Geochemical effects on metals following permanganate oxidation of DNAPLs

The application of in situ chemical oxidation for dense, nonaqueous phase liquid (DNAPL) remediation requires delivery of substantial levels of oxidant chemicals into the subsurface to degrade target DNAPLs and to satisfy natural oxidant demand. This practice can raise questions regarding changes in subsurface conditions, yet information regarding potential effects, especially at the field scale, has been lacking. This paper describes an evaluation of the effects on metals associated with in situ chemical oxidation using potassium permanganate at Launch Complex 34 (LC34), Cape Canaveral Air Station, Florida. At LC34, high concentrations of permanganate (1 to 2 wt%) were injected into the subsurface as part of a demonstration of DNAPL remediation technologies. In a companion experimental effort at the Colorado School of Mines, field samples were characterized and laboratory batch and mini-column studies were completed to assess effects of permanganate oxidation on metals in the subsurface one year after completion of the field demonstration. Results indicated there was potential for long-term immobilization of a portion of introduced manganese and no treatment-induced loss in subsurface permeability due to deposition of manganese oxides particles, which are a product of the oxidation reactions. Permanganate treatment did cause elevated manganese, chromium, and nickel concentrations in site ground water within the treated region. Some of these metals effects can be attenuated during downgradient flow through uncontaminated and untreated aquifer sediments.     

Consumers’ knowledge about climate change

Several studies have unveiled various misconceptions about climate change that the public holds, for instance, confusion about climate change and ozone depletion. However, so far, there has been no uniform and standardized way to measure climate-related knowledge, which complicates comparisons between different countries or samples. To develop an extensive knowledge scale, we therefore examined the Swiss public??s understanding of climate change in a mail survey and related this scale to attitudes toward climate change. We thereby aimed to consider a broad range of climate-related knowledge, namely physical knowledge about CO₂ and the greenhouse effect, knowledge about climate change and its causes, knowledge about the expected consequences of climate change, and action-related knowledge. The questionnaire included items of different degrees of difficulty, ranging from knowledge that is covered by newspapers to experts?? knowledge. Our findings indicate that people still hold several misconceptions, although people??s knowledge related to CO₂ seems to have increased compared to previous studies. Of all knowledge subscales, knowledge about climate change and causes was most strongly related to attitudes toward climate change.     

ISCO for Groundwater Remediation: Analysis of Field Applications and Performance

A critical analysis of in situ chemical oxidation (ISCO) projects was performed to characterize situations in which ISCO is being implemented, how design and operating parameters are typically employed, and to determine the performance results being achieved. This research involved design of a database, acquisition and review of ISCO project information, population of the database, and analyses of the database using statistical methods. Based on 242 ISCO projects included in the database, ISCO has been used to treat a variety of contaminants; however, chlorinated solvents are by far the most common. ISCO has been implemented at sites with varied subsurface conditions with vertical injection wells and direct push probes being the most common delivery methods. ISCO has met and maintained concentrations below maximum contaminant levels (MCLs), although not at any sites where dense nonaqueous phase liquids (DNAPL) were presumed to be present. Alternative cleanup levels and mass reduction goals have also been attempted, and these less stringent goals are met with greater frequency than MCLs. The use of pilot testing is beneficial in heterogeneous geologic media, but not so in homogeneous media. ISCO projects cost $220,000 on average, and cost on average $94/yd³ of target treatment zone. ISCO costs vary widely based on the size of the treatment zone, the presence of DNAPL, and the oxidant delivery method. No case studies were encountered in which ISCO resulted in permanent reductions to microbial populations or sustained increases in metal concentrations in groundwater at the ISCO-treated site.     

