Electroless Production of Fertilizer (Struvite) and Hydrogen from Synthetic Agricultural Wastewaters.

The drive toward sustainable phosphorus (P) recovery from agricultural and municipal wastewater streams has intensified. However, combining P recovery with energy conservation is perhaps one of the greatest challenges of this century. In this study, we report for the first time the simultaneous electroless production of struvite and dihydrogen from aqueous ammonium dihydrogen phosphate (NH4H2PO4) solutions in contact with either a pure magnesium (Mg) or a Mg alloy as the anode and 316 stainless steel (SS) as the cathode placed in a bench-scale electrochemical reactor. During the electroless process (i.e., in the absence of external electrical power), the open circuit potential (OCP), the formation of struvite on the anode, and the generation of dihydrogen at the cathode were monitored. We found that struvite is formed, and that struvite crystal structure/morphology and precipitate film thickness are affected by the concentration of the HnPO4n-3/NH4+ in solution and the composition of the anode. The pure Mg anode produced a porous 0.6-4.1 µm thick film, while the AZ31 Mg alloy produced a more compact 1.7-9.9 µm thick struvite film. Kinetic analyses revealed that Mg dissolution to Mg2+ followed mostly a zero-order kinetic rate law for both Mg anode materials, and the rate constants (k) depended upon the struvite layer morphology. Fourier-transform infrared spectrometry, X-ray diffraction, and scanning electron microscopy indicated that the synthesized struvite was of high quality. The dihydrogen and Mg2+ in solution were detected by a gas chromatography-thermal conductivity detector and ion chromatography, respectively. Furthermore, we fully demonstrate that the reactor was able to remove ∼73% of the HnPO4n-3 present in a natural poultry wastewater as mainly struvite. This study highlights the feasibility of simultaneously producing struvite and dihydrogen from wastewater effluents with no energy input in a green and sustainable approach.

Electrochemical nutrient removal from natural wastewater sources and its impact on water quality.

In this study, a suite of natural wastewater sources is tested to understand the effects of wastewater composition and source on electrochemically driven nitrogen and phosphorus nutrient removal. Kinetics, electrode behavior, and removal efficiency were evaluated during electrochemical precipitation, whereby a sacrificial magnesium (Mg) anode was used to drive precipitation of ammonium and phosphate. The electrochemical reactor demonstrated fast kinetics in the natural wastewater matrices, removing up to 54% of the phosphate present in natural wastewater within 1 min, with an energy input of only 0.04 kWh.m-3. After 1 min, phosphate removal followed a zero-order rate law in the 1 min - 30 min range. The zero-order rate constant (k) appears to depend upon differences in wastewater composition, where a faster rate constant is associated with higher Cl- and NH4+ concentrations, lower Ca2+ concentrations, and higher organic carbon content. The sacrificial Mg anode showed the lowest corrosion resistance in the natural industrial wastewater source, with an increased corrosion rate (vcorr) of 15.8 mm.y-1 compared to 1.9-3.5 mm.y-1 in municipal wastewater sources, while the Tafel slopes (ß) showed a direct correlation with the natural wastewater composition and origin. An overall improvement of water quality was observed where important water quality parameters such as total organic carbon (TOC), total suspended solids (TSS), and turbidity showed a significant decrease. An economic analysis revealed costs based upon experimental Mg consumption are estimated to range from 0.19 $.m-3 to 0.30 $.m-3, but costs based upon theoretical Mg consumption range from 0.09 $.m-3 to 0.18 $.m-3. Overall, this study highlights that water chemistry parameters control nutrient recovery, while electrochemical treatment does not directly produce potable water, and that economic analysis should be based upon experimentally-determined Mg consumption data. Synopsis Statement: Magnesium-driven electrochemical precipitation of natural wastewater sources enables fast kinetics for phosphate removal at low energy input.

Disinfection/ammonia removal from aquaculture wastewater and disinfection of irrigation water using electrochemical flow cells: A case study in Hawaii.

This field case study reports findings on disinfection/ammonia removal from aquaculture wastewater and disinfection of irrigation water carried out at an aquaculture farm and two irrigation locations in Hawaii. We used a flow cell incorporating PtRu/graphite anode and graphite cathode for the disinfection/ammonia removal from aquaculture wastewater, and a flow cell assembled with graphite plates as both anode and cathode for the disinfection of irrigation water. The removal of ammonia followed the indirect oxidation mechanism mediated by free chlorine electro-generated at the PtRu/graphite anode. Ammonia removal rate increased with the increase in NaCl concentration, applied current density, or flow rate. The disinfection of aquaculture wastewater can be readily achieved due to the presence of highly germicidal free chlorine species. The disinfection of irrigation water was realized without the addition of chemicals. The disinfection mechanism was attributed to the formation of free chlorine from the anodic oxidation of chloride ions naturally occurring in the water sources. The disinfection efficiency decreased with increasing organic matter concentration. In addition to the flow cell approach, we also successfully demonstrated the disinfection of irrigation water by adding electrolyzed NaCl solution or purging with a mixture of air and chlorine gas, both of which were generated on-site. PRACTITIONER POINTS: Field case study on disinfection/ammonia removal from aquaculture wastewater and disinfection of irrigation water was carried out in Hawaii. Electrochemical flow cell assembled with PtRu/graphite anode and graphite cathode effectively removes ammonia from aquaculture wastewater. Ammonia removal proceeds via the indirect oxidation mechanism mediated by free chlorine electro-generated at the PtRu/graphite anode. Electrochemical flow cell assembled with commercial graphite electrodes enables fast disinfection of coliform bacteria and E. coli. The primary disinfection mechanism is through chlorine species electro-generated from chloride oxidation at the graphite anode.

