Pb isotopic fingerprinting of uranium pollution: New insight on uranium transport in stream-river sediments.

Uranium mill tailings (UMT) present a significant environmental concern due to high levels of radioactive and toxic elements, including uranium (U), thorium (Th), and lead (Pb), which can pose serious health risks to aquatic ecosystems. While Pb isotopic tracers have been widely utilized in environmental studies to identify elemental sources and geological processes, their application in U geochemistry remains relatively limited. In this study, we investigate the distribution and migration of U in stream-river sediments surrounding a decommissioned U hydrometallurgical area, employing Pb isotopes as tracers. Our findings reveal significant enrichment and ecological risk of U, Pb, and Th in the sediments. Uranium predominantly associates with quartz and silicate minerals, and its dispersion process is influenced by continuous leaching and precipitation cycles of typical U-bearing minerals. Furthermore, we establish a compelling positive relationship (r2 = 0.97) between 208Pb/207Pb and 206Pb/207Pb in the stream-river sediments and sediment derived from UMT. Application of a binary Pb mixing model indicates that anthropogenic hydrometallurgical activities contribute to 2.5-62.7% of the stream-river sediments. Notably, these values are lower than the 6.6-89.6% recorded about 10 years ago, prior to the decommissioning of the U hydrometallurgical activity. Our results underscore the continued risk of U pollution dispersion even after decommission, highlighting the long-term environmental impact of UMT.

MnFe2O4-biochar decreases bioavailable fractions of thallium in highly acidic soils from pyrite mining area.

The prevalence of toxic element thallium (Tl) in soils is of increasing concern as a hidden hazard in agricultural systems and food chains. In the present work, pure biochar (as a comparison) and jacobsite (MnFe2O4)-biochar composite (MFBC) were evaluated for their immobilization effects in Tl-polluted agricultural soils (Tl: ∼10 mg/kg). Overall, MFBC exhibited an efficient effect on Tl immobilization, and the effect was strengthened with the increase of amendment ratio. After being amended by MFBC for 15 and 30 days, the labile fraction of Tl in soil decreased from 1.55 to 0.97 mg/kg, and from 1.51 to 0.88 mg/kg, respectively. In addition, pH (3.05) of the highly acidic soil increased to a maximum of 3.97 after the immobilization process. Since the weak acid extractable and oxidizable Tl were the preponderantly mitigated fractions and displayed a negative correlation with pH, it can be inferred that pH may serve as one of the most critical factors in regulating the Tl immobilization process in MFBC-amended acidic soils. This study indicated a great potential of jacobsite-biochar amendment in stabilization and immobilization of Tl in highly acidic and Tl-polluted agricultural soils; and it would bring considerable environmental benefit to these Tl-contaminated sites whose occurrence has significantly increased in recent decades near the pyrite or other sulfide ore mining and smelting area elsewhere.

Adsorption of strontium at K-feldspar-water interface.

Feldspars, a type of important and prevalent primary mineral in soils, play a significant role in the migration of radioactive strontium in the environment. Nevertheless, there are rare studies on strontium adsorption on feldspars. This work presents a study on the interaction between strontium and K-feldspar at the solid-water interface. The effects of environmental factors were evaluated using batch experiments with 90Sr tracer. Surface complexation contributed to the chemical adsorption of strontium in the slightly acidic condition.

Insight into the adsorption of europium(III) on muscovite and phlogopite: Effects of pH, electrolytes, humic substances and mica structures.

Europium(III), i.e., Eu(III), is chemically analogous to the trivalent lanthanides (Ln) and actinides (An). A good understanding of the adsorption behaviour of Eu(III) on mica group minerals is critical to the safety evaluation of the radioactive contamination. Nevertheless, the structural complexity of micaceous minerals makes it difficult to draw a consistent conclusion in the study of Eu(III) migration. In this work, we contrastively studied Eu(III) adsorption on dioctahedral muscovite and trioctahedral phlogopite as functions of pH, ionic strength, background electrolytes, interaction sequence, and fulvic acid (FA). Batch experiments showed that Eu(III) adsorption on both micas was strongly dependent on pH but quite independent on ionic strength that is determined by Na+. Planar sites are available on both muscovite and phlogopite while interlayer sites only on phlogopite under Na+ and Ca2+ electrolytes (not for K+ and Cs+). An interlayer expansion of phlogopite, as indicated by a newly appeared diffraction peak at ~6° 2-theta, occurred along with Eu(III) adsorption, which was also confirmed by transmission electron microscopy. Furthermore, the initial Eu(III) concentrations, the concentration ratios between Eu(III) and Cs+, and the reaction sequences of Eu(III)-electrolytes-FA affected both the adsorption behaviour of Eu(III) and reversely the structural alteration of phlogopite. The sequential extraction showed that the adsorbed Eu(III) was mainly in the ion-exchangeable form while the addition of FA could increase the portion of coordinative species. The currently proposed Eu(III) adsorption mechanism can shed new light on predicting the migration of Ln/An(III) at the mica-rich solid-liquid interface on a molecular scale.

