwater sediments. Batch dissolution experiments were conducted both in the absence (pH 4-9) and in the presence of 100 μM DFOB (pH 5-9). In the absence of the ligand, there is a sharp decrease in the extent of proton-promoted dissolution above pH 5 and no appreciable dissolution above pH 8. The resulting aqueous Mn²⁺ activities were in good agreement with previous studies, indirectly supporting the accepted two-step mechanism involving the formation of manganite and reprecipitation of hausmannite. Desferrioxamine B enhanced hausmannite dissolution over the entire pH range investigated, both via the formation of a Mn(III) complex and through surface-catalyzed reductive dissolution. Above pH 8, non-reductive ligand-promoted dissolution dominated, whereas below pH 8, dissolution was non-stoichiometric with respect to DFOB. Concurrent proton-promoted, ligand-promoted, reductive, and induced dissolution was observed, with Mn release by either reductive or induced dissolution increasing linearly with decreasing pH. The fast kinetics of the DFOB-promoted dissolution of hausmannite, as compared to iron oxides, suggest that the siderophore-promoted dissolution of Mn(III)-bearing minerals may compete with the siderophore-promoted dissolution of Fe(III)-bearing minerals.