Electrochemical disinfection of irrigation water with a graphite electrode flow cell.

In this work, we report experimental studies on the disinfection of irrigation water using a flow cell assembled with low-cost graphite plates as both anode and cathode. Natural irrigation waters collected from two irrigation locations (Reservoir 225 and Bott Well Pond) in Hawaii were used, and synthetic irrigation waters were prepared based on the chemical analysis of natural irrigation waters. The concentration of chloride was 10.2 mg/L in the synthetic Reservoir 225 water and 6.9 mg/L in the synthetic Bott Well pond water. Escherichia coli K12 ER2738 was selected as a model bacterium to evaluate the disinfection capability of the flow cell. Experiments performed in the synthetic irrigation waters showed that E. coli was inactivated by free chlorine species electro-generated from oxidation of chloride ions at the graphite anode. Complete removal of E. coli was achieved within 10 min in the synthetic irrigation waters. The disinfection of the natural irrigation waters took about four times longer than the disinfection of the synthetic irrigation waters. This result is most likely due to the presence of organic matter (and possibly other oxidizable species) in the natural irrigation waters. PRACTITIONER POINTS: Electrochemical flow cell disinfects to 99.9% with commercial graphite electrodes. E. coli is removed in 10 min from synthetic irrigation water by a flow cell. E. coli removal takes 4× longer in natural irrigation water. A minimum current density of ≥1 mA/cm2 is required for disinfection. The primary disinfection mechanism is through chlorine generated from chloride ions.

Combined Osmotic and Membrane Distillation for Concentration of Anthocyanin from Muscadine Pomace.

Bioactive anthocyanins from aqueous extracts of muscadine grape pomace were concentrated using osmotic distillation (OD) and direct contact membrane distillation (DCMD) using polypropylene (PP) and poly(ethylene chlorotrifluoroethylene) (ECTFE) membranes. The driving force for OD is created by using a high concentration brine solution while the driving force for DCMD is generated by elevating the feed temperature relative to the permeate temperature. The brine concentration used was 4 M. The lowest fluxes were obtained for OD. Given the temperature sensitive nature of anthocyanins, the maximum temperature difference during DCMD was limited to 30 °C. The feed temperature was 40 °C and the permeate at 10 °C. Consequently, the maximum flux during DCMD was also limited. A combination of OD and DCMD was found to give the highest fluxes. High-performance liquid chromatography (HPLC) and HPLC-electrospray mass spectrometry were used to identify and quantify anthocyanins, cyanidin-3,5-O-diglucoside, delphinidin-3,5-O-diglucoside, petunidin-3,5-O-diglucoside, peonidin-3,5-O-diglucoside, and malvidin-3,5-O-diglucoside. The results obtained here suggest that, though water fluxes for DI water feed streams for PP and ECTFE membrane were similar, the fluxes obtained for the two membranes when using muscadine pomace extracts were different. Concentration factors of close to 3 was obtained for anthocyanins. Membranes also showed slightly different performance in the concentration process. Membrane surfaces were analyzed using scanning electron microscopy and Fourier-transformed infrared spectroscopy. The results suggest that adsorption of these anthocyanins on the membrane surface lead to performance differences. In an actual operation, selection of an appropriate membrane and regeneration of the membrane will be important for optimized performance. PRACTICAL APPLICATIONS: Anthocyanins are valuable therapeutic compounds, which are found in the solid residue left following fruit juice pressing. However, recovery and concentration of these therapeutic compounds remains challenging due to their stability. Here, a novel membrane-based unit operation has been investigated in order to concentrate the anthocyanins that have been extracted into aqueous solutions. The unit operation investigated here use mild processing conditions. Insights into the factors that need to be considered when optimizing of the unit operation for commercialization are discussed.

Surface Oxidation of Ethylenechlorotrifluoroethylene (ECTFE) Membrane for the Treatment of Real Produced Water by Membrane Distillation.

Modification of ethyleneechlorotrifluoroethylene (ECTFE) membranes by simple surface oxidation was reported in the present investigation in order to induce thin hydrophilic layer on hydrophobic membrane surface for the treatment of real produced water (PW). FTIR spectra indicates the appearance of hydrophilic functional groups (⁻OH and ⁻COOH) on the membrane surface due to modification, while water contact angle, zeta potential measurement, EDX, XPS analysis confirmed the presence of O functionalized hydrophilic groups on the surface. The effect of modification temperature and the time of surface oxidation on the performance of the resulting membranes were studied systematically, which revealed that induction of optimized hydrophilicity can successfully reduce the organic fouling. However, too much hydrophilic surface induces polar/electrostatic interaction resulting salt deposition on membrane surface. A simple on site cleaning procedure was demonstrated to be successful for the treatment PW for at least three consecutive cycles of membrane distillation (MD).