Direct dissolution of UO2 in carboxyl-functionalized ionic liquids in the presence or absence of Fe-containing ionic liquids.

Dissolution of UO2 is a prerequisite for the reprocessing of spent nuclear fuel. This study showed that UO2 could be directly dissolved in a single carboxyl-functionalized ionic liquid (IL), [HOOCMmim][Tf2N] 1-carboxymethyl-3-methylimidazolium bistriflimide, or [HOOCEtmim][Tf2N] 1-carboxyethyl-3-methylimidazolium bistriflimide. The addition of an extra Fe-containing IL, [Emim][FeCl4] (Emim, 1-ethyl-3-methylimidazolium) or [Bmim][FeCl4] (Bmim, 1-butyl-3-methylimidazolium) could significantly improve the dissolution kinetics. Results demonstrated that the dissolution process in the early stage could be described by using the pseudo first-order rate law. The apparent activation energy for UO2 dissolution in the mixture of the Fe-containing IL and carboxyl-functionalized IL was calculated to be ∼67 kJ mol-1, implying that the reaction was mainly controlled by a chemical process. Nevertheless, the influence of the diffusion process is non-negligible since the IL has a relatively high viscosity that can retard the diffusion of the formed uranyl species from the UO2 surface. Spectroscopic studies and density functional theory calculations indicated that the uranyl ion coordinated with carboxylate groups is the predominant product for UO2 dissolution in the single carboxyl-functionalized IL, while uranyl chloride complexes would also form in the mixed ILs. The dissolved uranyl species can be successfully recovered from the ILs by extraction. The success of UO2 dissolution in the carboxyl-functionalized IL with or without the Fe-containing IL indicates that the Fe-containing IL and oxygen can serve as an effective catalyst and oxidant for the dissolution of UO2, respectively.

Comparative study of strontium adsorption on muscovite, biotite and phlogopite.

Micaceous minerals are the natural materials that can block radioactive strontium (Sr) released in the environment, and their adsorption capacity and mechanism are highly divergent owing to the different properties of micas. In this work, we comparatively studied the adsorption of Sr(II) on three typical micas, muscovite, biotite and phlogopite. The effects of pH, contact time, ionic strength, and background electrolyte were evaluated. It was found that phlogopite and muscovite had the largest solid-liquid distribution coefficient (Kd) for a reaction time of 48 h under acidic and alkaline conditions, respectively. Under alkaline conditions, as the reaction time increased to 44 days, phlogopite and muscovite showed the highest and lowest Kd, respectively. The Kd for Sr(II) adsorption on biotite and phlogopite increased with increasing pH but decreased with increasing pH for muscovite. X-ray diffraction analysis revealed that the interlayer weathering of phlogopite (a new diffraction peak appeared at 2-theta of ~6.1°) occurred along with the adsorption of Sr(II) below pH 9.0 under 0.01 mol/L NaCl. Furthermore, the adsorption of Sr(II) was significantly inhibited in the presence of 10-5 and 10-2 mol/L Cs+, resulting in similar adsorption capacity for phlogopite and muscovite at pH ~4.1. Consequently, the difference in Sr(II) adsorption on muscovite, biotite and phlogopite mainly came from the synergistic process of adsorption and weathering, which induced the differences in availability of interlayer sites among micas over a certain time.

Influence of Surface Compositions on the Reactivity of Pyrite toward Aqueous U(VI).

