Role of reactor type on Cr(VI) removal by zero-valent iron in the presence of pyrite: Batch versus sequential batch reactors.

This study was conducted to understand the role of application sequence of pyrite and zero-valent iron (Fe0) (simultaneous vs. sequential) on chromium (VI) removal by Fe0. In batch experiments, pyrite and Fe0 were homogeneously mixed in batch reactors maintained at a constant total solids loading of 2 g L-1. In sequential batch experiments, however, the first reactor containing variable doses of pyrite was operated for 20 min, and the liquid fraction from the first reactor was then subsequently loaded into the second reactor containing a fixed Fe0 dose of 1.2 g L-1. The batch reactors achieved much higher Cr(VI) removal efficiency than sequential batch reactors under similar operating conditions due to discrepancies in Fe redox cycling activities between these two systems. In batch reactors, the Fe0 particles deposited on pyrite surface due to electrostatic attraction between negatively charged pyrite and positively charged Fe0, thus, rendering the overall solids surface charge neutral at optimum pyrite and Fe0 doses. As a result, the whole system behaved like a composite material, with pyrite functioning as a support material for Fe0. This stimulated Fe redox cycling more effectively to generate new Fe(II) sites on Fe0 for enhanced Cr(VI) removal relative to Fe0 only system. In sequential batch reactors, however, the Fe redox cycling activity was limited, but significantly increased with increasing pyrite dose in the first reactor. Overall, our results indicate that the stimulatory effect of pyrite on Cr(VI) removal by Fe0 may be much higher if the reactors are operated in batch mode.

Comparison of treatability of four different chlorophenol-containing wastewater by pyrite-Fenton process combined with aerobic biodegradation: Role of sludge acclimation.

Aerobic biodegradation combined with pyrite-Fenton process was used for the treatment of wastewater containing different chlorophenols (4-CP, 2,3-DCP, 2,4-DCP, 2,4,6-TCP). Fenton degradation using pyrite as the low cost iron catalyst was used as a pre-treatment step to lower the toxicity of CPs prior to aerobic biodegradation. Synthetic wastewater spiked directly with either 100 mg/L CPs or pyrite-Fenton pre-treated CPs was fed to the batch bioreactors inoculated with unacclimated or acclimated activated sludge using glucose as the C-source. The results show that the CP biodegradation under aerobic conditions was highly dependent on the type of CP treated. Except for 2,4-DCP, all other CPs investigated caused severe sludge toxicity, and thus significantly hindered glucose degradation by unacclimated sludge. The CP toxicity decreased in the order of: 2,4,6-TCP > 2,3-DCP > 4-CP > 2,4-DCP. The toxic effect was explained through an interaction of CPs with the lipid fraction of cell membrane. While the pyrite-Fenton pre-treatment improved the COD removal efficiency using unacclimated sludge, the sCOD removal efficiency was still less than the control reactor operated with no CP addition. With sludge acclimation, however, the sCOD removal efficiencies increased, and approached 74% for 2,4-DCP, 61% for 4-CP, 56% for 2,4,6-TCP and 46% for 2,3-DCP, suggesting an enhanced biomass tolerance to CP toxicity. On the other hand, the sludge acclimation combined with pyrite Fenton pre-treatment provided the best bioreactor performance for all CPs with the sCOD removal efficiencies reaching 81% for 2,4,6-TCP, 78% for 2,4-DCP, 73% for 4-CP and 62% for 2,3-DCP. This suggests that the dechlorination of CPs with Fenton process, in conjunction with sludge acclimation, not only reduced the sludge toxicity, but also enhanced the bioavailability of CP-containing wastewater for microorganisms, especially for highly chlorinated toxic CPs such as 2,4,6-TCP. Overall, the findings highlight the need for sludge acclimation for effective treatment of chlorophenol-containing wastewater by a combined pyrite-Fenton and aerobic biodegradation system.

Ligand enhanced pharmaceutical wastewater treatment with Fenton process using pyrite as the catalyst: Column experiments.

