Enhanced semi-volatile DNAPL accessibility at sub-boiling temperature during electrical resistance heating in heterogeneous porous media.

Successful remediation of semi-volatile contaminants using electrical resistance heating (ERH) coupled technologies requires a deep understanding of contaminant migration and accessibility, especially with stratigraphic heterogeneity and dense nonaqueous phase liquid (DNAPL) occurrence. Here, we chose nitrobenzene (NB) as a model contaminant of semi-volatile DNAPL and uniquely demonstrated that temperature variation during ERH could induce NB DNAPL migration out of the low permeability zone (LPZ) even below water boiling temperature. When heating the system using alternating current (AC) of 140 V to a temperature range of 50-79 °C, obvious DNAPL migration was visually observed. The upward migration of DNAPL would considerably increase the mass of accessible contaminant by other remediation measures. The downstream cumulative NB mass of 1092 mg in 140 V system raised 56-folds compared to that of 19 mg in the control experiment with only groundwater flow. This migration was mainly attributed to a complex natural convection caused by temperature gradient. Comparing with traditional AC heating, ERH powered by pulsed direct current (PDC-ERH) showed a higher and more uneven heating pattern, resulting in a stronger convection at the same voltage that enhanced the DNAPL migration out of LPZ. These results revealed the importance of natural convection in the ERH process, which could be further optimized to improve the energy efficiency of remediation.

Enhancing DNAPL removal from low permeability zone using electrical resistance heating with pulsed direct current.

Electrical resistance heating (ERH) has been widely applied for contaminant remediation in heterogeneous sites especially when low permeability zones exist, yet requires high energy input. To address the low energy-efficiency of ERH using conventional alternating current (AC), pulsed direct current (PDC) obtained by current rectification was introduced for heating to enhance dense nonaqueous phase liquid (DNAPL) migration in low permeability zones. Here we showed the proof-of-concept in a lab-scale two-dimensional heterogeneous sand system (40 cm × 30 cm) with trichloroethylene (TCE) DNAPL in the central low permeability zone. Applying PDC achieved faster temperature increase compared to that with the conventional AC of the same voltage gradient. The overall TCE removal efficiency from the cell increased from 79.0% to 89.6% with increasing PDC voltage gradient from 3 to 3.75 V cm-1, compared to that of 9.4-91.1% with conventional AC. The lowest energy consumption of PDC was 390 kWh kg-1 at a medium voltage gradient of 3.5 V cm-1, which was 27.8% lower compared to that with AC at the same voltage gradient. These results suggest that remediation using pulsed direct current is a promising approach to improve the energy-efficiency and effectiveness of ERH.

Significantly enhanced base activation of peroxymonosulfate by polyphosphates: Kinetics and mechanism.

Base activation of peroxydisulfate (PDS) is a common process aiming for water treatment, but requires high doses of PDS and strongly basic solutions. Peroxymonosulfate (PMS), another peroxygen of sulfurate derived from PDS, may also be activated by a less basic solution. However, enhancing the base-PMS reactivity is still challenging. Here it is reported that pyrophosphate (PA) and tripolyphosphate (PB) can efficiently enhance PMS activation under weakly alkaline conditions (pH 9.5) via the formation of superoxide anion radical (O2•-) and singlet oxygen (1O2). The rate constant of Acid Orange 7 (AO7) degradation in PA/PMS system (kPA/PMS) was nearly 4.4-15.9 fold higher than that in PMS/base system (kPMS/base) without any polyphosphates. Increases in PA (or PB) concentration, PMS dose and pH favored the rapid dye degradation. Gas chromatograph-mass spectrometer (GC-MS) data confirmed AO7 and 2,4,6-trichlorophenol (2,4,6-TCP) were decomposed to a series of organic intermediates. The radical quenching and probe oxidation experiments indicate the degradation of organic compounds in the PA/PMS and PB/PMS processes was not reliant on sulfate radical (SO4•-) and hydroxyl radical (OH) species but on O2- and 1O2 reactive species. Comparison experiments show that the polyphosphate/PMS process was much more favorable than PDS/base process. The present work provides a novel way to activate PMS for contaminant removal using industrial polyphosphate wastewaters.