Pyrite plays a significant role in governing the mobility of toxic uranium in an anaerobic environment via an oxidation-reduction process occurring at the mineral-water interface, but the factors influencing the reaction kinetics remain poorly understood. In this study, natural pyrites with different impurities (Pb, As, and Si) and different surface pretreatments were used to react with aqueous U(VI) from pH ∼3.0 to ∼9.5. Both aqueous and solid results indicated that freshly crushed pyrites, which do have more surface Fe2+/Fe3+ and S2- sites that were generated from breakage of Fe(S)-S bonds during ball milling, exhibited a much stronger reactivity than those treated with acid washing. Besides, U(VI) reduction which involves the possible intermediate U(V) and the formation of hyperstoichiometric UO2+x(s) was found to preferentially occur at Pb- and As-rich spots on the pyrite surface, suggesting that the incorporated impurities could act as reactive sites because of the generation of lattice defects and galena- and arsenopyrite-like local configurations. These reactive surface sites can be removed by acid washing, leaving a pyrite surface nearly inert toward aqueous U(VI). Thus, reactivity of pyrite toward U(VI) is largely governed by its surface compositions, which provides an insight into the chemical behavior of both pyrite and uranium in various environments.

Factors influencing the reduction of U(VI) by magnetite.

Under suboxic and anoxic environments, magnetite is one corrosion product of iron being used in nuclear waste canisters. Previous studies have reported a complete reduction of U(VI) on the surfaces of biogenic and natural magnetite crystals, while incomplete reductions to U(V)/U(IV)-containing species have been observed on chemosynthetic magnetite. To date, the reasons behind such disparities remain poorly studied. This study shows that uranyl nitrate or uranyl acetate is mainly reduced to UO2+x oxides (e.g., U4O9, U3O8, etc.) by chemosynthetic magnetite under acidic conditions. When extra zero valent-iron was added, the reaction rate was significantly increased, and an improved but still incomplete U(VI) reduction was observed. Nitrate and ferric ions are ubiquitous in natural environment. Results demonstrate that the nitrate ion associated with uranyl and the ferric ion contained in magnetite or generated from U(VI) reduction have a non-negligible oxidative effect on the final products, which could mainly account for the incomplete reduction of U(VI) by chemosynthetic magnetite in the absence or presence of extra zero valent-iron observed in this study. Furthermore, the surface loading of uranium in U-Fe systems can, in part, unravel the discrepancies in various observations. An enhanced understanding of the U-Fe reaction mechanism can facilitate predictions of the extent of uranium mobility with respect to nuclear waste disposal and radioactive decontamination.

The redox behavior of uranium on Beishan granite: Effect of Fe2+ and Fe3+ content.

The Beishan granitic area in Gansu Province is a site with the greatest potential for a repository of high-level radioactive waste (HLW) in China. In this study, the redox behavior of uranium on Beishan granite was investigated at pH values from ~4.4 to ~9.2. Due to the presence of Fe2+-containing fluorannite, results showed that U(VI) was partially reduced by the granites from boreholes 2 (486 m) and 28 (670 m) at a relatively low initial pH whether Na2CO3/NaCl or native groundwater was used as a background electrolyte. Partial oxidation of UO2 was observed when UO2 contacted Beishan granite directly. Therefore, this incomplete reduction of U(VI) was mainly attributed to minor Fe3+ that was either originally contained in the granite or generated during U(VI) reduction. Consequently, aliovalent oxides (e.g., U3O8, U3O7, U4O9, etc.) should be the thermodynamically stable phase in Beishan granite. A mechanism involving the dissolution of Fe2+ from the granite structure followed by interfacial adsorption/reaction was proposed for the U(VI) reduction. This study demonstrates that Beishan granite has a good reducing capacity, which is suitable for the immobilization of redox-sensitive radionuclides. However, potential oxidation of spent fuel by Fe3+ in the granite should also been taken into account.

Migration of 75Se(IV) in crushed Beishan granite: Effects of the iron content.

The diffusion of selenite (labeled with 75Se) in compacted Beishan granite (BsG) was investigated using the in-diffusion capillary method at pH values from ∼2.0 to ∼11.0 under oxic and anoxic conditions. The results indicate that the apparent diffusion coefficient (Da) values of selenite in BsG always reached the minimum at approximately pH 5. Unexpectedly, the Da values under oxic conditions are nearly one order of magnitude lower than those under the anoxic conditions. Further characterization reveals the existence of redox-sensitive Fe(II)-containing components, which can be responsible for the great difference in Da values. Fe(2p) X-ray photoelectron spectroscopy (XPS) results show that more Fe(III)-oxyhydroxide coating is formed on the granite's surface under aerobic conditions than is formed under anaerobic conditions. Correspondingly, Se(3d) spectra indicate that more selenium is sorbed under oxic conditions, and the sorbed amount always reached the maximum at pH values from ∼4 to ∼5. A linear combination fit of X-ray absorption near edge structure (XANES) spectroscopy data revealed that Se(0) was formed under anoxic condition and that selenite preferred to form inner-sphere complexes with Fe(III)-oxyhydroxide. Overall, this study indicates that natural Fe-bearing minerals can greatly attenuate selenite diffusion and the retardation would be enhanced under aerobic conditions.