Advanced oxidation processes offer practical and cost effective solutions for the treatment of poorly biodegradable industrial wastewaters. Here, column experiments were performed to understand the role of a complexing agent, citrate, on Fenton-treatment of an actual pharmaceutical wastewater with pyrite as the catalyst under dynamic flow conditions. Our results suggest that the pharmaceutical wastewater treatment with Fenton reaction using pyrite as the catalyst was mainly regulated by the extent of Fe dissolution from pyrite, which, in turn, resulted in formation of hydroxyl radicals in solution. The Fenton treatment efficiency was much lower in the absence of citrate compared to citric acid containing systems due to clogging of column pores with oxidized Fe species. On the other hand, the addition of citrate to wastewater significantly improved Fenton process efficacy, and prolonged the lifecycle of pyrite-packed columns depending on solution pH. Low pH values were favorable for better Fenton efficiency in systems containing citrate due to combined effect of proton and ligand promoted dissolution and mobilization of oxidized Fe species.

Role of complexing agents on oxidative degradation of chlorophenolic compounds by pyrite-Fenton process: Batch and column experiments.

This study involves batch reactor and fixed-bed continuous flow experiments to determine the effects of complexing agents (e.g., tartrate and citrate) on the treatment of chlorophenolic (CP) compounds using heterogeneous Fenton system with pyrite mineral as the iron source. While the addition of organic ligands to the batch systems adversely affected CP removal, organic ligands had a beneficial effect on CP removal in column systems. Although the ligands extended the life span of pyrite-packed columns by removing surface oxidation products through the formation of soluble Fe-ligand complexes, the ligands competed against CPs for hydroxyl radicals (HO*). The competitive effect was much higher in batch systems since pyrite loading was very low in order to generate sufficient hydroxyl radicals. On the other hand, at much higher pyrite loading of column experiments, the HO* radicals generated during Fenton process were sufficient to overcome the competitive effect exerted by organic ligands. In spite of much higher Fe solubility in the presence of citrate, citrate was less effective in enhancing CP removal in column systems compared to tartrate since the competitive effect caused by citrate for HO* radicals was more than that exerted by tartrate.

Diclofenac removal by pyrite-Fenton process: Performance in batch and fixed-bed continuous flow systems.

This study provides experimental results from batch and column studies to investigate diclofenac degradation by pyrite-Fenton process under variable chemical conditions (e.g., pyrite loading). Batch experiments show that diclofenac removal increased with increasing hydrogen peroxide and pyrite concentration. On the other hand, the addition of organic chelating agents such as citrate had an adverse effect on diclofenac removal by pyrite-Fenton process in batch systems due to scavenging effect of these agents for hydroxyl radicals. Batch results showed a direct correlation between the rate of diclofenac degradation and the rate of iron dissolution from pyrite, suggesting that diclofenac removal by pyrite-Fenton process was mainly controlled by solution phase hydroxyl radical attack on aromatic structure. Column experiments show that the effluent diclofenac concentration initially reached a peak value, and then sharply decreased to zero at higher pore volumes. The initial diclofenac breakthrough coincided well with the highest Fe(II) concentration observed in the breakthrough curve, implying that the generation of excess Fe(II) had a detrimental effect on removal efficiency due to scavenging effect of excess Fe(II) for hydroxyl radicals. The column system continued to function with 100% diclofenac removal efficiency when the effluent Fe(II) concentration decreased to a level at which the scavenging effect was minimized.

Oxidative degradation of chlorophenolic compounds with pyrite-Fenton process.

