A Water Quality Monitoring Network Design Methodology for the Selection of Critical Sampling Points: Part I

The principal instrument to temporally and spatially manage water resources is a water quality monitoring network. However, to date in most cases, there is a clear absence of a concise strategy or methodology for designing monitoring networks, especially when deciding upon the placement of sampling stations. Since water quality monitoring networks can be quite costly, it is very important to properly design the monitoring network so that maximum information extraction can be accomplished, which in turn is vital when informing decision-makers. This paper presents the development of a methodology for identifying the critical sampling locations within a watershed. Hence, it embodies the spatial component in the design of a water quality monitoring network by designating the critical stream locations that should ideally be sampled. For illustration purposes, the methodology focuses on a single contaminant, namely total phosphorus, and is applicable to small, upland, predominantly agricultural-forested watersheds. It takes a number of hydrologic, topographic, soils, vegetative, and land use factors into account. In addition, it includes an economic as well as logistical component in order to approximate the number of sampling points required for a given budget and to only consider the logistically accessible stream reaches in the analysis, respectively. The methodology utilizes a geographic information system (GIS), hydrologic simulation model, and fuzzy logic.     

Soil-mediated prion transmission: is local soil-type a key determinant of prion disease incidence?

Prion diseases, including chronic wasting disease (CWD) and scrapie, can be transmitted via indirect environmental routes. Animals habitually ingest soil, and results from laboratory experiments demonstrate prions can bind to a wide range of soils and soil minerals, retain the ability to replicate, and remain infectious, indicating soil could serve as a reservoir for natural prion transmission and a potential prion exposure route for humans. Preliminary epidemiological modeling suggests soil texture may influence the incidence of prion disease. These results are supported by experimental work demonstrating variance in prion interactions with soil, including variance in prion soil adsorption and soil-bound prion replication with respect to soil type. Thus, local soil type may be a key determinant of prion incidence. Further experimental and epidemiological work is required to fully elucidate the dynamics of soil-mediated prion transmission, an effort that should lead to effective disease management and mitigation strategies.     

Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO₄). Both the high density (1025 gL^− 1) and reactivity of the treatment solution influence the fate of permanganate (MnO₄) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO₄ utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer–aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO₄ have a negligible effect on solution density and MnO₄ delivery.     

Deriving the factor structure of safety climate scales

Since the original formulation of the notion of safety climate, many people have developed safety climate measures and conducted factor analyses to identify distinct dimensions. Typically, these analyses were based on samples of workers in a limited number of workplaces, but since they did not allow for the non-independence of the data, they are incorrect. An appropriate analysis should use a multi-level method. This flaw in the analyses to date may at least partly explain the different factor structures of safety climate reported in the literature.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Uptake and accumulation of antimicrobials,triclocarban and triclosan,by food crops in a hydroponic system

Commonly used in personal care products, triclocarban (TCC) and triclosan (TCS) are two chemicals with antimicrobial properties that have recently been recognized as environmental contaminants with the potential to adversely affect human health. The objective of the study described herein was to evaluate the potential of food crops to uptake TCC and TCS. Eleven food crops, grown in hydroponic nutrient media, were exposed to a mixture of 500 μg L^?1 TCC and TCS. After 4 weeks of exposure, roots accumulated 86–1,350 mg kg^?1 of antimicrobials and shoots had accumulated 0.33–5.35 mg kg^?1 of antimicrobials. Translocation from roots to shoots was less than 1.9 % for TCC and 3.7 % for TCS, with the greatest translocation for TCC observed for pepper, celery, and asparagus and for TCS observed for cabbage, broccoli, and asparagus. For edible tuber- or bulb-producing crops, the concentrations of both TCC and TCS were lower in the tubers than in the roots. Exposure calculations using national consumption data indicated that the average exposure to TCC and TCS from eating contaminated crops was substantially less than the exposure expected to cause adverse effects, but exceeded the predicted exposure from drinking water. Exposure to antimicrobials through food crops would be substantially reduced through limiting consumption of beets and onions.     

Sampling Frequency Guidance for Ambient Air Toxics Monitoring

Abstract

The U.S. Environmental Protection Agency (EPA) is in the process of designing a national network to monitor hazardous air pollutants (HAPs), also known as air toxics. The purposes of the expanded monitoring are to (1) characterize ambient concentrations in representative areas; (2) provide data to support and evaluate dispersion and receptor models; and (3) establish trends and evaluate the effectiveness of HAP emission reduction strategies. Existing air toxics data, in the form of an archive compiled by EPA’s Office of Air Quality Planning and Standards (OAQPS), are used in this paper to examine the relationship between estimated annual average (AA) HAP concentrations and their associated variability. The goal is to assess the accuracy, or bias and precision, with which the AA can be estimated as a function of ambient concentration levels and sampling frequency. The results suggest that, for several air toxics, a sampling schedule of 1 in 3 days (1:3) or 1:6 days may be appropriate for meeting some of the general objectives of the national network, with the more intense sampling rate being recommended for areas expected to exhibit relatively high ambient levels.     

Evaluation of the SO2 and NOX offset ratio method to account for secondary PM2.5 formation

The U.S. Environmental Protection Agency (EPA), state and local agencies have focused their efforts in assessing secondary fine particulate matter (aerodynamic diameter ≤2.5 µm; PM_2.5) formation in prevention of significant deterioration (PSD) air dispersion modeling. The National Association of Clean Air Agencies (NACAA) developed a method to account for secondary PM_2.5 formation by using sulfur dioxide (SO₂) and nitrogen oxides (NO_x) offset ratios. These ratios are used to estimate the secondary formation of sulfate and nitrate PM_2.5. These ratios were first introduced by the EPA for nonattainment areas in the Implementation of the New Source Review (NSR) Program for Particulate Matter Less than 2.5 Micrometers (PM_2.5), 73 FR 28321, to offset emission increases of direct PM_2.5 emissions with reductions of PM_2.5 precursors and vice versa. Some regulatory agencies such as the Minnesota Pollution Control Agency (MPCA) have developed area-specific offset ratios for SO₂ and NO_x based on Comprehensive Air Quality Model with Extensions (CAMx) evaluations for air dispersion modeling analyses. The current study evaluates the effect on American Meteorological Society/Environmental Protection Agency Regulatory Model (AERMOD) predicted concentrations from the use of EPA and MPCA developed ratios. The study assesses the effect of these ratios on an electric generating utility (EGU), taconite mine, food processing plant, and a pulp and paper mill. The inputs used for these four scenarios are based on common stack parameters and emissions based on available data. The effect of background concentrations also evaluates these scenarios by presenting results based on uniform annual PM_2.5 background values. This evaluation study helps assess the viability of the offset ratio method developed by NACAA in estimating primary and secondary PM_2.5 concentrations. An alternative Tier 2 approach to combine modeled and monitored concentrations is also presented.

Implications:

On January 4, 2012, the EPA committed to engage in rulemaking to evaluate updates to the Guideline on Air Quality Models (Appendix W of 40 CFR 51) and, as appropriate, incorporate new analytical techniques or models for secondary PM_2.5. As a result, the National Association of Clean Air Agencies (NACAA) developed a screening method involving offset ratios to account for secondary PM_2.5 formation. The use of this method is promising to evaluate total (direct and indirect) PM_2.5 impacts for permitting purposes. Therefore, the evaluation of this method is important to determine its viability for widespread use.     

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.