The influence of precipitate formation on the chemical oxidation of TCE DNAPL with potassium permanganate

A three-dimensional two-phase flow model is coupled to a non-linear reactive transport model to study the efficacy of potassium permanganate treatment on dense, non-aqueous phase liquid (DNAPL) source removal in porous media. A linear relationship between the soil permeability (k) and concentration of manganese dioxide precipitate ([MnO_2(s)]), k = k_o + S_rind [MnO_2(s)], is utilized to simulate nodal permeability reductions due to precipitate formation. Using published experimental column studies, an S_rind = −5.5 × 10⁻¹⁶ m² L/mg was determined for trichloroethylene (TCE) DNAPL. This S_rind was then applied to treatment simulations on three-dimensional TCE DNAPL source zones comprising either DNAPL at residual saturations, or DNAPL at pooled saturations.     

Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons

Atmospheric hydroxyl (OH), hydroperoxy (HO₂), total peroxy (HO₂ and organic peroxy radicals, RO₂) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO₂ mixing ratios were measured with laser induced fluorescence (LIF); HO₂ + RO₂ mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO₂, and 45 pptv for HO₂ + RO₂. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO₂ and HO₂ + RO₂ concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO₂ + NO → OH + NO₂, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO₂ is 1.0 on average, although daytime HO₂ is underpredicted by a factor of 1.2 and nighttime HO₂ is over-predicted by a factor of ∼2. The average measured and modeled HO₂ + RO₂ agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO₂ + RO₂ values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO₂ + RO₂ with the CIMS technique confirms the observed increase of HO₂ above expected values at higher NO mixing ratios in HO₂ measurements with the LIF technique. The maximum instantaneous O₃ production rate calculated from HO₂ and RO₂ reactions with NO was as high as 10–15 ppb h⁻¹ at midday; the total daily O₃ production varied from 13 to 113 ppbv d⁻¹ and was 48 ppbv d⁻¹ on average during this campaign.     

Book reviews

Theory and management of tropical fisheries. Edited by D. Pauly and G. I. Murphy. Proceedings of the ICLARM/CSIRO Workshop on the Theory and Management of Tropical Multispecies Stocks. 12–21 January 1981, Cronulla, Australia. 1982. 360 p. $US21.50 surface; hardbound.

Animals of the estuary shore : illustrated guide and ecology. By Malcolm B. Jones, 1983. University of Canterbury publication No. 32. 162p., 140 figures, 11 keys. ISBN 0900–392–32–0 (soft cover, spiral bound). Price NZ$7.50.

Numerical ecology. By L. Legendre and P. Legendre, 1983. Elsevier Scientific Publishing Company, Amsterdam. $US83.00.

The control of oil pollution (revised edition). Edited by J Wardley‐Smith. Graham & Trot‐man Limited, London. 1983. 285 p., 98 figures, 17 tables. ISBN 0.86010 3382. £19.00/$US35.00.

Physical oceanography in Australia. Edited by J. Imberger. Reprinted from the Australian Journal of Marine and Freshwater Research, Volume 34, 1–230, 1983. CSIRO, Melbourne 1983.