Batch experiments, in conjunction with chromatographic and spectroscopic measurements, were performed to comparatively investigate the degradation of various chlorophenolic (CP) compounds (e.g., 2-CP, 4-CP, 2,3-DCP, 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TeCP) by a modified Fenton process using pyrite as the catalyst. The batch results show that the CP removal by pyrite-Fenton process was highly dependent on chemical conditions (e.g., pH, CP and pyrite concentration), CP type, number and location of chlorine atoms on the aromatic ring. With the exception of 2,3,4,6-TeCP and 2,3-DCP, the CP removal decreased with increasing the number of chlorine constituents. While the main mechanism responsible for monochlorophenol removal (e.g., 2-CP and 4-CP) was the hydroxyl radical attack on aromatic rings, the CP removal for multichlorophenolic compounds (e.g., 2,3,4,6-TeCP) was driven by both: (1) hydroxyl radical attack on aromatic rings by both solution and surface-bound hydroxyl radicals and (2) adsorption onto pyrite surface sites. The adsorption affinity increased with increasing the number of Cl atoms on the aromatic ring due to enhanced hydrophobic effect. The TOC removal was not 100% complete for all CPs investigated due to formation of chemically less degradable chlorinated intermediate organic compounds as well as low molecular weight organic acids such as formic and acetic acid. Spectroscopic measurements with SEM-EDS, zeta potential and XPS provided evidence for the partial oxidation of pyrite surface Fe(II) and disulfide groups under acidic conditions.

Role of low molecular weight organic acids on pyrite dissolution in aqueous systems: implications for catalytic chromium (VI) treatment.

A systematic study combining batch experiments with spectroscopic analyses was carried out to better understand the effects of various organic acids on pyrite dissolution and subsequent Cr(VI) removal in aqueous systems. Our results suggest that organic acids had no effect on total Fe dissolution from pyrite relative to systems containing no acid. However, while nearly 100% of total Fe dissolved from pyrite was in Fe(II) form in the absence of ligands, the addition of organic acids led to significant oxidation of Fe(II) species to Fe(III). The degree and extent of Fe(II) oxidation increased in the order: tartrate < salicylate < oxalate ≈ citrate < EDTA. Except for salicylate (an aromatic compound), this stimulatory effect observed in Fe(II) oxidation was well correlated with the strength of Fe-ligand complexes. In systems containing Cr(VI), the amount of Fe dissolved increased significantly relative to non-Cr(VI) containing system, and the ligands enhanced the dissolution of surface oxidation products from pyrite. Overall, it is clear that the dissolution of pyrite with organic acids had very little effect on solution phase Cr(VI) removal, but significantly stimulated surface phase Cr(VI) reduction by removing surface oxidation products, and thus creating new surface sites for extended Cr(VI) removal.

Comparison of different chelating agents to enhance reductive Cr(VI) removal by pyrite treatment procedure.

New technologies involving in-situ chemical hexavalent chromium [Cr(VI)] reduction to trivalent chromium [Cr(III)] with natural Fe(II)-containing minerals can offer viable solutions to the treatment of wastewater and subsurface systems contaminated with Cr(VI). Here, the effects of five different chelating agents including citrate, EDTA, oxalate, tartrate and salicylate on reductive Cr(VI) removal from aqueous systems by pyrite were investigated in batch reactors. The Cr(VI) removal was highly dependent on the type of ligand used and chemical conditions (e.g., ligand concentration). While salicylate and EDTA had no or little effect on Cr(VI) removal, the ligands including citrate, tartrate and oxalate significantly enhanced Cr(VI) removal at pH < 7 relative to non-ligand systems. In general, the efficiency of organic ligands on Cr(VI) removal decreased in the order: citrate ≥ oxalate ≈ tartrate > EDTA > salicylate ≈ non-ligand system. Organic ligands enhanced Cr(VI) removal by 1) removing surface oxide layer via the formation of soluble Fe-Cr-ligand complexes, and 2) enhancing the reductive iron redox cycling for the regeneration of new surface sites. While citrate, oxalate and tartrate eliminated the formation of surface Cr (III)-Fe(III)-oxides, the surface phase Cr (III) species was observed in the presence of EDTA and salicylate indicating that Cr(III) complexed with EDTA and salicylate sorbed or precipitated onto pyrite surface, thereby blocking the access of CrO4(2-) to pyrite surface. The binding of Fe(III) with the disulfide reactive sites (≡Fe-S-S-Fe(III)) was essential for the regeneration of new surface sites through pyrite oxidation. Although Fe(III)-S species was detected at the pyrite surface in the presence of citrate, oxalate and tartrate, Fe(III) complexed with EDTA and salicylate did not strongly interact with the disulfide reactive sites due to the formation of non-sorbing Fe(III)-ligand complexes. The absence of surface Fe(III)-S species indicated that no new reactive sites were generated through Fe redox cycling in the presence of salicylate and EDTA.

