Acid Mine Drainage Sulfate Research Articles

Potassium-Bicarbonate-Induced Mineralized Acid Mine Drainage into Iron Hydroxyl Sulfate Minerals for Better Water Remediation and Resource Reuse

Iron hydroxyl sulfate minerals (IHSMs, including schwertmannite and jarosite) are a promising material for environmental applications with excellent adsorption of metal oxygen anions. The acid mine drainage (AMD) abundant in iron and sulfate ions holds potential for the production of valuable IHSMs, thereby achieving resource recycling whilst simultaneously mitigating water contamination, which is important for the sustainable remediation of AMD. Conventional mineralization, which promotes the generation of minerals from Fe3+ and SO42− through the energy provided by chemical or biological oxidation, can only partially mineralize iron in AMD containing substantial quantities of Fe2+. In this study, an improved method for mineralizing AMD containing iron of a different valence into IHSMs under the induction of KHCO3 was proposed. For AMD containing Fe2+, the combination of KHCO3 and H2O2 was used to promote the hydrolysis of iron (92.7%) and sulfate (11.1%) into IHK minerals, which resulted in a significant increase in iron removal of 75.2% and a minor increase in sulfate removal of 4.9%, compared with the formation of schwertmannite from oxidation solely involving H2O2. For the AMD containing Fe3+, the energy generated by the acid–base reaction in water could also directly promote the formation of IK minerals from 97.2% iron and 6.9% sulfate. XRD and FTIR analyses confirmed the identification of the IHK and IK minerals as IHSMs transitioning from schwertmannite to jarosite. SEM and elemental analyses indicated that the mineral exhibited denser aggregate spheres with the incorporation of KHCO3 in mineralization yet displayed enhanced mineralization abilities for the contaminant ions in AMD. Moreover, despite the SSA of the modified minerals being diminished (2.02, 1.83 and 1.83 m2/g for IH, IHK and IK, respectively), the presence of more sulfate in the mineral enhanced the adsorption capacity of Cr(VI). Furthermore, the water quality results also illustrated that the removal ratios of iron and sulfate in AMD notably increased with the involvement of KHCO3 in mineralization. In conclusion, the KHCO3-induced mineralization of iron-containing (either divalent or trivalent) AMD into IHSMs not only improved the mineralization ratios and contaminant removal ratios for better remediation of AMD but also obtained mineral resources with better adsorption of Cr(VI), thereby fostering the sustainable advancement of the remediation of AMD. Therefore, this innovative strategy employing KHCO3-assisted chemical mineralization to form IHSMs holds ample potential and promises to be an efficacious methodology for the sustainable remediation of iron-rich AMD.

Assessment of the induced effect of selected iron hydroxysulfates biosynthesized using Acidithiobacillus ferrooxidans for biomineralization of acid mine drainage.

Soluble iron and sulfate in acid mine drainage (AMD) can be greatly removed through the formation of minerals facilitated by seed crystals. However, the difference in the effects of jarosite and schwertmannite as endogenous seed crystals to induce AMD mineralization remains unclear. This paper intends to study the effect of Fe2+ oxidation and Fe3+ mineralization in the biosynthesis of minerals using different addition amounts and methods of jarosite or schwertmannite. The results showed that the addition amount and method of different seed crystals had no effect on the Fe2+ bio-oxidation but would change the Fe3+ mineralization efficiency. With the same amount of seed crystals added, jarosite exhibited a higher capacity to promote Fe3+ mineralization than schwertmannite. Adding seed crystals before the initiation of Fe2+ oxidation (0 h) could significantly promote Fe3+ mineralization efficiency. With the increase of seed crystals, jarosite could not only shorten the time required for mineral synthesis but also improve the final mineral yield, whereas schwertmannite could only shorten the time required for mineral synthesis. When Fe2+ was completely oxidized to Fe3+ (48 h), the supplementary of jarosite could still effectively improve Fe3+ mineralization efficiency, but the addition of schwertmannite no longer affected the final mineralization degree.