Effect of hydraulic loading rate on pollutant removal efficiency in subsurface infiltration system under intermittent operation and micro-power aeration.

The low hydraulic loading rate (HLR) greatly restricts the wide application of subsurface wastewater infiltration system (SWIS) in densely populated areas. To increase the HLR, an innovative SWIS was developed using cyclic operation mode. In each cycle, a wastewater feeding period is followed by a drying period, in which the aeration is conducted by a medium-pressure fan. Results indicated that the removal rate of TOC and NH4(+)-N were more than 85% at HLR of 0.5m(3)/m(2)d, whereas the TN removal rate was lower than 20%, indicating that the aeration was efficient and denitrification process was largely limited in the SWIS. When HLR decreased from 0.5 to 0.2m(3)/m(2)d, the pollutant removal efficiency enhanced slightly except for TN. Overall, the intermittent operation and micro-power aeration, combined with shunting the pollutant loading were really helpful for SWIS to achieve higher HLR, which offers a reference for the design of innovative SWIS.

Assessment of trace element contamination in sediment cores from the Pearl River and estuary, South China: geochemical and multivariate analysis approaches.

Twenty-four major and trace elements and the mineralogical composition of four sediment cores along the Pearl River and estuary were analyzed using ICP-AES, ICP-MS, and X-ray diffraction (XRD) to evaluate contamination levels. The dominant minerals were quartz, kaolinite, and illite, followed by montmorillonite and feldspars, while small amounts of halite and calcite were also observed in a few samples. Cluster analysis (CA) and principal component analysis (PCA) were performed to identify the element sources. The highest metal concentrations were found at Huangpu, primarily due to wastewater treatment plant discharge and/or the surreptitious dumping of sludge, and these data differed from those of other sources. Excluding the data from Huangpu, the PCA showed that most elements could be considered as lithogenic; few elements are the combination of lithogenic and anthropogenic sources. An antagonistic relationship between the anthropogenic source metals (K, Ba, Zn, Pb, Cd, Ag, Tl, and U) and marine source metals (Na, Mg, Ti, V, and Ca) was observed. The resulting normalized Al enrichment factor (EF) indicated very high or significant pollution of Cd, Ag, Cu, Zn, Mo, and Pb at Huangpu, which may cause serious environmental effects. Conflicting results between the PCA and EF can be attributed to the background values used, indicating that background values must be selected carefully.

Inhibition of U(VI) reduction by synthetic and natural pyrite.

Reductive precipitation is an effective method of attenuating the mobility of uranium (U) in subsurface environments. The reduction of U(VI) by synthetic and naturally occurring pyrite was investigated at pH 3.0-9.5. In contrast to thermodynamic calculations that were used to predict UO2(s) precipitation, a mixed U(IV) and U(VI) product (e.g., U3O8/U4O9/U3O7) was only observed at pH 6.21-8.63 and 4.52-4.83 for synthetic and natural pyrite, respectively. Under acidic conditions, the reduction of UO2(2+) by surface-associated Fe(2+) may not be favored because the mineral surface is nearly neutral or not negative enough. At high pH, the sorption of negatively charged U(VI) species is not favored on the negatively charged mineral surface. Thus, the redox reaction is not favored. Trace elements generally contained within the natural pyrite structure can affect the reactivity of pyrite and lead to a different result between the natural and synthetic pyrite. Because UO2(s) is extremely redox-sensitive toward U(VI), the observed UO2+x(s) phase reduction product indicates a surface reaction that is largely controlled by reaction kinetics and pyrite surface chemistry. These factors may explain why most laboratory experiments have observed incomplete U(VI) reduction on Fe(II)-bearing minerals.

The reductive immobilization of aqueous Se(IV) by natural pyrrhotite.