Cr(VI) removal from aqueous systems using pyrite as the reducing agent: batch, spectroscopic and column experiments.

Laboratory batch and column experiments, in conjunction with geochemical calculations and spectroscopic analysis, were performed to better understand reaction mechanisms and kinetics associated with Cr(VI) removal from aqueous systems using pyrite as the reactive material under both static and dynamic flow conditions similar to those observed in in situ permeable reactive barriers (PRBs). The X-ray photoelectron spectroscopy (XPS) and geochemical calculations suggest that the Cr(VI) removal by pyrite occurred due to the reduction of Cr(VI) to Cr(III), coupled with the oxidation of Fe(II) to Fe(III) and S2(2-) to SO4(2-) at the pyrite surface. Zeta potential measurements indicate that although the pyrite surface was negatively charged under a wide pH range in the absence of Cr(VI), it behaved more like a "metal oxide" surface with the surface potential shifting from positive to negative values at pH values >pH 6 in the presence of Cr(VI). Batch experiments show that increasing solution pH led to a significant decrease in Cr(VI) removal. The decrease in Cr(VI) removal at high Cr(VI) concentrations and pH values can be explained through the precipitation of sparingly soluble Cr(OH)(3(s)), Fe(OH)(3(s)) and Fe(III)-Cr(III) (oxy) hydroxides onto pyrite surface which may, then, lead to surface passivation for further Cr(VI) reduction. Batch results also suggest that the reaction kinetics follow a first order model with rate constants decreasing with increasing solution pH, indicating proton consumption during Cr(VI) reduction by pyrite. Column experiments indicate that nearly 100% of total Fe in the column effluent was in the form of Fe(II) species with a [SO4(2-)]/[Fe(2+)] stoichiometric ratio of 2.04, indicating that the reduction of Cr(VI) by pyrite produced about 2 mol of sulfate per mole of Fe (II) release under excess surface sites relative to Cr(VI) concentration. Column experiments provide further evidence on the accumulation of oxidation products which consequently led to a significant pressure build up in pyrite packed columns over time.

Chromium(VI) bioremoval by Pseudomonas bacteria: role of microbial exudates for natural attenuation and biotreatment of Cr(VI) contamination.

Laboratory batch and column experiments were conducted to investigate the role of microbial exudates, e.g., exopolymeric substance (EPS) and alginic acid, on microbial Cr(VI) reduction by two different Pseudomonas strains (P. putida P18 and P. aeuroginosa P16) as a method for treating subsurface environment contaminated with Cr(VI). Our results indicate that microbial exudates significantly enhanced microbial Cr(VI) reduction rates by forming less toxic and highly soluble organo-Cr(III) complexes despite the fact Cr(III) has a very low solubility under the experimental conditions studied (e.g., pH 7). The formation of soluble organo-Cr(III) complexes led to the protection of the cells and chromate reductases from inactivation. In systems with no organic ligands, soluble organo-Cr(III) end products were formed between Cr(III) and the EPS directly released by bacteria due to cell lysis. Our results also provide evidence that cell lysis played an important role in microbial Cr(VI) reduction by Pseudomonas bacteria due to the release of constitutive reductases that intracellularly and/or extracellularly catalyzed the reduction of Cr(VI) to Cr(III). The overall results highlight the need for incorporation of the release and formation of organo-Cr(III) complexes into reactive transport models to more accurately design and monitor in situ microbial remediation techniques for the treatment of subsurface systems contaminated with Cr(VI).

Role of microbial exopolymeric substances (EPS) on chromium sorption and transport in heterogeneous subsurface soils: I. Cr(III) complexation with EPS in aqueous solution.

