Citrate Addition Increased Phosphorus Bioavailability and Enhanced Gasoline Bioremediation

Phosphorus (P) bioavailability often limits gasoline biodegradation in calcareous cold-region soils. One possible method to increase P bioavailability in such soils is the addition of citrate. Citrate addition at the field scale may increase hydrocarbon degradation by: (i) enhancing inorganic and organic P dissolution and desorption, (ii) increasing hydrocarbon bioavailability, and/or (iii) stimulating microbial activity. Alternatively, citrate addition may inhibit activity due to competitive effects on carbon metabolism. Using a field-scale in situ biostimulation study, we evaluated if citrate could stimulate gasoline degradation and what the dominant mechanism of this stimulation will be. Two large bore injectors were constructed at a site contaminated with gasoline, and a biostimulation solution of 11 mM MgSO4, 1 mM H3PO4, and 0.08 mM HNO3 at pH 6.5 in municipal potable water was injected at similar to 5000 L d(-1) for about 4 mo. Following this, 10 mM citric acid was incorporated into the existing biostimulation solution and the site continued to be stimulated for 8 mo. After citrate addition, the bioavailable P fraction in groundwater and soil increased. Iron(II) groundwater concentrations increased and corresponded to decreases in benzene, toluene, ethylbenzene, xylenes (BTEX) in groundwater, as well as a decrease in F1(-BTEX) in the soil saturated zone. Overall, citrate addition increased P bioavailability and may stimulate anaerobic microbial activity, resulting in accelerated anaerobic gasoline bioremediation in cold-region calcareous soils.