A Discussion of Regulatory Requirements and Air Dispersion Modeling Approaches Applicable to U.S. Chemical Demilitarization Facilities

ABSTRACT

Owners of hazardous waste treatment, storage, and disposal facilities, and certain major air pollution sources, must conduct several separate ambient air dispersion modeling analyses before beginning construction of new facilities or modifying existing facilities. These analyses are critical components of the environmental permitting and facility certification processes and must be completed to the satisfaction of federal, state, and local regulatory authorities.

The U.S. Army has conducted air dispersion modeling for its proposed chemical agent disposal facilities to fulfill the following environmental regulatory and risk management requirements: (1) Resource Conservation and Recovery Act human health and ecological risk assessment analysis for the hazardous waste treatment and storage permit applications, (2) Quantitative Risk Assessment to support the site-specific risk management programs, and (3) Prevention of Significant Deterioration ambient air impact analysis for the air permit applications. The purpose of these air dispersion modeling studies is to show that the potential impacts on human health and the environment, due to operation of the chemical agent disposal facilities, are acceptable. This paper describes and compares the types of air dispersion models, modeling input data requirements, modeling algorithms, and approaches used to satisfy the three environmental regulatory and risk management requirements listed above. Although this paper discusses only one industry (i.e., chemical demilitarization), the information it contains could help those in other industries who need to communicate to the public the purpose and objectives of each modeling analysis. It may also be useful in integrating the results of each analysis into an overarching summary of compliance and potential risks.     

Preparing to Measure the Effects of the NOx SIP Call— Methods for Ambient Air Monitoring of NO,NO2, NOy,and Individual NOz Species

Abstract

The capping of stationary source emissions of NO_x in 22 states and the District of Columbia is federally mandated by the NO_x SIP Call legislation with the intended purpose of reducing downwind O₃ concentrations. Monitors for NO, NO₂, and the reactive oxides of nitrogen into which these two compounds are converted will record data to evaluate air quality model (AQM) predictions. Guidelines for testing these models indicate the need for semicontinuous measurements as close to real time as possible but no less frequently than once per hour. The measurement uncertainty required for AQM testing must be less than ±20% (±10% for NO₂) at mixing ratios of 1 ppbv and higher for NO, individual NO_z component compounds, and NO_y. This article is a review and discussion of different monitoring methods, some currently used in research and others used for routine monitoring. The performance of these methods is compared with the monitoring guidelines. Recommendations for advancing speciated and total NO_y monitoring technology and a listing of demonstrated monitoring approaches are also presented.     

Consistency of Ozone and Nitrogen Oxides Standards at Tropospherically Relevant Mixing Ratios

Abstract

The absolute accuracy and long‐term precision of atmospheric measurements hinge on the quality of the instrumentation and calibration standards. To assess the consistency of the ozone (O₃) and nitrogen oxides (NO_x) standards maintained at the National Institute of Standards and Technology (NIST), these standards were compared through the gas‐phase titration of O3 with nitric oxide (NO). NO and O₃ were monitored using chemiluminescence and UV absorption, respectively. Nitrogen dioxide (NO₂) was monitored directly by laser‐induced fluorescence and indirectly by catalytic conversion to NO, followed by chemiluminescence. The observed equivalent loss of both NO and O₃ and the formation of NO₂ in these experiments was within 1% on average over the range of 40–200 nmol mol^?1 of NO in excess O3, indicating that these instruments, when calibrated with the NIST O₃ and NO standards and the NO₂ permeation calibration system, are consistent to within 1% at tropospherically relevant mixing ratios of O₃. Experiments conducted at higher initial NO mixing ratios or in excess NO are not in as good agreement. The largest discrepancies are associated with the chemiluminescence measurements. These results indicate the presence of systematic biases under these specific conditions. Prospects for improving these experiments are discussed.     

The Recovery of Ammonia and Hydrogen Sulflde from Ground-Level Area Sources Using Dynamic Isolation Flux Chambers: Bench-Scale Studies

Abstract

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH₃) and hydrogen sulflde (H₂S) from dynamic isolation flux chambers. H₂S (80–4000 ppb) and NH₃ (5000–40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H₂S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H₂S could be recovered during the given sampling period. NH₃ emissions exhibited similar behavior between concentrations of 5000–40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH₃ sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH₃ or H₂S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH₃ and H₂S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH₃ and H₂S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the full-scale sensitivity of the gas sensing equipment. The use of 46–90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Uncertainty associated with the gravimetric measurement of particulate matter concentration in ambient air

This work applied a propagation of uncertainty method to typical total suspended particulate (TSP) sampling apparatus in order to estimate the overall measurement uncertainty. The objectives of this study were to estimate the uncertainty for three TSP samplers, develop an uncertainty budget, and determine the sensitivity of the total uncertainty to environmental parameters. The samplers evaluated were the TAMU High Volume TSP Sampler at a nominal volumetric flow rate of 1.42 m³ min^–1 (50 CFM), the TAMU Low Volume TSP Sampler at a nominal volumetric flow rate of 17 L min^–1 (0.6 CFM) and the EPA TSP Sampler at the nominal volumetric flow rates of 1.1 and 1.7 m³ min^–1 (39 and 60 CFM). Under nominal operating conditions the overall measurement uncertainty was found to vary from 6.1 x 10^–6 g m^–3 to 18.0 x 10^–6 g m^–3, which represented an uncertainty of 1.7% to 5.2% of the measurement. Analysis of the uncertainty budget determined that three of the instrument parameters contributed significantly to the overall uncertainty: the uncertainty in the pressure drop measurement across the orifice meter during both calibration and testing and the uncertainty of the airflow standard used during calibration of the orifice meter. Five environmental parameters occurring during field measurements were considered for their effect on overall uncertainty: ambient TSP concentration, volumetric airflow rate, ambient temperature, ambient pressure, and ambient relative humidity. Of these, only ambient TSP concentration and volumetric airflow rate were found to have a strong effect on the overall uncertainty. The technique described in this paper can be applied to other measurement systems and is especially useful where there are no methods available to generate these values empirically.

