Predicting Extents of Mercury Oxidation in Coal-Derived Flue Gases

Abstract

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O₂, H₂O, HCl), emissions (NO_X, SO_X, CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MW_t. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl₂ and CaCl₂ injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO_X, LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Concentrations and Solubilities of PM2.5 Trace Elements and Their Implications for Source Apportionment and Health Research

Abstract

The elemental compositions of the water-soluble and acid-digestible fractions of 24-hr integrated fine particulate matter (PM_2.5) samples collected in Steubenville, OH, from 2000 to 2002 were determined using dynamic reaction cell inductively coupled plasma-mass spectrometry. The water-soluble elemental compositions of PM_2.5 samples collected at four satellite monitoring sites in the surrounding region were also determined. Fe was the most abundant but least water soluble of the elements determined at the Steubenville site, having a mean ambient concentration of 272 µg/m³ and a median fractional solubility of 6%. Fe solubility and its correlations with SO₄ ^2? and temperature varied significantly by season, consistent with the hypothesis that secondary sulfates may help to mobilize soluble Fe under suitable summertime photochemical conditions. Significantly higher ambient concentrations were observed at Steubenville than at each of the four satellite sites for 10 of the 18 elements (Al, As, Ca, Cd, Fe, Mg, Mn, Na, Pb, and Zn) determined in the water-soluble PM_2.5 fraction. Concentrations of Fe, Mn, and Zn at Steubenville were substantially higher than concentrations reported recently for larger U.S. cities. Receptor modeling identified seven sources affecting the Steubenville site. An (NH₄)₂SO₄-dominated source, likely representing secondary PM_2.5 from coal-fired plants to the west and southwest of Steubenville, accounted for 42% of the PM_2.5 mass, and two sources likely dominated by emissions from motor vehicles and from iron and steel facilities in the immediate Steubenville vicinity accounted for 20% and 10%, respectively. Other sources included an NH₄NO₃ source (15%), a crustal source (6%), a mixed nonferrous metals and industrial source (3%), and a primary coal combustion source (3%). Results suggest the importance of very different regional and local source mechanisms in contributing to PM_2.5 mass at Steubenville and reinforce the need for further research to elucidate whether metals such as Fe, Mn, and Zn play a role in the PM_2.5 health effects observed previously there.     

Hormesis and longevity with tannins: Free of charge or cost-intensive?

Hormetic lifespan extension is, for obvious reasons, beneficial to an individual. But is this effect really cost-neutral? To answer this question, four tannic polyphenols were tested on the nematode Caenorhabditis elegans. All were able to extend the lifespan, but only some in a hormetic fashion. Additional life trait variables including stress resistance, reproductive behavior, growth, and physical fitness were observed during the exposure to the most life extending concentrations. These traits represent the quality of life and the population fitness, being the most important parameters of a hormetic treatment besides lifespan. Indeed, it emerged that each life-extension is accompanied by a constraining effect in at least one other endpoint, for example growth, mobility, stress resistance, or reproduction. Thus, in this context, longevity could not be considered to be attained for free and therefore it is likely that other hormetic benefits may also incur cost-intensive and unpredictable side-effects.     

An examination of the efficacy of the precautionary principle as a robust environmental planning and management protocol

The precautionary principle is regularly cited in cases that involve development in eco-sensitive locations. We investigated whether the precautionary principle provides the basis for a coherent framework to prevent environmental harm, and does it work in practice? We suggest that, in principle, the precautionary principle makes good sense. In practice, however, it is imprecise in policy and law and fails to fulfil its promise because it is loosely defined and thus lacks substance and clarity. Consequently, it operates in a framework that is ambiguous, leaving it open to manipulation by discretionary powers. To counter such deficiencies, human-induced environmental harm should be formally observed as ‘criminogenic’ and environmental protection prioritised against which other competing priorities (e.g., ‘year on year’ economic growth) are measured. This would overcome the politico-legal obfuscation and contestations of climate change policy that currently impedes the precautionary principle's practical application.     