Fate of tributyltin in sewage sludge treatment

We have shown that municipal wastewater and sewage sludge are contaminated by organotins. Here, we investigate the behaviour and fate of tributyltin (TBT) in laboratory-scale sewage sludge treatment at various conditions including both aerobic and anaerobic, and mesophilic and thermophilic. Organotins were determined by capillary GC-FPD. Fresh raw sewage sludge was stored in a tank that was connected to five chemostats maintained at different conditions. Raw sludge contained TBT, dibutyltin (DBT) and monobutyltin (MBT) residues in the range of 0·28 to 0·83 mg/kg (dry weight). The volumetric TBT concentration was 10·5 μg/litre in the influent, and ranged from 7·4 to 8·3 μg/litre in the effluent of the different chemostats. In the anaerobic mesophilic treatment, concentrations of TBT did not decrease with increasing sludge residence time, DBT increased and MBT showed no clear trend. The DBT increase is suggested to be due to leaching from the PVC walls of the chemostats, and not to degradation of TBT alone. The TBT reduction did not show significant differences between the mesophilic and thermophilic anaerobic fermentors. These findings indicate that the degradation of TBT during sludge treatment is only low under all conditions tested.     

Effects of In Situ Remediation Using Oxidants or Surfactants on Subsurface Organic Matter and Sorption of Trichloroethene

In situ remediation technologies have the potential to alter subsurface properties such as natural organic matter (NOM) content or character, which could affect the organic carbon‐water partitioning behavior of chlorinated organic solvents, including dense nonaqueous phase liquids (DNAPLs). Laboratory experiments were completed to determine the nature and extent of changes in the partitioning behavior of trichloroethene (TCE) caused by in situ chemical oxidation or in situ surfactant flushing. Sandy porous media were obtained from the subsurface at a site in Orlando, Florida. Experiments were run using soil slurries in zero‐headspace reactors (ZHRs) following a factorial design to study the effects of porous media properties (sand vs. loamy sand with different total organic carbon [TOC] contents), TCE concentration (DNAPL presence or absence), and remediation agent type (potassium permanganate vs. activated sodium persulfate, Dowfax 8390 vs. Tween 80). Results revealed that the fraction of organic carbon (f_oc) of porous media after treatment by oxidants or surfactants was higher or lower relative to that in the untreated media controls. Isotherm experiments were run using the treated and control media to measure the distribution coefficient (K_d) of TCE. Organic carbon‐water partitioning coefficient values (K_oc) calculated from the experimental data revealed that K_oc values for TCE in the porous media were altered via treatment using oxidants and surfactants. This alteration can affect the validity of estimates of contaminant mass remaining after remediation. Thus, potential changes in partitioning behavior should be considered to help avoid decision errors when judging the effectiveness of an in situ remediation technology.     

Model parameters for simulating fate and transport of on-site wastewater nutrients

This paper presents a critical review of model-input parameters for transport of on-site wastewater treatment system (OWS) pollutants. Approximately 25% of the U.S. population relies on soil-based OWS for effective treatment and protection of public health and environmental quality. Mathematical models are useful tools for understanding and predicting the transport and fate of wastewater pollutants and for addressing water-budget issues related to wastewater reclamation from site to watershed scales. However, input parameters for models that simulate fate and transport of OWS pollutants are not readily obtained. The purpose of this analysis is to illustrate an objective, statistically supported method for choosing model-input parameters related to nitrogen (N) and phosphorus (P). Data were gathered from existing studies reported in the literature. Cumulative frequency distributions (CFDs) are provided for OWS effluent concentrations of N and P, nitrification and denitrification rates, and linear sorption isotherm constants for P. When CFDs are not presented, ranges and median values are provided. Median values for model-input parameters are as follows: total N concentration (44 mg/L), nitrate-N (0.2 mg/L), ammonium (60 mg/L), phosphate-P (9 mg/L), organic N (14 mg/L), zero-order nitrification rate (264 mg/L/d), first-order nitrification (2.9/d), first-order dentrification (0.025/d), maximum soil capacity for P uptake (237 mg/kg), linear sorption isotherm constant for P (15.1 L/kg), and OWS effluent flow rates (260 L/person/d).