Smart Characterization—An Integrated Approach for Evaluating a Complex 1,4‐Dioxane Site

Smart characterization approaches apply the latest high‐resolution site characterization methods to find the contaminant mass flux, by integrating relative permeability mapping, classical hydrostratigraphy interpretation, and high‐density groundwater and saturated soil sampling. The key factor that makes Smart characterization different is the application of quantitative saturated soil sampling in less permeable slow advection and storage zones to diagnose plume maturity and understand its implications for remedy selection and performance. Because direct sensing tools like the membrane interface probe are capable of providing screening‐level assessments for hydrocarbons and chlorinated solvents in storage zones, but not 1,4‐dioxane, the recommended Smart approach involves application of specialized high‐capacity mobile laboratories or rapid turn‐around using fixed commercial labs. In addition to the benefit of rapidly characterizing sites, Smart characterization facilitates a flux‐based conceptual site model, which allows stakeholders to focus remedies on the mobile portion of the contaminant mass or, in effect, the mass that matters. Through systematic planning and implementation, predesign characterization can be completed to optimize source and plume remedy strategies, balancing investment in Smart characterization with reductions in total life‐cycle costs to ensure that an appropriate return on investigation is obtained.  © 2016 Wiley Periodicals, Inc.     

Assessing the extent and nature of wildlife trade on the dark web

Use of the internet as a trade platform has resulted in a shift in the illegal wildlife trade. Increased scrutiny of illegal wildlife trade has led to concerns that online trade of wildlife will move onto the dark web. To provide a baseline of illegal wildlife trade on the dark web, we downloaded and archived 9852 items (individual posts) from the dark web, then searched these based on a list of 121 keywords associated with illegal online wildlife trade, including 30 keywords associated with illegally traded elephant ivory on the surface web. Results were compared with items known to be illegally traded on the dark web, specifically cannabis, cocaine, and heroin, to compare the extent of the trade. Of these 121 keywords, 4 resulted in hits, of which only one was potentially linked to illegal wildlife trade. This sole case was the sale and discussion of Echinopsis pachanoi (San Pedro cactus), which has hallucinogenic properties. This negligible level of activity related to the illegal trade of wildlife on the dark web relative to the open and increasing trade on the surface web may indicate a lack of successful enforcement against illegal wildlife trade on the surface web.     

Isothermal Oxidation of White Phosphorus Dispersed in Water in a Stirred-Tank Reactor

ABSTRACT

A global, first-order kinetic model was found to fit the data for the isothermal wet oxidation of elemental white phosphorus (P₄) in a batch, stirred-tank reactor. The initial concentration of white phosphorus solids was held constant at 1 g/L and an air flow of 2.0 standard liters per minute was used to supply the oxygen for the reaction. A CD6-like turbine and an A2 impeller were evaluated at speeds from 1000-2250 rpm. For the CD6-like turbine, mass transfer effects were assumed to be eliminated above 2000 rpm. Thus, the CD6-like turbine with a speed of 2250 rpm was selected for the isothermal studies. Particle size and temperature were varied. For the isothermal conditions, the first order kinetic constant varied from 0.022 min^-1 at 46 °C to 0.078 min^-1 at 80 °C. The apparent activation energy was 6.78 kcal/mol. Oxygen reacted with the suspended P₄ particles forming oxides of phosphorus, primarily phosphorus pentoxide (P₄0₁₀ or P₂ O₅). Some of the P₂O₅ reacted with the water to form PO₄ ^3- as the primary product of white phosphorus oxidation. The amount of phosphorus pentoxide absorbed in the water increased with temperature. The rate of phosphate formation followed zero order kinetics and was independent of particle size. As the temperature increased, the ratio of PO₄/ PO₃ increased. This observation and the apparently low activation energy suggest that diffusion effects may not have been eliminated completely.     

A comparative evaluation of the performance of full-scale high-rate methane biofilter (HMBF) systems and flow-through laboratory columns

Methane biofilter (MBF) technology, a cost effective method to control atmospheric emission of CH₄, is usually developed as a passively aerated system to control low-volume point-source emissions such as those from landfills with gas collection systems. Actively aerated high-rate methane biofilter (HMBF) systems are designed to overcome the shortcomings of passively aerated systems by ensuring the entire filter bed is utilized for CH₄ oxidation. Flow-through column experiments point to the fact that CH₄ oxidation rates of actively aerated systems could be several times higher than that of passively aerated systems. However, reports of the performance of field HMBF systems are not available in literature. Furthermore, there are no studies that demonstrate the possibility of using laboratory data in the design and operation of field systems. The current study was conducted to fill this research gap and involve a comparative study of the performance of laboratory columns to field performance of a HMBF system using solution gas produced at an oil battery site as the CH₄ source. The actively aerated column studies confirmed past results with high CH₄ oxidation rates; one column received air at two injection points and achieved an oxidation rate of 1417 g/m³/d, which is the highest reported value to date for compost-filled columns. Subsequent studies at a specially designed field HMBF filled with compost showed a higher oxidation rate of 1919 g/m³/d, indicating the possibility of exceeding the high CH₄ oxidation rates observed in the laboratory. The achievement of observed field oxidation rates being higher than those in the laboratory is attributed to the capability of maintaining higher temperatures in field HMBFs. Furthermore, results show that field HMBFs could operate at lower than stoichiometric air to CH₄ ratios, and lower retention times than that of laboratory columns. Results indicated that laboratory columns may not truly represent field behavior, and said results could only be used in the preliminary design of field HMBFs.     

Errors in representing regional acid deposition with spatially sparse monitoring: Case studies of the eastern US using model predictions

The current study uses case studies of model-predicted regional precipitation and wet ion deposition over 5-year periods to estimate errors in corresponding regional values derived from the means of site-specific values within regions of interest located in the eastern US. The mean of model-predicted site-specific values for sites within each region was found generally to overestimate the corresponding model-predicted regional wet ion deposition. On an annual basis across four regions in the eastern US, these overestimates of regional wet ion deposition were typically between 5 and 25% and may be more exaggerated for individual seasons. Corresponding overestimates of regional precipitation were typically <5%, but may be more exaggerated for individual seasons. Period-to-period relative changes determined from the mean of site-based model-predicted wet deposition for the current regional ensembles of sites generally estimated larger beneficial effects of pollutant emissions reductions in comparison to changes based on model-predicted regional wet deposition. On an annual basis site-based relative changes were generally biased low compared to regional relative changes: differences were typically <7%, but they may also be more exaggerated for individual seasons. Spatial heterogeneities of the wet ion deposition fields with respect to the sparse monitoring site locations prevented the monitoring sites considered in the current study from providing regionally representative results. Monitoring site locations considered in the current study over-represent the geographical areas subject to both high emissions and high wet ion deposition and under-represent the geographical areas subject to low emissions and low wet deposition. Since the current case studies consider only those eastern US site locations that have supported concurrent wet and dry deposition monitoring, similar errors may be expected for dry and total deposition using results from the same monitoring site locations. Current case study results illustrate the approximate range of potential errors and suggest caution when inferring regional acid deposition from a network of sparse monitoring sites.