A novel approach for treating acid mine drainage through forming schwertmannite driven by a mixed culture of Acidiphilium multivorum and Acidithiobacillus ferrooxidans prior to lime neutralization

As the predominant treatment approach of acid mine drainage (AMD), lime neutralization often exhibits inefficiencies since the abundance of iron and sulfate in AMD usually form iron hydroxide and gypsum precipitate coatings on the surface of lime. In this study, a novel approach of biomineralization prior to lime neutralization for treating AMD was proposed, in which iron and sulfate were biologically precipitated as schwertmannite through iron biological reduction-oxidation driven by a culture mixed with Acidiphilium multivorum JZ-6 and Acidithiobacillus ferrooxidans LX5. It was found that only five cycles of iron reduction by A. multivorum JZ-6 followed by iron oxidation by A. ferrooxidans LX5 could remove completely iron and nearly 40% of sulfate in AMD, while non-ferrous metals (Al, Mn, Cu, Ni, and Zn) were hardly removed. Consequently, the amounts of lime required and sludge generated in the subsequent lime neutralization process were reduced by 56% and 68%, respectively. As a result, the content of non-ferrous metals in the sludge was increased by 3.2 folds. The level of Al was increased surprisingly to 19% (wt/wt), a level similar to the commercially valuable bauxite. The novel process of biomineralization prior to lime neutralization provides a sustainable way for AMD treatment.

Kraft pulp mill dregs and grits as permeable reactive barrier for removal of copper and sulfate in acid mine drainage

Mining is an essential human activity, but results in several environmental impacts, notably the contamination of ground and surface water through the presence of toxic substances such as metals and sulfates in mine drainage. Permeable reactive barriers (PRB) have been applied to remediate this environmental impact, but the high costs associated with the maintenance of this system are still a challenge. The main objective of this study was to evaluate the use of kraft pulp mill alkaline residues, known as dregs and grits, as material for PRB, and to determine their capacity for retaining copper and sulfate. The work was carried out in laboratory adsorption kinetics assays, batch assays and column tests. Tests for elemental characterization, point of zero charge, acid neutralization capacity, total porosity, bulk density and moisture of the dregs and grits were conducted. The results showed high retention of Cu due to a chemical precipitation mechanism, notably for dregs (99%) at 5 min in adsorption kinetics. The grits presented similar results after 180 min for the same assay. Sulfate retention was effective at pH below 5, with an efficiency of 79% and 89% for dregs and grits, respectively. Dregs presented the best results for acid drainage remediation, notably with a solid:liquid (S:L) ratio of 1:10.

A novel approach to rapidly purify acid mine drainage through chemically forming schwertmannite followed by lime neutralization

Acid mine drainage (AMD) has been recognized as a major challenge to the global mining industry due to its environmental consequences. Lime neutralization has been a traditional treatment for AMD, but the abundance of iron and sulfate in AMD usually renders it ineffective by forming iron hydroxide and gypsum precipitate coating on the surface of lime. In light of ubiquitous biological mineralization phenomena present at AMD sites, a rapid chemical mineralization was developed to reduce iron and sulfate and recovery of iron from AMD prior to lime neutralization. Through a cyclic reduction-oxidation process by the addition of iron powder and hydrogen peroxide (H2O2), over 90% Fe3+ and 40% SO42− could be removed beforehand by forming schwertmannite. The pretreated AMD drastically reduced both the required lime slurry in the subsequent lime neutralization process and the amount of neutralized sludge. The resultant schwertmannite had a specific surface area of 3.9 m2/g and a formula of Fe8O8(OH)4·5(SO4)1.75. This technique could reduce lime consumption, increase metal level in neutralized sludge, and harvest environmentally friendly materials. These results demonstrate that the integrated chemical mineralization and lime neutralization treatment is expected to be widely used in practical application.

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage.

Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid production, and mixed valence state sulfur species generated by the oxidation of the two different substrates suggests a metabolic flexibility in response to sulfur substrate availability. Our results demonstrate that microbial processing of mixed-valence-state sulfur species generates a significant sulfur isotope fractionation in acidic environments and oxidation of mixed-valence state sulfur species may produce sulfate with characteristic sulfur and oxygen isotope signatures. Elemental sulfur and tetrathionate are not only intermediate-valence state sulfur compounds that play a central role in sulfur oxidation pathways, but also key factors in shaping these isotope patterns.

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ 18O and δ 34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O 2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III) aq as an oxidant with varying δ 18O H 2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ∼2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ∼2.7. The δ 34S SO 4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (∼−0.7‰) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O 2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O 2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water ( ε 18 O SO 4 – H 2 O ) of ∼3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured ε 18 O SO 4 2 - – H 2 O value was then used to estimate the oxygen isotope fractionation effects ( ε 18 O SO 4 2 - – O 2 ) between sulfate and dissolved oxygen in the aerobic experiments which were −10.0‰, −10.8‰, and −9.8‰ for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between δ 18O SO 4 values in the biological and abiotic experiments, it is suggested that δ 18O SO 4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III) aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water–oxygen under both aerobic and anaerobic conditions.