Seasonal Impact of Phosphate-Based Fire Retardants on Soil Chemistry Following the Prophylactic Treatment of Vegetation.

A preventative treatment of fire retardants at high-risk locales can potentially stop a majority of wildfires. For example, over 80% of wildfire ignitions in California occur at high-risk locales such as adjacent to roadsides and utility infrastructure. Recently a new class of ammonium polyphosphate retardants was developed with enhanced adherence and retention on vegetation to enable prophylactic treatments of these high-risk locals to provide season-long prevention of ignitions. Here, we compare three different ammonium (poly)phosphate-based wildland retardant formulations and evaluate their resistance to weathering and analyze their seasonal impact on soil chemistry following application onto grass. Soil samples from all three treatments demonstrated no changes in soil pH and total soil carbon and nitrogen amounts. Total soil phosphorus amounts increased by ∼2-3× following early precipitation, always remaining within typical topsoil amounts, and returned to the same level as control soil before spring. Available indices of ammonium, nitrate, and phosphate levels for all groups were elevated compared to the untreated control samples, again remaining within typical topsoil ranges across all time points and rainfall amounts evaluated. Microbial activity was decreased, potentially because the addition of available nutrients from retardant application reduced the need for organic decomposition. These results demonstrate that the application of ammonium (poly)phosphate-based retardants does not alter soil chemistry beyond typical topsoil compositions and are thus suitable for use in prophylactic wildfire prevention strategies.

Impacts of phosphorus amendments on legacy soil contamination from lead-based paint on a California, USA university campus.

Lead (Pb) is one of the most common heavy metal urban soil contaminants with well-known toxicity to humans. This incubation study (2-159 d) compared the ability of bone meal (BM), potassium hydrogen phosphate (KP), and triple superphosphate (TSP), at phosphorus:lead (P:Pb) molar ratios of 7.5:1, 15:1, and 22.5:1, to reduce bioaccessible Pb in soil contaminated by Pb-based paint relative to control soil to which no P amendment was added. Soil pH and Mehlich 3 bioaccessible Pb and P were measured as a function of incubation time and amount and type of P amendment. XAS assessed Pb speciation after 30 and 159 d of incubation. The greatest reductions in bioaccessible Pb at 159 d were measured for TSP at the 7.5:1 and 15:1 P:Pb molar ratios. The 7.5:1 KP treatment was the only other treatment with significant reductions in bioaccessible Pb compared to the control soil. It is unclear why greater reductions of bioaccessible Pb occurred with lower P additions, but it strongly suggests that the amount of P added was not a controlling factor in reducing bioaccessible Pb. This was further supported because Pb-phosphates were not detected in any samples using XAS. The most notable difference in the effect of TSP versus other amendments was the reduction in pH. However, the relationship between increasing TSP additions, resulting in decreasing pH and decreasing Pb bioaccessibility was not consistent. The 22.5:1 P:Pb TSP treatment had the lowest pH but did not significantly reduce bioaccessible Pb compared to the control soil. The 7.5:1 and 15:1 P:Pb TSP treatments significantly reduced bioaccessible Pb relative to the control and had significantly higher pH than the 22.5:1 P:Pb treatment. Clearly, impacts of P additions and soil pH on Pb bioaccessibility require further investigation to decipher mechanisms governing Pb speciation in Pb-based paint contaminated soils.

Sequential sorption of lead and cadmium in three tropical soils.

It is important to examine mechanisms of Pb and Cd sorption in soils to understand their bioavailability. The ability of three tropical soils to retain Pb, Cd, and Ca was evaluated. The objectives of this study were to (1) determine the extent to which soil sorption sites are metal specific, (2) investigate the nature of reactions between metals and soil surfaces, and (3) identify how metals compete for sorption sites when they are introduced to soils sequentially or concurrently. Lead was shown to be much less exchangeable than Cd and inhibited Cd sorption. Cadmium had little effect on Pb sorption, though both Ca and Cd inhibited the adsorption of Pb at exchange sites. Lead appears to more readily undergo inner-sphere surface complexation with soil surface functional groups than either Cd or Ca. Thus, regardless of when Pb is introduced to a soil, it should be less labile than Cd.

Mechanisms of lead, copper, and zinc retention by phosphate rock.

The solid-liquid interface reaction between phosphate rock (PR) and metals (Pb, Cu, and Zn) was studied. Phosphate rock has the highest affinity for Pb, followed by Cu and Zn, with sorption capacities of 138, 114, and 83.2 mmol/kg PR, respectively. In the Pb-Cu-Zn ternary system, competitive metal sorption occurred with sorption capacity reduction of 15.2%, 48.3%, and 75.6% for Pb, Cu, and Zn, respectively compared to the mono-metal systems. A fractional factorial design showed the interfering effect in the order of Pb>Cu>Zn. Desorption of Cu and Zn was sensitive to pH change, increasing with pH decline, whereas Pb desorption was decreased with a strongly acidic TCLP extracting solution (pH = 2.93). The greatest stability of Pb retention by PR can be attributed to the formation of insoluble fluoropyromorphite [Pb(10)(PO(4))(6)F(2)], which was primarily responsible for Pb immobilization (up to 78.3%), with less contribution from the surface adsorption or complexation (21.7%), compared to 74.5% for Cu and 95.7% for Zn. Solution pH reduction during metal retention and flow calorimetry analysis both supported the hypothesis of retention of Pb, Cu, and Zn by surface adsorption or complexation. Flow calorimetry indicated that Pb and Cu adsorption onto PR was exothermic, while Zn sorption was endothermic. Our research demonstrated that PR can effectively remove Pb from solutions, even in the presence of other heavy metals (e.g. Cu, Zn).

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils.

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.