The interaction of Se(IV) with natural pyrrhotite was investigated at pH conditions ranging from acidic to nearly neutral. The results indicate that the reduction rate can be described in terms of a pseudo-first order reaction. At pH ∼4.0 to ∼5.0, the rate decreased with increasing pH. Unexpectedly, at pH ∼5.0, the rate increased with increasing reaction time. This response was also observed at pH ∼6.0. Two different reaction mechanisms were proposed to explain pyrrhotite oxidation by Se(IV). Because pyrrhotite is acid-soluble and can be attacked by both Fe(3+) and protons, direct reduction by the released aqueous sulfide dominates the reaction at low pH, whereas the cyclic oxidation of aqueous Fe(2+) adsorbed on pyrrhotite surfaces becomes predominant at high pH. Phosphate, which can be irreversibly bound to Fe(3+) intermediates even under acidic conditions, can significantly decrease the reaction rate by an order of magnitude at pH ∼4.5. In contrast to the thermodynamic calculations and the predicted prevalence of FeSe based on previous reports of aqueous Se(IV) reduction by synthetic mackinawite or troilite, only Se(0) was observed as the reaction product in this study. This observation confirmed that a slow reaction favors the formation of Se(0) rather than iron selenides.

Influence of gamma irradiation on uranium determination by Arsenazo III in the presence of Fe(II)/Fe(III).

Arsenazo III is a widely used reagent for the concentration measurement of uranium and other actinides in aqueous samples. This study indicates that, for routine aqueous samples, due to the strong complexing ability with Arsenazo III, Fe(III) can significantly decrease the UV-Vis absorbance of the U(VI)-Arsenazo III complex, whereas the influence of Fe(II) on the absorbance is negligible. However, when Fe(II) is present in a gamma-irradiated U(VI) aqueous sample, it can give rise to the Fenton reaction, which produces oxidizing radicals that decompose the subsequently added Arsenazo III, leading to a sharp decrease in the absorbance of the U(VI)-Arsenazo III complex. The decrease in absorbance depends on the iron content and irradiation dose. Furthermore, the oxidizing radicals from the Fenton reaction induced by gamma irradiation can be continually produced. Even if the irradiated solution has been aged for more than one month in the absence of light at room temperature and without the exclusion of oxygen, the reactivity of the radicals did not decrease toward the subsequently added Arsenazo III. This finding demonstrates that the presence of Fe(II) in gamma-irradiated U(VI) aqueous samples can lead to incorrect U(VI) measurement using the Arsenazo III method, and a new method needs to be developed for the quantitative determination of U(VI) in the presence of gamma radiation and ferrous iron.

Interaction of aqueous Se(IV)/Se(VI) with FeSe/FeSe2: implication to Se redox process.

Since reductive precipitation is considered as the most effective way to immobilize (79)Se, interaction of aqueous Se(IV)/Se(VI) with Fe(II)-bearing minerals has received extensive attention. In contrast to the thermodynamic calculations, as well as the prevalence of iron selenide phases observed in soil, sediments and ore deposits, most laboratory experiments have found that Se(0) was the reaction product. In this study, the interaction of Se(IV)/Se(VI) with FeSe/FeSe2 were investigated. The results demonstrate that FeSe and FeSe2 can be oxidized to Se(0) by Se(IV) with relatively fast kinetics, while reaction between Se(VI) and FeSe/FeSe2 only occurs under limited conditions (i.e. in the presence of high ferrous content and higher pH) with much slower kinetics, and there is no evident reaction in most case. Therefore, reduction of Se(IV) by Fe(II)-bearing minerals, in particular by natural occurring minerals, is envisioned to produce Se(0) at the early stage of experiments, rather than FeSe or FeSe2. Due to the formation of bulk Se(0) and its low solubility, the Fe-Se-O-H2O system will maintain redox disequilibrium in laboratory time-scale. This study also reveals that iron selenides, like iron sulfides, have strong reactivity toward Fe(3+). The findings in this study give insight into possible controls on Se redox process.

Molecular dynamics simulation of the diffusion of uranium species in clay pores.