Waste prevention for sustainable resource and waste management

Although the 2Rs (reduce and reuse) are considered high-priority approaches, there has not been enough quantitative research on effective 2R management. The purpose of this paper is to provide information obtained through the International Workshop in Kyoto, Japan, on 11–13 November 2015, which included invited experts and researchers in several countries who were in charge of 3R policies, and an additional review of 245 previous studies. It was found that, regarding policy development, the decoupling between environmental pressures and economy growth was recognized as an essential step towards a sustainable society. 3R and resource management policies, including waste prevention, will play a crucial role. Approaches using material/substance flow analyses have become sophisticated enough to describe the fate of resources and/or hazardous substances based on human activity and the environment, including the final sink. Life-cycle assessment has also been developed to evaluate waste prevention activities. Regarding target products for waste prevention, food loss is one of the waste fractions with the highest priority because its countermeasures have significant upstream and downstream effects. Persistent organic pollutants and hazardous compounds should also be taken into account in the situation where recycling activities are globally widespread for the promotion of a material-cycling society.     

On the scope and management of pesticide pollution of Swedish groundwater resources: The Scanian example

Twenty-three south-Swedish public supply wells were studied to assess pesticide pollution of regional groundwater resources. Relations between pesticide occurrence, hydrogeology, and land use were analyzed using Kohonen’s Self-Organizing Maps approach. Pesticides are demonstrated to be substantially present in regional groundwater, with detections in 18 wells. Concentrations above the drinking water threshold are confirmed for nine wells. Observations indicate considerable urban influence, and lagged effects of past, less restricted use. Modern, oxic waters from shallow, unconfined, unconsolidated or fracture-type bedrock aquifers appear particularly vulnerable. Least affected waters appear primarily associated with deeper wells, anoxic conditions, and more confined sediment aquifers lacking urban influence. Comprehensive, standardized monitoring of pesticides in groundwater need to be implemented nationwide to enable sound assessments of pollution status and trends, and to develop sound groundwater management plans in accordance with the Water Framework Directive. Further, existing water protection areas and associated regulations need to be reassessed.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-014-0548-1) contains supplementary material, which is available to authorized users.     

Modelling the photooxidation of ULP,E5 and E10 in the CSIRO smog chamber

The photooxidation of fuel vapour was investigated in a smog chamber and simulated using three chemical mechanisms, the Master Chemical Mechanism (MCMv3.1), SAPRC-99 and the Carbon Bond chemical mechanism (CB05). Three varieties of fuel were used, unleaded petrol (ULP) and two ULP-ethanol blends which contained 5% and 10% ethanol (E5, E10). The fuel vapours were introduced into the chamber using two methods, by injecting the vapours from wholly evaporated fuel directly, and by injecting the headspace vapour from fuel equilibrated at 38 °C. The chamber experiments were simulated using the selected mechanisms and comparisons made with collected experimental data.The SAPRC-99 mechanism reproduced Δ(O₃–NO) more accurately for almost all fuel types and injection modes, with negligible model error for both injection modes. The average model error for MCM simulations was ?16% and for CB05 the average model error was ?34%. The predictions for the CB05 mechanism varied depending on injection mode, the Δ(O₃–NO) model error for wholly evaporated experiments was ?44%, compared to ?24% for headspace vapour experiments. The difference in aromatic content between experiments of different injection modes was likely to be the cause of the difference in model error for CB05. The model error for all headspace experiments was dependent upon the initial carbon monoxide concentrations.The results for Δ(O₃–NO) were matched by the prediction of other key products, with formaldehyde predicted to within 20% by both SAPRC and the MCM. The addition of ethanol to the base SAPRC mechanism altered the predictions of Δ(O₃–NO) by less than 2%. Changes observed in the concentrations of formaldehyde and acetaldehyde were consistent with the expected yields from ethanol oxidation.     

