Inactivation of Rhizoctonia solani in fertigation water using regenerative in situ electrochemical hypochlorination.

The capture and re-use of greenhouse fertigation water is an efficient use of fertilizer and limited water resources, although the practice is not without risk. Plant pathogens and chemical contaminants can build up over successive capture and re-use cycles; if not properly managed they can lead to reduced productivity or crop loss. There are numerous established and emerging water treatment technologies available to treat fertigation water. Electrochemical processes are emerging as effective means for controlling pathogens via in situ regenerative hypochlorination; a process that is demonstrated here to achieve pathogen control in fertigation solutions without leading to the accumulation of potentially phytotoxic free chlorine residuals associated with other chlorination processes. An electrochemical flow cell (EFC) outfitted with ruthenium dioxide (RuO2) dimensionally stable anodes (DSA) was characterized and evaluated for free chlorine production and Rhizoctonia solani inactivation in both irrigation and fertigation solutions. Pathogen inactivation was achieved at low current densities and short residence or cell contact times. Effluent free chlorine concentrations were significantly lower than commonly reported phytotoxic threshold values (approximately 2.5 mg/L) when fertilizer (containing ammonium) was present in the test solution; an effect attributable to reactions associated with breakpoint chlorination, including chloramine formation, as well as the presence of other oxidizable compounds in the fertilizer. Chloride concentrations were stable under the test conditions suggesting that the EFC was operating as a regenerative in situ electrochemical hypochlorination system. No significant changes to macronutrient concentrations were found following passage through the EFC.

Electrolytic debromination of PBDEs in DE-83 technical decabromodiphenyl ether.

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 in partly aqueous tetrahydrofuran (THF) solution gave lower brominated congeners by sequential loss of bromine atoms. Hydrodebromination was most facile for the most heavily brominated congeners. It involves initial electron transfer and proton transfer from water, rather than hydrogen atom abstraction from THF, as shown by experiments with deuterated water. The product distribution from electrolysis involves preferential loss of bromine meta- and para- to the ether linkage, comparable with the products of metabolism of BDE-209 in various organisms. Significantly, the environmentally relevant congeners BDE-47, BDE-99, and BDE-154 were not major products of debromination of BDE-209 by the electron transfer mechanism.

Catalytic and electrocatalytic hydrogenolysis of brominated diphenyl ethers.

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants due to their use as additive flame-retardants. Conventional catalytic hydrogenolysis in methanol solution and electrocatalytic hydrogenolysis in aqueous methanol were examined as methods for debrominating mono- and di-bromodiphenyl ethers, as well as a commercial penta-PBDE mixture, in each case using palladium on alumina as the catalyst. Electrocatalytic hydrogenolysis employed a divided flow-through batch cell, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes. Both methods gave efficient sequential debromination, with essentially complete removal of bromine from the PBDEs, but the electrocatalytic method was limited by the poor solubility of PBDEs in aqueous methanol.

Electrochemical reduction of hexahydro-1,3,5-trinitro-1,3,5-triazine in aqueous solutions.

Electrochemical reduction of RDX, hexahydro-1,3,5-trinitro-1,3,5-triazine, a commercial and military explosive, was examined as a possible remediation technology for treating RDX-contaminated groundwater. A cascade of divided flow-through cells was used, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes, initially using acetonitrile/water solutions to increase the solubility of RDX. The major degradation pathway involved reduction of RDX to the corresponding mononitroso compound, followed by ring cleavage to yield formaldehyde and methylenedinitramine. The reaction intermediates underwent further reduction and/or hydrolysis, the net result being the complete transformation of RDX to small molecules. The rate of degradation increased with current density, but the current efficiency was highest at low current densities. The technique was extended successfully both to 100% aqueous solutions of RDX and to an undivided electrochemical cell.

Removal of arsenic from synthetic acid mine drainage by electrochemical pH adjustment and coprecipitation with iron hydroxide.

Acid mine drainage (AMD), which is caused by the biological oxidation of sulfidic materials, frequently contains arsenic in the form of arsenite, As(III), and/or arsenate, As(V), along with much higher concentrations of dissolved iron. The present work is directed toward the removal of arsenic from synthetic AMD by raising the pH of the solution by electrochemical reduction of H+ to elemental hydrogen and coprecipitation of arsenic with iron(III) hydroxide, following aeration of the catholyte. Electrolysis was carried out at constant current using two-compartment cells separated with a cation exchange membrane. Four different AMD model systems were studied: Fe(III)/As(V), Fe(III)/As(III), Fe(II)/As(V), and Fe(II)/As(III) with the initial concentrations for Fe(III) 260 mg/L, Fe(II) 300 mg/L, As(V), and As(III) 8 mg/L. Essentially quantitative removal of arsenic and iron was achieved in all four systems, and the results were independent of whether the pH was adjusted electrochemically or by the addition of NaOH. Current efficiencies were approximately 85% when the pH of the effluent was 4-7. Residual concentrations of arsenic were close to the drinking water standard proposed by the World Health Organization (10 microg/L), far below the mine waste effluent standard (500 microg/L).