Implications:?This work addresses measurement uncertainty of TSP samplers used in ambient conditions. Estimation of uncertainty in gravimetric measurements is of particular interest, since as ambient particulate matter (PM) concentrations approach regulatory limits, the uncertainty of the measurement is essential in determining the sample size and the probability of type II errors in hypothesis testing. This is an important factor in determining if ambient PM concentrations exceed regulatory limits. The technique described in this paper can be applied to other measurement systems and is especially useful where there are no methods available to generate these values empirically.     

Wood pellet fly ash and bottom ash as an effective liming agent and nutrient source for rye grass (Lolium perenne L.) and oats (Avena sativa)

Fly ash (FA) and bottom ash (BA) from a softwood pellet boiler were characterized and evaluated as soil amendments. In a greenhouse study, two plant species (rye grass, Lolium perenne L. and oats, Avena sativa) were grown in three different treatments (1% FA, 1% BA, non-amended control) of a silty loam soil. Total concentrations of plant nutrients Ca, K, Mg, P and Zn in both ashes were elevated compared to conventional wood ash. Concentrations of Cd, Cr, Pb, Se and Zn were found to be elevated in the FA relative to BA and the non-amended soil. At 28 d, oat above-ground biomass was found to be significantly greater in soil amended with FA. Potassium and Mo plant tissue concentrations were significantly increased by addition of either ash, and FA significantly increased Zn tissue concentrations. Cadmium and Hg tissue concentrations were elevated in some cases. As soil amendments, either pellet ash is an effective liming agent and nutrient source, but high concentrations of Cd and Zn in FA may preclude its use as an agricultural soil amendment in some jurisdictions. Lower ash application rates than those used in this study (i.e. <1%) may still provide sufficient nutrients and effective neutralization of soil acidity.     

Influence of Sampling Frequency on Estimation of Annual Total Phosphorus and Total Suspended Solids Loads1

Abstract: The determination of sediment and nutrient loads is typically based on the collection and analysis of grab samples. The frequency and regularity of traditional sampling may not provide representation of constituent loading, particularly in systems with flashy hydrology. At two sites in the Little Bear River, Utah, continuous, high‐frequency turbidity was used with surrogate relationships to generate estimates of total phosphorus and total suspended solids concentrations, which were paired with discharge to estimate annual loads. The high frequency records were randomly subsampled to represent hourly, daily, weekly, and monthly sampling frequencies and to examine the effects of timing, and resulting annual load estimates were compared to the reference loads. Higher frequency sampling resulted in load estimates that better approximated the reference loads. The degree of bias was greater at the more hydrologically responsive site in the upper watershed, which required a higher sampling frequency than the lower watershed site to achieve the same level of accuracy in estimating the reference load. The hour of day and day of week of sampling impacted load estimation, depending on site and hydrologic conditions. The effects of sampling frequency on the determination of compliance with a water quality criterion were also examined. These techniques can be helpful in determining necessary sampling frequency to meet the objectives of a water quality monitoring program.     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.     

Nonpoint source of nutrients and herbicides associated with sugarcane production and its impact on Louisiana coastal water quality

A watershed analysis of nonpoint-source pollution associated with sugarcane (Saccharum officinarum L.) production was conducted. Runoff water samples following major rainfall events from two representative sugarcane fields (SC1 and SC2) were collected and analyzed. The impact of runoff on two receiving water bodies, St. James canal (SJC) and Bayou Chevreuil (BC) in a drainage basin (Baratarian Basin), was studied. Results show that runoff flow/rainfall ratios at the SC1 were significantly higher (P < 0.0001, n = 14) than at the SC2, probably mainly due to higher sand content and higher infiltration rate of surface soil at the SC2. In runoff water samples, total suspended solids (TSS) showed a significant correlation with the concentrations of N and P. Sugarcane runoff showed a direct impact on the SJC and BC locations where seasonal variations of pollutant concentrations in the waters followed the patterns of runoff loadings. Swamp forest runoff (SFR) location showed a buffering effect of forested wetlands on water quality with the lowest measured pollutant concentrations. The ratios in total N/total P and in inorganic N/organic N in runoff waters indicated that fertilization in spring greatly contributed to the temporal increase of N loadings, especially in forms of inorganic N. Isotope signature of (15)N-nitrate in the water samples verified that the nitrate was derived from fertilizers and was consumed during transportation. Both N and P concentrations in the receiving water bodies were above the eutrophic level. During the study period, herbicide concentrations in the receiving water bodies rarely exceeded the drinking water standards.     

Demolish it and They Will Come: Estimating the Economic Impacts of Restoring a Recreational Fishery1

Abstract: This paper presents the results of an ex post survey of recreational anglers for the lower Kennebec River, post‐Edwards Dam removal. To the best of our knowledge, this study represents one of the first ex post analyses of fisheries restoration from dam removal. We find significant benefits have accrued to anglers using the restored fishery. Specifically, anglers are spending more to visit the fishery, a direct indication of the increased value anglers place on the improved fishery. Anglers are also willing to pay for increased angling opportunities on the river. These findings have policy implications for other privately owned dams that are currently undergoing relicensing and/or dam removal considerations. Our findings may also hold implications for fisheries that have deteriorated due to historic dam construction.