Chromium (III) binding by exopolymeric substances (EPS) isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 strains were investigated by the determination of conditional stability constants and the concentration of functional groups using the ion-exchange experiments and potentiometric titrations. Spectroscopic (EXAFS) analysis was also used to obtain information on the nature of Cr(III) binding with EPS functional groups. The data from ion-exchange experiments and potentiometric titrations were evaluated using a non-electrostatic discrete ligand approach. The modeling results show that the acid/base properties of EPSs can be best characterized by invoking four different types of acid functional groups with arbitrarily assigned pK(a) values of 4, 6, 8 and 10. The analysis of ion-exchange data using the discrete ligand approach suggests that while the Cr binding by EPS from P. aeruginosa can be successfully described based on a reaction stoichiometry of 1:2 between Cr(III) and HL(2) monoprotic ligands, the accurate description of Cr binding by EPSs extracted from P. putida and P. stutzeri requires postulation of 1:1 Cr(III)-ligand complexes with HL(2) and HL(3) monoprotic ligands, respectively. These results indicate that the carboxyl and/or phosphoric acid sites contribute to Cr(III) binding by microbial EPS, as also confirmed by EXAFS analysis performed in the current study. Overall, this study highlights the need for incorporation of Cr-EPS interactions into transport and speciation models to more accurately assess microbial Cr(VI) reduction and chromium transport in subsurface systems, including microbial reactive treatment barriers.

Role of microbial exopolymeric substances (EPS) on chromium sorption and transport in heterogeneous subsurface soils: II. Binding of Cr(III) in EPS/soil system.

Laboratory batch sorption and column experiments were performed to investigate the effects of microbial EPSs isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 on Cr(III) mobility in heterogeneous subsurface soils. Our batch and column results indicate that microbial EPS may have a pronounced effect on Cr(III) sorption and transport behavior depending on system conditions (e.g., pH, type of EPS). While EPS had no effect on Cr(III) sorption at pH<5, it led to a significant decrease in Cr(III) sorption under slightly acidic to alkaline pH range. Column experiments performed at pH 7.9 suggest that, in the presence of EPS, chromium(III) was significantly mobilized relative to non-EPS containing system due to the formation less sorbing and highly soluble Cr-EPS complexes and competition of EPS against Cr for surface sites. A two-site non-electrostatic surface chemical model incorporating a discrete ligand approach for the description of Cr-EPS interactions accurately predicted Cr(III) sorption and transport behavior in the presence of EPS under variable chemical conditions. Our simulations show that an accurate description of Cr(III) transport in the presence of EPS requires incorporation of proton and Cr(III) binding by EPS, EPS binding by soil minerals, Cr(III) binding by soil minerals, and ternary Cr(III)-EPS surface complexes into the transport equations. Although this approach may not accurately describe the actual mechanisms at the molecular level, it can improve our ability to accurately describe the effects of EPS on Cr(III) mobility in subsurface environment relative to the use of distribution coefficients (K(d)).

Modeling Cd(II) adsorption to heterogeneous subsurface soils in the presence of citric acid using a semi-empirical surface complexation approach.

Laboratory batch sorption experiments were conducted to understand the effect of citrate on cadmium sorption to heterogeneous subsurface soils. Our results indicate that citrate may have a pronounced effect on Cd(II) sorption depending on system conditions (e.g. pH, ligand concentration). While the presence of citrate had no effect on Cd(II) sorption at pH < 4, it led to a decrease in Cd sorption under slightly acidic to alkaline pH range depending on the concentration of citrate used. Maximum effect of citrate on Cd(II) sorption was observed at pHs between 5 and 7. This coincides with the observed range of maximum citrate adsorption and the formation of Cd-citrate complexes. A two-site non-electrostatic surface chemical model (SCM) based on the Generalized Composite (GC) approach was able to describe the experimental data well over a wide range of conditions, with only six different surface reactions including two ternary (Cd/citrate/soil) surface complexes. Although the semi-empirical surface model used in the simulations does not accurately represent the actual mechanisms at the molecular level, it is relatively simple, and can be effectively used in transport calculations as an alternative to the K(d) approach.

