A sulfate reducing bioreactor controlled by an electrochemical system enables near-zero chemical treatment of metallurgical wastewater.

Metallurgical wastewaters are characterized by a low pH (<4), high concentrations of sulfate (15 gSO42- L-1), and metal(loid)s. Current treatment requires the consumption of chemicals such as alkali and high levels of waste sludge generation. In this study, we have shown that combining water electrolysis and sulfate reducing bioreactors enables the in-situ generation of base and H2, eliminating the need for base and electron donor addition, resulting in the near-zero treatment of metallurgical wastewater. By extracting cations from the effluent of the system to the bioreactor, the bioreactor pH could be maintained by the in-situ production of alkali. The current for pH control varied between 112-753 mol electrons per m³ wastewater or 5-48 A m-2 electrode area. High concentrations of sulfate in the influent and addition of CO2 increased the current required to maintain a steady bioreactor pH. On the other hand, a high sulfate reduction rate and increased influent pH lowered the current required for pH control. Moreover, the current efficiency varied from 14% to 91% and increased with higher pH and cation (Na+, NH4+, K+, Mg2+, Ca2+) concentrations in the middle compartment of the electrochemical cell. The salinity was lowered from 70-120 mS cm-1 in the influent to 5-20 mS cm-1 in the system effluent. The energy consumption of the electrochemical pH control varied between 10 and 100 kWh m-3 and was affected by the conductivity of the wastewater. Industrial wastewater was treated successfully with an average energy consumption of 39 ± 7 kWh m-3, removing sulfate from 15 g SO42- L-1 to 0.5 ± 0.5 g SO42- L-1 at a reduction rate of 20 ± 1 gSO42- L-1 d-1..Metal(loid)s such as As, Cd, Cu, Pb, Te, Tl, Ni and Zn were removed to levels of 1-50 µg L-1.

Electrochemically assisted production of biogenic palladium nanoparticles for the catalytic removal of micropollutants in wastewater treatment plants effluent.

Biogenic palladium nanoparticles (bio-Pd NPs) are used for the reductive transformation and/or dehalogenation of persistent micropollutants. In this work, H2 (electron donor) was produced in situ by an electrochemical cell, permitting steered production of differently sized bio-Pd NPs. The catalytic activity was first assessed by the degradation of methyl orange. The NPs showing the highest catalytic activity were selected for the removal of micropollutants from secondary treated municipal wastewater. The synthesis at different H2 flow rates (0.310 L/hr or 0.646 L/hr) influenced the bio-Pd NPs size. The NPs produced over 6 hr at a low H2 flow rate had a larger size (D50 = 39.0 nm) than those produced in 3 hr at a high H2 flow rate (D50 = 23.2 nm). Removal of 92.1% and 44.3% of methyl orange was obtained after 30 min for the NPs with sizes of 39.0 nm and 23.2 nm, respectively. Bio-Pd NPs of 39.0 nm were used to treat micropollutants present in secondary treated municipal wastewater at concentrations ranging from µg/L to ng/L. Effective removal of 8 compounds was observed: ibuprofen (69.5%) < sulfamethoxazole (80.6%) < naproxen (81.4%) < furosemide (89.7%) < citalopram (91.7%) < diclofenac (91.9%) < atorvastatin (> 94.3%) < lorazepam (97.2%). Removal of fluorinated antibiotics occurred at > 90% efficiency. Overall, these data indicate that the size, and thus the catalytic activity of the NPs can be steered and that the removal of challenging micropollutants at environmentally relevant concentrations can be achieved through the use of bio-Pd NPs.

The influence of H2 partial pressure on biogenic palladium nanoparticle production assessed by single-cell ICP-mass spectrometry.

The production of biogenic palladium nanoparticles (bio-Pd NPs) is widely studied due to their high catalytic activity, which depends on the size of nanoparticles (NPs). Smaller NPs (here defined as <100 nm) are more efficient due to their higher surface/volume ratio. In this work, inductively coupled plasma-mass spectrometry (ICP-MS), flow cytometry (FCM) and transmission electron microscopy (TEM) were combined to obtain insight into the formation of these bio-Pd NPs. The precipitation of bio-Pd NPs was evaluated on a cell-per-cell basis using single-cell ICP-MS (SC-ICP-MS) combined with TEM images to assess how homogenously the particles were distributed over the cells. The results provided by SC-ICP-MS were consistent with those provided by "bulk" ICP-MS analysis and FCM. It was observed that heterogeneity in the distribution of palladium over an entire cell population is strongly dependent on the Pd2+ concentration, biomass and partial H2 pressure. The latter three parameters affected the particle size, ranging from 15.6 to 560 nm, and exerted a significant impact on the production of the bio-Pd NPs. The TEM combined with SC-ICP-MS revealed that the mass distribution for bacteria with high Pd content (144 fg Pd cell-1 ) indicated the presence of a large number of very small NPs (D50 = 15.6 nm). These results were obtained at high cell density (1 × 105 ± 3 × 104 cells µl-1 ) and H2 partial pressure (180 ml H2 ). In contrast, very large particles (D50 = 560 nm) were observed at low cell density (3 × 104 ± 10 × 102 cells µl-1 ) and H2 partial pressure (10-100 ml H2 ). The influence of the H2 partial pressure on the nanoparticle size and the possibility of size-tuned nanoparticles are presented.

High rate production of concentrated sulfides from metal bearing wastewater in an expanded bed hydrogenotrophic sulfate reducing bioreactor.