Molecular dynamics simulations were carried out to investigate the diffusive behavior of aqueous uranium species in montmorillonite pores. Three uranium species (UO(2)(2+), UO(2)CO(3), UO(2)(CO(3))(2)(2-)) were confirmed in both the adsorbed and diffuse layers. UO(2)(CO(3))(3)(4-) was neglected in the subsequent analysis due to its scare occurrence. The species-based diffusion coefficients in montmorillonite pores were then calculated, and compared with the water mobility and their diffusivity in aqueous solution/feldspar nanosized fractures. Three factors were considered that affected the diffusive behavior of the uranium species: the mobility of water, the self-diffusion coefficient of the aqueous species, and the electrostatic forces between the negatively charged surface and charged molecules. The mobility of U species in the adsorbed layer decreased in the following sequence: UO(2)(2+)>UO(2)CO(3)>UO(2)(CO(3))(2)(2-). In the diffuse layer, we obtained the highest diffusion coefficient for UO(2)(CO(3))(2)(2-) with the value of 5.48×10(-10) m(2) s(-1), which was faster than UO(2)(2+). For these two charged species, the influence of electrostatic forces on the diffusion of solutes in the diffuse layer is overwhelming, whereas the influence of self-diffusion and water mobility is minor. Our study demonstrated that the negatively charged uranyl carbonate complex must be addressed in the safety assessment of potential radioactive waste disposal systems.

Comprehensive assessment of heavy metal contamination in sediment of the Pearl River Estuary and adjacent shelf.

Total metal concentrations (Cr, Ni, Cu, Zn, and Pb), acid volatile sulfide and simultaneously extracted metals (AVS-SEM), and heavy metal fractionation were used to assess the heavy metals contamination status and ecological risk in the sediments of the Pearl River Estuary (PRE) and adjacent shelf. Elevated concentrations at estuarine sites and lower concentrations at adjacent shelf sites are observed, especially for Cu and Zn. Within the PRE, the concentration of heavy metals in the western shore was mostly higher than that in the middle shore. The metals from anthropogenic sources mainly occur in the labile fraction and may be taken up by organisms as the environmental parameters change. A combination of total metal concentrations, metal contamination index and sequential extraction analysis is necessary to get the comprehensive information on the baseline, anthropogenic discharge and bioavailability of heavy metals.

Nanocomposite pyrite-greigite reactivity toward Se(IV)/Se(VI).

A nanopyrite/greigite composite was synthesized by reacting FeCl(3) and NaHS in a ratio of 1:2 (Wei et al. 1996). Following this procedure, the obtained solid phases consisted of 30-50 nm sized particles containing 28% of greigite (Fe(2+)Fe(3+)(2)S(4)) and 72% pyrite (FeS(2)). Batch reactor experiments were performed with selenite or selenate by equilibrating suspensions containing the nanosized pyrite-greigite solid phase at different pH-values and with or without the addition of extra Fe(2+). XANES-EXAFS spectroscopic techniques revealed, for the first time, the formation of ferroselite (FeSe(2)) as the predominant reaction product, along with elemental Se. In the present experimental conditions, at pH 6 and in equilibrium with Se(0), the solution is oversaturated with respect to ferrosilite. Furthermore, thermodynamic computations show that reaction kinetics likely played a significant role in our experimental system.

Effect of pH on aqueous Se(IV) reduction by pyrite.

Interaction of aqueous Se(IV) with pyrite was investigated using persistently stirred batch reactors under O2-free (<1 ppm) conditions at pH ranging from 4.5 to 6.6. Thermodynamic calculations, an increase in pH during the experiments, and spectroscopic observation indicate that the reduction of aqueous Se(IV) by pyrite is dominated by the following reaction: FeS2+3.5HSeO3−+1.5H+=2SO4(2−)+Fe2++3.5Se(0)+2.5H2O. The released Fe(II) was partitioned between the bulk solution and pyrite surface at pH≈4.5 and 4.8, with the Fe2+ density at pyrite-solution interface about 4 orders of magnitude higher than that in the bulk solution, while iron oxyhydroxide precipitated at pH≈6.6, resulting in the decrease of dissolved iron. In the Se(IV) concentration range of the experiments, aqueous Se(IV) reduction rate follows the pseudofirst order which is in the form of ln mSe(IV)=−k't+ln mSe(IV)0, where k' is apparent rate constant combining the rate constant k and pyrite surface area to mass of solution ratio (A/M). And the aqueous Se(IV) reduction rate constant for a standard system (k) with 1 m2 pyrite surface area per 1 kg solution was obtained to be 1.65×10(−4) h(−1), 3.28×10(−4) h(−1), and 4.76×10(−4) h(−1) at pH around 4.5, 4.8, and 5.1, respectively. The positive correlation between reaction rate and pH disagrees with the theories that protons are consumed when HSeO3− is reduced to Se0, and negative charge density on pyrite surface increases as pH increases. Thus, a ferrous iron mediated electron transfer mechanism is proposed to operate during the reduction of aqueous Se(IV) by pyrite. pH and iron concentration affect significantly on Se(IV) reaction rate and reaction product.