Hydrogen peroxide stabilization in one-dimensional flow columns

Rapid hydrogen peroxide decomposition is the primary limitation of catalyzed H(2)O(2) propagations in situ chemical oxidation (CHP ISCO) remediation of the subsurface. Two stabilizers of hydrogen peroxide, citrate and phytate, were investigated for their effectiveness in one-dimensional columns of iron oxide-coated and manganese oxide-coated sand. Hydrogen peroxide (5%) with and without 25 mM citrate or phytate was applied to the columns and samples were collected at 8 ports spaced 13 cm apart. Citrate was not an effective stabilizer for hydrogen peroxide in iron-coated sand; however, phytate was highly effective, increasing hydrogen peroxide residuals two orders of magnitude over unstabilized hydrogen peroxide. Both citrate and phytate were effective stabilizers for manganese-coated sand, increasing hydrogen peroxide residuals by four-fold over unstabilized hydrogen peroxide. Phytate and citrate did not degrade and were not retarded in the sand columns; furthermore, the addition of the stabilizers increased column flow rates relative to unstabilized columns. These results demonstrate that citrate and phytate are effective stabilizers of hydrogen peroxide under the dynamic conditions of one-dimensional columns, and suggest that citrate and phytate can be added to hydrogen peroxide before injection to the subsurface as an effective means for increasing the radius of influence of CHP ISCO.     

Comparative assessment of municipal wastewater disposal methods in southeast Florida.

A comparative assessment of the risks of three effluent disposal alternatives currently available to wastewater utilities in Southeast Florida is presented in this paper. The alternatives are: deep well injection and ocean outfalls following secondary treatment, and surface water (canal) discharges following secondary wastewater treatment, filtration and nutrient removal. Water quality data, relative to disposal of wastewater treatment plant effluent were gathered, along with water quality data on the receiving waters, from utilities. Comparisons and conclusions regarding potential health concerns associated with the three disposal alternatives are presented. The results indicated that health risks associated with deep wells were generally lower than those of the other two alternatives. The proximity of injection wells to aquifer storage and recovery wells was a determining factor relative to injection well risk. Urban ecological risks were also indicated to be lower, though impacts of urban water use/reuse to the Everglades were not studied. Additional data collection and analysis were recommended to understand the effects of wastewater management on the cycling of water, nutrients and other constituents on southeast Florida. In particular, it was recommended that monitoring of effluents for nitrosamines and pharmaceutically active substances be implemented on a broad scale.     

Characterization of microbial communities from coastal waters using microarrays

Molecular methods, including DNA probes, were used to identify and enumerate pathogenic Vibrio species in the Chesapeake Bay; our data indicated that Vibrio vulnificus exhibits seasonal fluctuations in number. Our work included a characterization of total microbial communities from the Bay; development of microarrays that identify and quantify the diversity of those communities; and observation of temporal changes in those communities. To identify members of the microbial community, we amplified the 16S rDNA gene from community DNA isolated from a biofilm sample collected from the Chesapeake Bay in February, 2000. The resultant 75 sequences were 95% or more similar to 7 species including two recently described Shewanella species, baltica and frigidimarina, that have not been previously isolated from the Chesapeake. When the genera of bacteria from biofilm after culturing are compared to those detected by subcloning amplified 16S fragments from community DNA, the cultured sample exhibited a strong bias. In oysters collected in February, the most common bacteria were previously unknown. Based on our 16S findings, we are developing microarrays to detect these and other microbial species in these estuarine communities. The microarrays will detect each species using four distinct loci, with the multiple loci serving as an internal control. The accuracy of the microarray will be measured using sentinel species such as Aeromonas species, Escherichia coli, and Vibrio vulnificus. Using microarrays, it should be possible to determine the annual fluctuations of bacterial species (culturable and non-culturable, pathogenic and non-pathogenic). The data may be applied to understanding patterns of environmental change; assessing the health of the Bay; and evaluating the risk of human illness associated with exposure to and ingestion of water and shellfish.     