Water Quality Functions of a 15-Year-Old Riparian Forest Buffer System1

Newbold, J. Denis, Susan Herbert, Bernard W. Sweeney, Paul Kiry, and Stephen J. Alberts, 2010. Water Quality Functions of a 15-Year-Old Riparian Forest Buffer System. Journal of the American Water Resources Association (JAWRA) 46(2):299-310. DOI: 10.1111/j.1752-1688.2010.00421.x Abstract: We monitored long-term water quality responses to the implementation of a three-zone Riparian Forest Buffer System (RFBS) in southeastern Pennsylvania. The RFBS, established in 1992 in a 15-ha agricultural (row crop) watershed, consists of: Zone 1, a streamside strip (∼10 m wide) of permanent woody vegetation for stream habitat protection; Zone 2, an 18- to 20-m-wide strip reforested in hardwoods upslope from Zone 2; and Zone 3, a 6- to 10-m-wide grass filter strip in which a level lip spreader was constructed. The monitoring design used paired watersheds supplemented by mass balance estimates of nutrient and sediment removal within the treated watershed. Tree growth was initially delayed by drought and deer damage, but increased after more aggressive deer protection (1.5 m polypropylene shelters or wire mesh protectors) was instituted. Basal tree area increased ∼20-fold between 1998 and 2006, and canopy cover reached 59% in 2006. For streamwater nitrate, the paired watershed comparison was complicated by variations in both the reference stream concentrations and in upslope groundwater nitrate concentrations, but did show that streamwater nitrate concentrations in the RFBS watershed declined relative to the reference stream from 2002 through the end of the study in early 2007. A subsurface nitrate budget yielded an average nitrate removal by the RFBS of 90 kg/ha/year, or 26% of upslope subsurface inputs, for the years 1997 through 2006. There was no evidence from the paired watershed comparison that the RFBS affected streamwater phosphorus concentration. However, groundwater phosphorus did decline within the buffer. Overland flow sampling of 23 storms between 1997 and 2006 showed that total suspended solids concentration in water exiting the RFBS to the stream was on average 43% lower than in water entering the RFBS from the tilled field. Particulate phosphorus concentration was lower by 22%, but this removal was balanced by a 26% increase in soluble reactive phosphorus so that there was no net effect on total phosphorus.     

Water extractable organic carbon in untreated and chemical treated biochars

Biochar, as a soil amendment, can increase concentrations of soil organic matter, especially water-extractable organic carbon (WEOC). This can affect the adsorption-desorption equilibrium between the dissolved solid phases in soil organic matter. Dissolved organic carbon (DOC) represents a small proportion of soil organic matter, but is of significant importance in the soil ecosystem due to its mobility and reactivity. Here, water extracts obtained from twelve non-herbaceous biochars (before, and after, chemical treatment with either H(3)PO(4) or KOH), were tested by Liquid Chromatography - Organic Carbon Detection (LC-OCD) to identify the effects of both pyrolysis conditions and chemical treatments on WEOC content. LC-OCD has the capacity to provide a fingerprint of WEOC, which allows analysis of the various fractions present. WEOC content was affected by both the pyrolysis temperature and the feedstock used. High mineral ash contents deriving from the feedstock can prompt thermochemical reactions of lignocelluloses to produce a relatively high WEOC content, which includes low molecular weight neutrals and humic acids as dominant components. A significant change in WEOC occurred during pyrolysis due to secondary reactions which resulted in a much lower WEOC in the high temperature biochars where fractions of low molecular weight acids and neutrals are dominant. Chemical treatments with H(3)PO(4) or KOH increased WEOC concentration, possibly by promoting hydrolysis reactions on biochar surfaces. These observations assist in assessing the contribution of biochar additions to the soil ecosystem and demonstrate the utility of LC-OCD in providing an understanding of how biochar additions to soil can alter DOC.