Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (<a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems. In this study, effects of common groundwater ions (i.e., nitrate and sulfate) on Cr(VI) sorption to magnetite were investigated using batch geochemical experiments in conjunction with X-ray absorption spectroscopy.
Results
In both nitrate and sulfate electrolytes, batch sorption experiments showed that Cr(VI) sorption decreases with increasing pH from 4 to 8. In this pH range, Cr(VI) sorption decreased with increasing ionic strength of sulfate from 0.01 to 0.1 M whereas nitrate concentrations did not alter the Cr(VI) sorption behavior. This indicates the background electrolyte specific Cr(VI) sorption process in magnetite. Under the same ionic strength, Cr(VI) removal in sulfate containing solutions was greater than that in nitrate solutions. This is because the oxidation of Fe(II) by nitrate is more thermodynamically favorable than by sulfate, leaving less reduction capacity of magnetite to reduce Cr(VI) in the nitrate media. X-ray absorption spectroscopy analysis supports the macroscopic evidence that more than 75 % of total Cr on the magnetite surfaces was adsorbed Cr(VI) species after 48 h.
Conclusion
This experimental geochemical study showed that the adsorption process of Cr(VI) anions was as important as the reductive precipitation of Cr(III) in describing the removal of Cr(VI) by magnetite, and these interfacial adsorption processes could be impacted by common groundwater ions like sulfate and nitrate. The results of this study highlight new information about the large quantity of adsorbed Cr(VI) surface complexes at the magnetite-water interface. It has implications for predicting the long-term stability of Cr at the magnetite-water interface.
High salinity and arsenic (As) concentrations in groundwater are widespread problems in the tidal deltaplain of southwest Bangladesh. To identify the sources of dissolved salts and As, groundwater samples from the regional shallow Holocene aquifer were collected from tubewells during the dry (May) and wet (October) seasons in 2012–2013. Thirteen drill cores were logged and 27 radiocarbon ages measured on wood fragments to characterize subsurface stratigraphy.
Results
Drill cuttings, exposures in pits and regional studies reveal a >5 m thick surface mud cap overlying a ~30 m thick upper unit of interbedded mud and fine sand layers, and a coarser lower unit up to 60 m thick dominated by clean sands, all with significant horizontal variation in bed continuity and thickness. This thick lower unit accreted at rates of ~2 cm/year through the early Holocene, with local subsidence or compaction rates of 1–3 mm/year. Most tubewells are screened at depths of 15–52 m in sediments deposited 8000–9000 YBP. Compositions of groundwater samples from tubewells show high spatial variability, suggesting limited mixing and low and spatially variable recharge rates and flow velocities. Groundwaters are Na–Cl type and predominantly sulfate-reducing, with specific conductivity (SpC) from 3 to 29 mS/cm, high dissolved organic carbon (DOC) 11–57 mg/L and As 2–258 ug/L, and low sulfur (S) 2–33 mg/L.
Conclusions
Groundwater compositions can be explained by burial of tidal channel water and subsequent reaction with dissolved organic matter, resulting in anoxia, hydrous ferric oxide (HFO) reduction, As mobilization, and sulfate (SO4) reduction and removal in the shallow aquifer. Introduction of labile organic carbon in the wet season as rice paddy fertilizer may also cause HFO reduction and As mobilization. Variable modern recharge occurred in areas where the clay cap pinches out or is breached by tidal channels, which would explain previously measured 14C groundwater ages being less than depositional ages. Of samples collected from the shallow aquifer, Bangladesh Government guidelines are exceeded in 46 % for As and 100 % for salinity.
Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).
Results
The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe3+. The water molecules capping surface Fe3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe3+, those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism.
Conclusions
Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe–OH2 distances in the DFT calculations it was proposed that the surface Fe3+ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination.
Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe3+ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe3+ is coordinated with only 5 neighbors.
The coexistence of Cd2+ and Zn2+ ions in nature has a significant influence on their environmental behaviors in soils and bioavailability for plants. While many studies have been done on the mutual toxicity of Cd2+ and Zn2+, few studies can be found in the literature focused on the interaction of Cd2+ and Zn2+ on soil clay fractions especially in terms of energy relationship.
Results
The binding energies of Cd2+ on boggy soil (Histosols) particles and Zn2+ on yellow brown soil (Haplic Luvisols) particles were the highest, while those of Cd2+ and Zn2+ on paddy soil (Inceptisols) particles were the lowest. These results indicated that Cd2+ and Zn2+ have a strong capacity to adsorb in the solid phase at the soil–water interface of boggy soil and yellow brown soil, respectively. However, both Cd2+ and Zn2+ adsorbed on paddy soil particles easily release into the solution of the soil suspension. Unlike the binding energy, the higher adsorption energies of ions in boggy and yellow brown soils showed a weak binding force of ions in boggy soil and yellow brown soil. A 1:1 ratio of Cd2+ to Zn2+ promotes the mutual inhibition of their retentions. Cd2+ and Zn2+ have high mobility and bioavailability in paddy soil and yellow drab soil (Ustalfs), whereas they have high potential mobility and bioavailability in boggy soil and yellow brown soil.
Conclusion
In the combined system, Zn2+ had preferential adsorption than Cd2+ on soil clay fractions. Boggy soil and yellow brown soil have a low environmental risk with lower mobility and bioavailability of Cd2+ and Zn2+ while paddy soil and yellow drab soil present a substantial environmental risk. In the combined system, Cd2+ and Zn2+ restrain each other, resulting in the weaker binding force between ions and soil particles at a 1:1 ratio of Cd2+–Zn2+.
The interaction between Ca-HAP and Pb2+ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(PbxCa1?x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (PbxCa1?x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.
Results
Dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb2+ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00–0.80), the aqueous Pb2+ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.
