Mining Available Data from the United States Environmental Protection Agency to Support Rapid Life Cycle Inventory Modeling of Chemical Manufacturing.

Demands for quick and accurate life cycle assessments create a need for methods to rapidly generate reliable life cycle inventories (LCI). Data mining is a suitable tool for this purpose, especially given the large amount of available governmental data. These data are typically applied to LCIs on a case-by-case basis. As linked open data becomes more prevalent, it may be possible to automate LCI using data mining by establishing a reproducible approach for identifying, extracting, and processing the data. This work proposes a method for standardizing and eventually automating the discovery and use of publicly available data at the United States Environmental Protection Agency for chemical-manufacturing LCI. The method is developed using a case study of acetic acid. The data quality and gap analyses for the generated inventory found that the selected data sources can provide information with equal or better reliability and representativeness on air, water, hazardous waste, on-site energy usage, and production volumes but with key data gaps including material inputs, water usage, purchased electricity, and transportation requirements. A comparison of the generated LCI with existing data revealed that the data mining inventory is in reasonable agreement with existing data and may provide a more-comprehensive inventory of air emissions and water discharges. The case study highlighted challenges for current data management practices that must be overcome to successfully automate the method using semantic technology. Benefits of the method are that the openly available data can be compiled in a standardized and transparent approach that supports potential automation with flexibility to incorporate new data sources as needed.

Mercury contaminated sediment sites-an evaluation of remedial options.

Mercury (Hg) is a naturally-occurring element that is ubiquitous in the aquatic environment. Though efforts have been made in recent years to decrease Hg emissions, historically-emitted Hg can be retained in the sediments of aquatic bodies where they may be slowly converted to methylmercury (MeHg). Consequently, Hg in historically-contaminated sediments can result in high levels of significant exposure for aquatic species, wildlife and human populations consuming fish. Even if source control of contaminated wastewater is achievable, it may take a very long time, perhaps decades, for Hg-contaminated aquatic systems to reach relatively safe Hg levels in both water and surface sediment naturally. It may take even longer if Hg is present at higher concentration levels in deep sediment. Hg contaminated sediment results from previous releases or ongoing contributions from sources that are difficult to identify. Due to human activities or physical, chemical, or biological processes (e.g. hydrodynamic flows, bioturbation, molecular diffusion, and chemical transformation), the buried Hg can be remobilized into the overlying water. Hg speciation in the water column and sediments critically affect the reactivity (i.e. conversion of inorganic Hg(II) to MeHg), transport, and its exposure to living organisms. Also, geochemical conditions affect the activity of methylating bacteria and its availability for methylation. This review paper discusses remedial considerations (e.g. key chemical factors in fate and transport of Hg, source characterization and control, environmental management procedures, remediation options, modeling tools) and includes practical case studies for cleaning up Hg-contaminated sediment sites.

In-situ subaqueous capping of mercury-contaminated sediments in a fresh-water aquatic system, Part I-Bench-scale microcosm study to assess methylmercury production.

Bench-scale microcosm experiments were designed to provide a better understanding of the potential for Hg methylation in sediments from an aquatic environment. Experiments were conducted to examine the function of sulfate concentration, lactate concentration, the presence/absence of an aqueous inorganic Hg spike, and the presence/absence of inoculums of Desulfovibrio desulfuricans, a strain of sulfate-reducing bacteria (SRB) commonly found in the natural sediments of aquatic environments. Incubations were analyzed for both the rate and extent of (methylmercury) MeHg production. Methylation rates were estimated by analyzing MeHg and Hg after 2, 7, 14, 28, and 42 days. The production of metabolic byproducts, including dissolved gases as a proxy for metabolic utilization of carbon substrate, was also monitored. In all treatments amended with lactate, sulfate, Hg, and SRB, MeHg was produced (37ng/g-sediment dry weight) after only 48h of incubation and reached a maximum sediment concentration of 127ng/g-sediment dry weight after the 42 day incubation period. Aqueous phase production of MeHg was observed to be 10ng/L after 2 day, reaching a maximum observed concentration of 32.8ng/L after 14 days, and declining to 10.8ng/L at the end of the incubation period (42 day). The results of this study further demonstrates that, in the presence of an organic carbon substrate, sulfate, and the appropriate consortia of microorganisms, sedimentary Hg will be transformed into MeHg through bacterial metabolism. Further, this study provided the basis for evaluation of an in-situ subaqueous capping strategy that may limit (or potentially enhance) MeHg production.

