The poly(methacrylic acid) (PMAA) was synthesized in the pores of commercial microfiltration PVDF membranes to allow incorporation of catalytic palladium/iron (Pd/Fe) nanoparticles for groundwater remediation. Particles of 17.1 ± 4.9 nm size were observed throughout the pores of membranes using a focused ion beam. To understand the role of Pd fractions and particle compositions, 2-chlorobiphenyl was used as a model compound in solution phase studies. Results show H 2 production (Fe 0 corrosion in water) is a function of Pd coverage on the Fe. Insufficient H 2 production caused by higher coverage (> 10.4% for 5.5 wt%) hindered dechlorination rate. With 0.5 wt% Pd, palladized-Fe reaction rate (surface area normalized reaction rate, k sa = 0.12 L/(m 2-h) was considerably higher than isolated Pd and Fe particles. For groundwater, in a single pass of Pd/Fe-PMAA-PVDF membranes (0.5 wt% Pd), chlorinated organics, such as trichloroethylene (177 ppb) and carbon tetrachloride (35 ppb), were degraded to 16 and 0.3 ppb, respectively, at 2.2 seconds of residence time. The degradation rate (observed k sa) followed the order of carbon tetrachloride > trichloroethylene > tetrachloroethylene > chloroform. A 36 h continuous flow study with organic mixture and the regeneration process show the potential for on-site remediation.
Sulfate reducing conditions are widely observed in groundwater plumes associated with petroleum hydrocarbon releases. This leads to sulfate depletion in groundwater which can limit biodegradation of hydrocarbons (usually benzene, toluene, ethylbenzene, xylenes [ BTEX ] compounds) and can therefore result in extended timeframes to achieve groundwater cleanup objectives by monitored natural attenuation. Under these conditions, sulfate addition to the subsurface can potentially enhance BTEX biodegradation and facilitate enhanced natural attenuation. However, a delivery approach that enables effective contact with the hydrocarbons and is able to sustain elevated and uniform sulfate concentrations in groundwater remains a key challenge. In this case study, sulfate addition to a groundwater plume containing predominantly benzene by land application of agricultural gypsum and Epsom salt is described. Over 4 years of groundwater monitoring data from key wells subjected to pilot-scale and site-wide land application events are presented. These are compared to data from pilot testing employing liquid Epsom salt injections as an alternate sulfate delivery approach. Sulfate land application, sulfate retention within the vadose zone, and periodic infi ltration following ongoing precipitation events resulted in elevated sulfate concentrations (>150 mg/L) in groundwater that were sustained over 12 months between application events and stimulated benzene biodegradation as indicated by declines in dissolved benzene concentration, and compound-specifi c isotope analysis data for carbon in benzene. Long-term groundwater benzene concentration reductions were achieved in spite of periodic rebounds resulting from water table fl uctuations across the smear zone. Land application of gypsum is a potentially cost-effective sulfate delivery approach at sites with open, unpaved surfaces, relatively permeable geology, and shallow hydrocarbon impacts. However, more research is needed to understand the fate and persistence of sulfate and to improve the likelihood of success and effectiveness of this delivery approach.
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