Interactions between uronic acids and chromium(III).

Laboratory ion-exchange experiments were performed to investigate the complexation behavior of Cr(III) with uronic acids, such as galacturonic, glucuronic, and alginic acid (main constituents of bacterial exopolymeric substances). The experimental data were analyzed with a chemical equilibrium model in FITEQL to determine the reaction stoichiometries and stability constants for the formation of Cr-ligand complexes. Analysis of ion-exchange data with a chemical model indicates that the accurate description of Cr(III) complexation with both glucuronic and galacturonic acids requires postulation of a mixture of 1:1/1:2 complexes between Cr(III) and ligands under the experimental conditions studied (e.g., pH 4), but that the Cr-alginic acid binding can be modeled based on a reaction stoichiometry of 1:1 Cr-alginic acid complexes. Because of the complex nature of alginic acid, a nonelectrostatic, discrete ligand approach was used to determine proton and Cr binding with the functional groups of alginic acid. In this approach, alginic acid was conceptualized as being composed of a suite of two monoprotic acids (HL1 and HL2) with arbitrarily assigned pKa values of two and four, respectively. The results indicate that Cr binding with uronic acids mainly occurs through carboxylic groups under acidic to slightly alkaline pH conditions (e.g., pH < 8). The overall results of the present study indicate that the formation of such Cr-ligand complexes may have a pronounced effect on Cr(III) transport, solubility and bioavailability in natural systems.

In situ stabilization of chromium(VI) in polluted soils using organic ligands: the role of galacturonic, glucuronic and alginic acids.

Laboratory batch sorption and column experiments were performed to investigate the role of organic ligands such as galacturonic, glucuronic and alginic acids (main constituents of bacterial exopolymeric substances (EPS)) on Cr(VI) uptake and transport in heterogeneous subsurface media. Our batch sorption experiments demonstrate the addition of galacturonic, glucuronic and alginic acids to soils enhances Cr(VI) uptake by soil at pH values <7.7 depending on the concentration of the ligand and pH used. The enhanced Cr(VI) uptake at pH values <7.7 may be explained through either the catalytic reduction of Cr(VI) to Cr(III) by the surface-bound organic matter/Fe oxides and/or the dissolved metal ions (e.g., Fe(III)) from the soil. On the other hand, organic ligands have no or little effect on Cr(VI) uptake under highly alkaline pH conditions since the catalytic Cr(VI) reduction decreases with increasing pH. Similarly, the results from column experiments show that, depending on the concentration of organic ligands, the Cr(VI) breakthrough curves were significantly retarded relative to the organic acid-free systems at pH 7.6. A significant portion of Cr(VI) initially added to the feed solution was not readily recoverable in the effluent, indicating Cr(VI) reduction in columns, most probably catalyzed by surface-bound metal-oxides (e.g., Fe oxides) or dissolved metal ions such as Fe(II; III). The overall results suggest that EPS constituents such as glucuronic, galacturonic and alginic acids may play a significant role on Cr(VI) stabilization in subsurface systems under acidic to slightly alkaline pH conditions.

Determination of stability constants of U(VI)-Fe(III)-citrate complexes.

Ion-exchange experiments were performed to evaluate the formation of the uranium-citrate and uranium-iron-citrate complexes over a wide concentration range; i.e., environmentally relevant concentrations (e.g., 10(-6) M in metal and ligand) and concentrations useful for spectroscopic investigations (e.g., 10(-4) M in metal and ligand). The stability of the well-known uranium-citrate complex was determined to validate the computational and experimental methods applied to the more complex system. Values of the conditional stability constants for these species were obtained using a chemical equilibrium model in FITEQL. At a pH of 4.0, the stability constant for uranium-citrate complex (log beta1,1) was determined to be 8.71+/-0.6 at I = 0. Analysis of the results of ion-exchange experiments for the U-Fe-citric acid system indicates the formation of the 1:1:1 and 1:1:2 ternary species with stability constants (log beta) of 17.10+/-0.41 and 20.47+/-0.31, respectively, at I= 0.