Pb speciation versus TCLP release in army firing range soils.

A series of soil parameter and mineralogical investigative techniques were applied to assess the Pb speciation in four US Army firing range soils that presented significantly different Pb leaching regimes and soil characteristics. Soil gradation tests were complemented by total chemical analyses, X-ray powder diffraction (XRPD), Rietveld quantification, optical microscopy and scanning electron microscopy (SEM) analyses. The bulk geotechnical, mineralogical and chemical analyses pointed to two possible Pb retention mechanisms: precipitation as lead carbonate and sorption in the case of fine-grained soils. Lead speciation and mobility was further investigated by the toxicity characteristic leaching procedure (TCLP) and sequential extraction test (SET). As the TCLP Pb concentrations did not necessarily reflect the total Pb analysis of the soils, the Pb leachability ratio (TCLP/total) was found to be controlled by soil mineralogy and its response to changes in system pH. Geochemical modeling, using Visual MINTEQ, was employed to evaluate the mechanisms that controlled the observed TCLP Pb leaching behavior. It was found that lead carbonate precipitation/dissolution reactions controlled Pb TCLP leachability in all soils, while sorptive phenomena did not seem to play a role even in the case of fine-grained soils. More specifically, TCLP Pb leachability was controlled by the pH, the available Pb and the available carbonate in solution. This indicates that geochemical modeling strongly complimented TCLP Pb analyses. Thus, geochemical modeling is an important assessment tool to evaluate the magnitude of site-specific Pb-related environmental problems in firing range soils. Carbonation reactions, involving metallic Pb, that occur during the SET obscure its ability to reliably ascertain Pb speciation. More specifically, SET lumps the extractable Pb into predetermined phase categories that may not be truly representative of the actual soil mineralogy or dominant forms of Pb in the soil. A thorough geotechnical, mineralogical and chemical investigation of firing range soils, complemented by geochemical modeling, was therefore found to be a more reliable approach to evaluate Pb speciation and TCLP release in firing range soils.

Recovery of dodecane, octane and toluene spills in sandpacks using ethanol.

This paper is an extension of the work of Grubb et al. on the recovery of lighter-than-water non aqueous phase liquids (LNAPLs) from sandpacks. Dodecane, toluene and octane (500 mL each) were used to simulate fresh and weathered petroleum spills. The ethanol flooding experiments evaluated the feasibility of recovering the LNAPLs from unconfined uniform sandpacks in a quasi two-dimensional apparatus. A combined pure ethanol and 50/50 (vol.%) ethanol-water blend flooding strategy successfully mobilized and recovered the simulated large-volume LNAPL spills (10x greater than previous studies). At flow rates < 7 m per day, the toluene and octane recoveries were approximately 84.9 and 88.1%, respectively, which are considered impressive as no optimization was even attempted.

Phosphate immobilization using an acidic type F fly ash.

Batch equilibration experiments using a low calcium ( approximately 1 wt.% as CaO), acidic (pH approximately 4.5) Type F fly ash demonstrated phosphate immobilization on the order of 100% to 75% for 50 and 100 mg P/l solutions, respectively. A loosely compacted column of fly ash similarly removed 10 mg P/l for over 85 pore volumes. While the interactions between phosphate and calcium-rich (Type C) ashes are relatively well understood, insight into the mechanisms of phosphate immobilization in Type F ash necessitated a review of the phosphate chemistry and interactions with acidic geomedia. Phosphate adsorption was subsequently modeled using a constant capacitance model approach (CCM) excluding precipitation reactions. Our CCM predictions of total phosphate immobilization (20%) were substantially less than the results of the batch equilibration experiments and phosphate adsorption predicted by other researchers examining near pure natural and synthetic geomedia due to the compositional heterogeneity of the fly ash. Nevertheless, for the amorphous and crystalline phases studied, the immobilization of phosphate in the Type F fly ash is attributed to the formation of insoluble aluminum and iron phosphates at low to medium values of pH.

Technologies for in situ cleanup of contaminated sites.

Groundwater contamination by non-aqueous phase liquids (NAPLs) and denser than water non-aqueous phase liquids (DNAPLs) poses one of the greatest remedial challenges in the field of environmental engineering. Due to low water solubilities and aqueous diffusivities, conventional pump-and-treat technologies have a poor record of success in remediation of DNAPL contaminated aquifers. Better success has been found with the removal of volatile LNAPLs due to higher gaseous diffusivities, propensity for aerobic biodegradation, and ease of pumping and handling large quantities of gas. An evaluation of in situ cleanup technologies on the basis of their applicability to in situ treatment of NAPL contaminated aquifers is presented. Emphasis is placed on treatment of the separate phase occurring in the saturated zone. Soil washing, air sparging, biodegradation, electro-osmosis, enhanced steam extraction, stabilization/solidification, treatment walls, radio frequency heating, and containment systems and barriers are among the in situ technologies reviewed. In the context of the governing contaminant fate and transport processes, the relative merits of each technology are assessed on the basis of its theoretical background, field implementability, level of demonstration and performance, waste, technical and site applicability/limitations, commercial availability, and cost and residuals management.