Conclusions
The dissolution process of the solids with high XPb (0.89–1.00) was different from that of the solids with low XPb (0.00–0.80). The average Ksp values were estimated to be 10?80.77±0.20 (10?80.57–10?80.96) for hydroxypyromorphite [Pb5(PO4)3OH] and 10?58.38±0.07 (10?58.31–10?58.46) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔGfo) were determined to be ?3796.71 and ?6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1?x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1?x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1?x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution.
Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3OH] at 25??C and an initial pH of 2.00.
The presence of natural and industrial jarosite type-compounds in the environment could have important implications in the mobility of potentially toxic elements such as lead, mercury, arsenic, chromium, among others. Understanding the dissolution reactions of jarosite-type compounds is notably important for an environmental assessment (for water and soil), since some of these elements could either return to the environment or work as temporary deposits of these species, thus would reduce their immediate environmental impact.
Results
This work reports the effects of temperature, pH, particle diameter and Cr(VI) content on the initial dissolution rates of K-Cr(VI)-jarosites (KFe3[(SO4)2 ? X(CrO4)X](OH)6). Temperature (T) was the variable with the strongest effect, followed by pH in acid/alkaline medium (H3O+/OH?). It was found that the substitution of CrO42?in Y-site and the substitution of H3O+ in M-site do not modify the dissolution rates. The model that describes the dissolution process is the unreacted core kinetic model, with the chemical reaction on the unreacted core surface. The dissolution in acid medium was congruent, while in alkaline media was incongruent. In both reaction media, there is a release of K+, SO42? and CrO42? from the KFe3[(SO4)2 ? X(CrO4)X](OH)6 structure, although the latter is rapidly absorbed by the solid residues of Fe(OH)3 in alkaline medium dissolutions. The dissolution of KFe3[(SO4)2 ? X(CrO4)X](OH)6 exhibited good stability in a wide range of pH and T conditions corresponding to the calculated parameters of reaction order n, activation energy EA and dissolution rate constants for each kinetic stages of induction and progressive conversion.
Conclusions
The kinetic analysis related to the reaction orders and calculated activation energies confirmed that extreme pH and T conditions are necessary to obtain considerably high dissolution rates. Extreme pH conditions (acidic or alkaline) cause the preferential release of K+, SO42? and CrO42? from the KFe3[(SO4)2 ? X(CrO4)X](OH)6 structure, although CrO42? is quickly adsorbed by Fe(OH)3 solid residues. The precipitation of phases such as KFe3[(SO4)2 ? X(CrO4)X](OH)6, and the absorption of Cr(VI) after dissolution can play an important role as retention mechanisms of Cr(VI) in nature.
This book review takes the authors to task for omitting numerous references when they wrote this first comprehensive work on thallium. Among the omissions noted are; 1) the extreme toxicity of thallium; 2) the occurrence of thallium in various minerals:
REVIEW OF THALLIUM, ITS GEOCHEMISTRY, MINERALOGY, PRINCIPAL GENETIC TYPES OF DEPOSITS, AND GEOCHEMICAL PROVINCES BY V.V. IVANOV, V.YU. VOLGIN, A.A. KRASNOV AND N.V. LIZUNOV
The available information on the graptolite faunas of the Chu-Illyskiye Mountains is synthesized and comparisons made with other faunas of Kazakhstan, Europe, North America, and China. Comparison with Bet-Pak-la, 400 km NW of the Chu-Iliyskiye, shows almost no species common to contemporaneous units, a discrepancy attributed to facies differences. Correlation with the English standard is good although many details of zonal equation are arbitrary. Fifty species, of which 17 are new, are described and illustrated. Twenty-two are typically European, five North American, two Russian, and one Chinese; three are not formally named. Correlation between the graptolite zones of the Chu-Iliyskiye Mountains and the English standard zones is as follows:
ORDOVICIAN GRAPTOLITES OF THE CHU-ILIYSKIYE MOUNTAINS
The rate of non-oxidative galena dissolution in seawater compositions over the pH range of 2–4.5 was determined from batch reactor experiments. The derivative at zero time of a polynomial fit of the Pb concentration versus time data for the first 30 min was used to determine the rate. A plot of RGn (rate of galena dissolution) versus pH for data from six experiments is linear (R2?=?0.96), with a slope of 0.5. The rate equation describing the rate of galena dissolution as a function of hydrogen ion activity is
Varying the concentration of dissolved oxygen produced no significant effect on the measured rates. The activation energy, based on four experiments carried out over the temperature range of 7–30 °C, is 61.1 kJ/mol.
The paper presents new data on the U–Pb zircon age, as well as results of isotopic geochemical analysis, of granites and rhyolites from Wrangel Island. The U–Pb age estimates of granites and rhyolites are grouped into two clusters (~690–730 and 590–610 Ma), which imply that these rocks crystallized in the Late Neoproterozoic. Granitic rocks dated back to 690–730 Ma are characterized by negative εNd(t) values and Paleoproterozoic Sm–Nd model age. The older inherited zircons corroborate the ancient age of their crustal source. The granitic rocks pertain to involved peraluminous granites of type I, which form at a continental margin of the Andean type and can be compared with coeval granites and orthogneisses from the Seward Peninsula in Alaska. Rhyolites and granites ~590–610 Ma in age are distinguished by a moderately positive εNd(t) and Mesoproterozoic model age. It is suggested that they have a heterogeneous magma source comprising crustal and mantle components. The geochemical features of granites and rhyolites correspond to type A granites. Together with coeval OIB-type basalts, they make up a riftogenic bimodal association of igneous rocks, which are comparable with orthogneisses (565 Ma) and gabbroic rocks (540 Ma) of Seward Peninsula in Alaska. 相似文献