Preparation, certification and interlaboratory analysis of workplace air filters spiked with high-fired beryllium oxide

Occupational sampling and analysis for multiple elements is generally approached using various approved methods from authoritative government sources such as the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), as well as consensus standards bodies such as ASTM International. The constituents of a sample can exist as unidentified compounds requiring sample preparation to be chosen appropriately, as in the case of beryllium in the form of beryllium oxide (BeO). An interlaboratory study was performed to collect analytical data from volunteer laboratories to examine the effectiveness of methods currently in use for preparation and analysis of samples containing calcined BeO powder. NIST SRM(?) 1877 high-fired BeO powder (1100 to 1200 °C calcining temperature; count median primary particle diameter 0.12 μm) was used to spike air filter media as a representative form of beryllium particulate matter present in workplace sampling that is known to be resistant to dissolution. The BeO powder standard reference material was gravimetrically prepared in a suspension and deposited onto 37 mm mixed cellulose ester air filters at five different levels between 0.5 μg and 25 μg of Be (as BeO). Sample sets consisting of five BeO-spiked filters (in duplicate) and two blank filters, for a total of twelve unique air filter samples per set, were submitted as blind samples to each of 27 participating laboratories. Participants were instructed to follow their current process for sample preparation and utilize their normal analytical methods for processing samples containing substances of this nature. Laboratories using more than one sample preparation and analysis method were provided with more than one sample set. Results from 34 data sets ultimately received from the 27 volunteer laboratories were subjected to applicable statistical analyses. The observed performance data show that sample preparations using nitric acid alone, or combinations of nitric and hydrochloric acids, are not effective for complete extraction of Be from the SRM 1877 refractory BeO particulate matter spiked on air filters; but that effective recovery can be achieved by using sample preparation procedures utilizing either sulfuric or hydrofluoric acid, or by using methodologies involving ammonium bifluoride with heating. Laboratories responsible for quantitative determination of Be in workplace samples that may contain high-fired BeO should use quality assurance schemes that include BeO-spiked sampling media, rather than solely media spiked with soluble Be compounds, and should ensure that methods capable of quantitative digestion of Be from the actual material present are used.     

Alternative carbon dioxide modelling approaches accounting for high residual gases in LandGEM

High Canadian waste disposal rates necessitate landfill gas monitoring and accurate forecasting. CO₂ estimates in LandGEM version 3.02 currently rest on the assumptions that CO₂ is a function of CH₄, where the two gases make up nearly 100% of landfill gas content, leading to overestimated CO₂ collection estimates. A total of 25 cases (five formulas, five approaches) compared annual CO₂ collection at four western Canadian landfills. Despite common use in literature, the 1:1 ratio of CH₄ to CO₂ was not recommended to forecast landfill gas collection in cold climates. The existing modelling approach significantly overestimated CO₂ production in three of four sites, resulting in the highest residual sum of squares. Optimization resulted in the most accurate results for all formulas and approaches, which had the greatest reduction in residual sums of squares (RSS) over the default approach (60.1 to 97.7%). The 1.4 Ratio approach for L _o:L _o-CO2 yielded the second most accurate results for CO₂ flow (mean RSS reduction of 50.2% for all sites and subsection models). The annual k-modified LandGEM calculated k’s via two empirical formulas (based on precipitation) and yielded the lowest accuracy in 12 of 20 approaches. Unlike other studies, strong relationships between optimized annual k’s and precipitation were not observed.

     

Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

Best Practices in Environmental Communication: A Case Study of Louisiana's Coastal Crisis

This mixed-method case study of environmental communication best practices in Louisiana, USA, identifies trends and approaches as informed by environmental psychology. The results provide key insights for environmental communicators, especially communicators in coastal regions. In-depth interviews with both environmental psychologists and environmental communicators showed that both groups emphasized knowing the audience, telling local stories, building relationships with target audiences and targeted messaging. Both psychologists and communicators also frequently mentioned general messaging concerns of source credibility, avoiding controversial terms and talking about issues, impacts and solutions to which the target audience can relate. A representative survey revealed that Louisiana residents are most interested in hearing about how environmental issues such as climate change, coastal land loss and flooding are affecting their own communities. This finding supports the idea that environmental communicators could do a better job tapping into strong place attachment and sense of community among coastal residents to promote action.