Metallurgical wastewaters contain high concentrations of sulfate, up to 15 g L-1. Sulfate-reducing bioreactors are employed to treat these wastewaters, reducing sulfates to sulfides which subsequently co-precipitate metals. Sulfate loading and reduction rates are typically restricted by the total H2S concentration. Sulfide stripping, sulfide precipitation and dilution are the main strategies employed to minimize inhibition by H2S, but can be adversely compromised by suboptimal sulfate reduction, clogging and additional energy costs. Here, metallurgical wastewater was treated for over 250 days using two hydrogenotrophic granular activated carbon expanded bed bioreactors without additional removal of sulfides. H2S toxicity was minimized by operating at pH 8 ± 0.15, resulting in an average sulfate removal of 7.08 ± 0.08 g L-1, sulfide concentrations of 2.1 ± 0.2 g L-1 and peaks up to 2.3 ± 0.2 g L-1. A sulfate reduction rate of 20.6 ± 0.9 g L-1 d-1 was achieved, with maxima up to 27.2 g L-1 d-1, which is among the highest reported considering a literature review of 39 studies. The rates reported here are 6-8 times higher than those reported for other reactors without active sulfide removal and the only reported for expanded bed sulfate-reducing bioreactors using H2. By increasing the influent sulfate concentration and maintaining high sulfide concentrations, sulfate reducers were promoted while fermenters and methanogens were suppressed. Industrial wastewater containing 4.4 g L-1 sulfate, 0.036 g L-1 nitrate and various metals (As, Fe, Tl, Zn, Ni, Sb, Co and Cd) was successfully treated with all metal(loid)s, nitrates and sulfates removed below discharge limits.

Electrified bioreactors: the next power-up for biometallurgical wastewater treatment.

Over the past decades, biological treatment of metallurgical wastewaters has become commonplace. Passive systems require intensive land use due to their slow treatment rates, do not recover embedded resources and are poorly controllable. Active systems however require the addition of chemicals, increasing operational costs and possibly negatively affecting safety and the environment. Electrification of biological systems can reduce the use of chemicals, operational costs, surface footprint and environmental impact when compared to passive and active technologies whilst increasing the recovery of resources and the extraction of products. Electrification of low rate applications has resulted in the development of bioelectrochemical systems (BES), but electrification of high rate systems has been lagging behind due to the limited mass transfer, electron transfer and biomass density in BES. We postulate that for high rate applications, the electrification of bioreactors, for example, through the use of electrolyzers, may herald a new generation of electrified biological systems (EBS). In this review, we evaluate the latest trends in the field of biometallurgical and microbial-electrochemical wastewater treatment and discuss the advantages and challenges of these existing treatment technologies. We advocate for future research to focus on the development of electrified bioreactors, exploring the boundaries and limitations of these systems, and their validity upon treating industrial wastewaters.

Separation and recovery of ammonium from industrial wastewater containing methanol using copper hexacyanoferrate (CuHCF) electrodes.

Ammonium is typically removed from wastewater by converting it to nitrogen gas using microorganisms, precluding its recovery. Copper hexacyanoferrate (CuHCF) is known to reversibly intercalate alkali cations in aqueous electrolytes due to the Prussian Blue crystal structure. We used this property to create a carbon-based intercalation electrode within an electrochemical cell. Depending on the electrode potential, it can recover NH4+ from wastewater via insertion/regeneration while leaving organics. In the first phase, different binders were evaluated towards creating a stable electrode matrix, with sodium carboxymethyl cellulose giving the best performance. Subsequently, based on voltammetry, we determined an intercalation potential for NH4+ removal of + 0.3 V vs. Ag/AgCl, while the regeneration potential of the electrode was + 1.1 V (vs. Ag/AgCl). Using the CuHCF electrodes 95% of the NH4+ in a synthetic wastewater containing 56 mM NH4+ and 68 mM methanol was removed with an energy input of 0.34 ± 0.01 Wh g-1 NH4+. A similar removal of 93% was obtained using an actual industrial wastewater (56 mM NH4+, 68 mM methanol, 0.02 mM NO2-, 0.05 mM NO3-, 0.04 mM SO42- and 0.34 mM ethanol), with an energy input of 0.40 ± 0.01 Wh g-1 NH4+. In both cases, there was negligible removal of organics. The stability of CuHCF electrodes was evaluated either by open circuit potential monitoring (61 h) or by cyclic voltammetry (50 h, 116 cycles). The stability during cycling of the electrode was determined in both synthetic and real streams for 25 h (125 cycles). The charge density (C cm-1) of the CuHCF electrodes declined by 17 % and 19% after 125 cycles in the synthetic stream and the actual wastewater, respectively. This study highlights the possibility of low-cost CuHCF coated electrodes for achieving separation of NH4+ from streams containing methanol. The stability of electrodes has been improved but needs to be further enhanced for large-scale applications and long-term operation.

Effect of speciation and composition on the kinetics and precipitation of arsenic sulfide from industrial metallurgical wastewater.

Precipitation of arsenic as As2S3 produces little waste sludge, has the potential for low chemical consumption and for selective metal(loid) removal. In this study, arsenic removal from acidic (pH 2), metallurgical wastewater was tested in industrially relevant conditions. Sulfides added at a S:As molar ratio of 2.5 and 5 resulted in removal of 99% and 84% of As(III) and As(V). Precipitation of As2S3 from the As(III) and industrial wastewater containing 17% As(V) was nearly instantaneous. For the synthetic As(V) solution, reduction to As(III) was the rate limiting step. At a S:As ratio of 20 and an observed removal rate (k2 = 4.8 (mol L-1) h-1), two hours were required to remove of 93% of arsenic from a 1 g As L-1 solution. In the case of As(V) in industrial samples this time lag was not observed, showing that components in the industrial wastewater affected the removal and reduction of arsenate. Speciation also affected flocculation and coagulation characteristics of As2S3 particles: As(V) reduction resulted in poor coagulation and flocculation. Selective precipitation of arsenic was possible, but depended on speciation, S:As ratio and other metals present.