In-situ subaqueous capping of mercury-contaminated sediments in a fresh-water aquatic system, Part II-evaluation of sorption materials.

The function and longevity of traditional, passive, isolation caps can be augmented through the use of more chemically active capping materials which have higher sorptive capacities, ideally rendering metals non-bioavailable. In the case of Hg, active caps also mitigate the rate and extent of methylation. This research examined low cost, readily available, capping materials for their ability to sequester Hg and MeHg. Furthermore, selected capping materials were evaluated to inhibit the methylation of Hg in an incubation study as well as the capacity of a selected capping material to inhibit translocation of Hg and MeHg with respect to ebullition-facilitated contaminant transport in a column study. Results indicated that bauxite had a better capacity for mercury sorption than the other test materials. However, bauxite as well as soil capping materials did not decrease methylation to a significant extent. Materials with larger surface areas, higher organic matter and acid volatile sulfide (AVS) content displayed a larger partitioning coefficient. In the incubation experiments, the presence of a carbon source (lactate), electron acceptor (sulfate) and the appropriate strains of SRB provided the necessary conditions for Hg methylation to occur. The column study showed effectiveness in sequestering Hg and MeHg and retarding transport to the overlying water column; however, disturbances to the soil capping material resulting from gas ebullition negated its effectiveness.

The assessment and remediation of mercury contaminated sites: A review of current approaches.

Remediation of mercury (Hg) contaminated sites has long relied on traditional approaches, such as removal and containment/capping. Here we review contemporary practices in the assessment and remediation of industrial-scale Hg contaminated sites and discuss recent advances. Significant improvements have been made in site assessment, including the use of XRF to rapidly identify the spatial extent of contamination, Hg stable isotope fractionation to identify sources and transformation processes, and solid-phase characterization (XAFS) to evaluate Hg forms. The understanding of Hg bioavailability for methylation has been improved by methods such as sequential chemical extractions and porewater measurements, including the use of diffuse gradient in thin-film (DGT) samplers. These approaches have shown varying success in identifying bioavailable Hg fractions and further study and field applications are needed. The downstream accumulation of methylmercury (MeHg) in biota is a concern at many contaminated sites. Identifying the variables limiting/controlling MeHg production-such as bioavailable inorganic Hg, organic carbon, and/or terminal electron acceptors (e.g. sulfate, iron) is critical. Mercury can be released from contaminated sites to the air and water, both of which are influenced by meteorological and hydrological conditions. Mercury mobilized from contaminated sites is predominantly bound to particles, highly correlated with total sediment solids (TSS), and elevated during stormflow. Remediation techniques to address Hg contamination can include the removal or containment of Hg contaminated materials, the application of amendments to reduce mobility and bioavailability, landscape/waterbody manipulations to reduce MeHg production, and food web manipulations through stocking or extirpation to reduce MeHg accumulated in desired species. These approaches often rely on knowledge of the Hg forms/speciation at the site, and utilize physical, chemical, thermal and biological methods to achieve remediation goals. Overall, the complexity of Hg cycling allows many different opportunities to reduce/mitigate impacts, which creates flexibility in determining suitable and logistically feasible remedies.

Coupling Computer-Aided Process Simulation and Estimations of Emissions and Land Use for Rapid Life Cycle Inventory Modeling.

A methodology is described for developing a gate-to-gate life cycle inventory (LCI) of a chemical manufacturing process to support the application of life cycle assessment in the design and regulation of sustainable chemicals. The inventories were derived by first applying process design and simulation to develop a process flow diagram describing the energy and basic material flows of the system. Additional techniques developed by the United States Environmental Protection Agency for estimating uncontrolled emissions from chemical processing equipment were then applied to obtain a detailed emission profile for the process. Finally, land use for the process was estimated using a simple sizing model. The methodology was applied to a case study of acetic acid production based on the Cativa process. The results reveal improvements in the qualitative LCI for acetic acid production compared to commonly used databases and top-down methodologies. The modeling techniques improve the quantitative LCI results for inputs and uncontrolled emissions. With provisions for applying appropriate emission controls, the proposed method can provide an estimate of the LCI that can be used for subsequent life cycle assessments.

Arsenic encapsulation using Portland cement with ferrous sulfate/lime and Terra-Bond™ technologies - Microcharacterization and leaching studies.

This work reports the results of an investigation on the treatment and encapsulation of arsenic-containing materials by Portland cement with ferrous sulfate and lime (PFL) and Terra-Bond™, a commercially available patented technology. The arsenic materials included: chromated copper arsenate (CCA)-treated wood materials; scorodite-rich mine tailings from the La Trinidad Mine in California; and a soil/smelter dust mixture from the Anaconda Superfund site spiked with monosodium methyl arsenate (MSMA) to simulate an organoarsenic soil material. SEM/EDS and XRD spectra of PFL treated samples showed similarity across all three waste materials while Terra-Bond treated samples showed predominance of elemental sulfur. SEM/EDS of PFL treated samples showed that calcium was imbedded in the structure while micrographs of Terra-Bond treated samples showed the appearance of an epoxy material on the surface. The epoxy material appears to be responsible for encapsulating and reducing the leachability of arsenic. XANES spectra for the PFL treatment of CCA-containing samples showed that arsenic has a predominant pentavalent form (As +5), and the PFL treatment process did not alter the arsenic oxidation state. But, distinct differences were observed for XANES spectra of untreated and PFL treated scorodite-rich mine tailing which changed the arsenic coordination structure from a mixture of As (+3/+5) to exclusively As (+5). Both S/S techniques reduced the amount of arsenic released in the leaching tests. Most cases show lower amounts of arsenic released from wastes treated by the Terra-Bond™ technique when compared to the PFL technique. The pH of the solution significantly affected the leachability, with the amount of arsenic released increasing with pH. Sequential extraction results indicate that sodium hydroxide was favorable in releasing arsenic in the mine tailings. This is due to ligand displacement reactions of hydroxyl ions with arsenic species and high pH conditions that prevent the readsorption of arsenic.

Evaluation of Needle Gun and Abrasive Blasting Technologies in Bridge Paint Removal Practices.

This paper reviews the results of a U.S. Environmental Protection Agency (EPA) study that assessed needle gun technology as an alternative to conventional abrasive blasting technology to remove lead-based paint from steel bridges in western New York State. The study analyzed the operational and logistical aspects as they relate to worker health and safety, environmental protection, hazardous waste generation, and costs as compared to those arising from conventional abrasive blasting. In this 1992 EPA study, the costs and the product quality aspects favored conventional abrasive blasting over the needle gun technology for removing lead paint. However, abrasive blasting exposed workers to airborne lead levels that exceeded Permissible Exposure Limits (PELs) as established by the Occupational Safety and Health Administration (OSHA), as well as emitting high levels of lead-contaminated dusts and debris into the environment. It was estimated that more than 500 lbs of lead-contaminated spent abrasives and paint waste were released into the environment during paint removal operations. The needle gun system reduced (up to 97.5%) the generation of hazardous waste and the airborne concentrations (up to 99%) of respirable dusts and lead-containing particulates generated during paint removal operations. However, labor costs for the needle gun were three times higher than those for abrasive blasting primarily because of slower production rates that necessitated more operating personnel. The higher labor costs of the needle gun are partially offset by the increased costs associated with the expendable abrasive blast media and hazardous waste disposal. In the EPA study, the productivity of the needle gun system was 12.2 ft2/hr vs. 147.5 ft2/hr for abrasive blasting. A post blast was needed for the needle gun system to meet surface preparation specifications. When factoring in the costs of full containment structures to meet OSHA's 1993 Lead Exposure in Construction regulation, the needle gun system has the potential to be economically competitive with conventional abrasive blasting.