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.     

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.     

Evaluating the Impacts of Mangrove Rehabilitation in Cogtong Bay,Philippines

Marine Protected Areas (MPAs) have been hailed worldwide as vehicles toward sustainable development (SD) in coastal zones. The prominent model by which MPAs operate is through a comanagement approach, a shift from traditional top-down management. This paradigm shift must be reviewed continuously to evaluate its social and ecological impacts, thereby allowing adaptive management. We evaluated the perceived impacts of the Cogtong Bay Mangrove Rehabilitation Project (CBMRP; Philippines) by using 12 perception indicators categorized into 3 comanagement impact criteria (equity, efficiency, and sustainability). We also collected 16 contextual attributes of each respondent to determine the correlates of perceived impacts. Our results showed that there were significant improvements in all indicators under the efficiency criterion but mixed impacts in the equity and sustainability criteria. Access to resource and household income (equity) and fisheries abundance (sustainability) were perceived to have decreased during the last 15 years and were not expected to improve in the future. Stepwise multiple regression analysis showed that the asymmetries of the perceived impacts of the CBMRP were principally caused by disparities in perceptions by gender and by location (Candijay and Mabini). This highlighted the importance of cross-scale institutional linkages between Cogtong Bay municipalities to systematically address baywide management issues. Our results further demonstrated the necessity of integrating gender issues into the evaluation of MPA impacts to ensure a robust evaluation. Finally, we recommend that a rigorous evaluation of MPAs using a common set of impact indicators should be encouraged to allow comparison of studies both spatially and temporally.     

Application of Sample Selection Model in Estimating Response Functions for Nitrate Percolation

The Seymour aquifer region of Texas has been identified as containing elevated levels of nitrate in ground water. Various state and federal agencies are currently studying policy options for the region by gathering more site-specific information. However, because of lack of sufficient information, cause and effect relationships between water quality and agricultural practices have not been well established for the region. Some recently available biophysical simulation models have impressive capabilities in generating large amounts of data on environmental pollution resulting from agricultural production practices. In this study, the data generated by a biophysical simulation model were used to estimate the nitrate percolation response functions for the Seymour aquifer region. Interestingly, nitrate percolation values obtained from simulation models often comprise acensoredsample because the non-zero percolation values are only observed under certain climatic events and input levels. It has been shown in the econometric literature that the use of Ordinary Least Squares (OLS) on censored sample data produces biased and inconsistent parameter estimates. Thus, a sample selection model was used in this study to estimate the response functions for nitrate percolation. The study provides some insight into the relationship between nitrate percolation and agricultural production practices. In particular, the study demonstrates the potential of selected design standards in minimizing agricultural nonpoint-source (NPS) pollution for the study area.     

Stress,work and professional satisfaction and militancy among Canadian physicians

The introduction of a national health care system in Canada has resulted in regular and increasing conflict between the medical profession, government and other political actors. The present study utilizes a stressor–strain framework to understand physician militancy in Canada. Data were collected from 2087 men and women physicians using questionnaires completed anonymously. Four groups of predictor variables identified in previous research were considered: individual demographic characteristics, practice characteristics, work stressors, and work and professional satisfactions. Empirical support for the model was found. Each panel of predictor variables had significant and unique relationships with measures of physician militancy.     

Managing the Commons Texas Style: Wildlife Management and Ground‐Water Associations on Private Lands1

Abstract: As nearly all of Texas’ rural lands are privately owned, landowner associations for the management of white‐tailed deer and ground‐water have become increasingly popular. Deer are a common‐pool resource with transboundary characteristics, requiring landowner cooperation for effective management. Ground‐water reserves are economically important to landowners, but are governed by the “rule of capture” whereby property rights are not defined. One ground‐water association and four wildlife management associations (WMAs) were surveyed to characterize their member demographics, land use priorities, attitudes, and social capital. Members of the ground‐water cooperative were part of a much larger, more heterogeneous, and more recently formed group than members of WMAs. They also placed greater importance on utilitarian aspects of their properties, as opposed to land stewardship for conservation as practiced by members of WMAs. If ground‐water association members could be more locally organized with more frequent meetings, social capital and information sharing may be enhanced and lead to land stewardship practices for improved hydrologic functions and sustained ground‐water supply. This, coupled with pumping rules assigned by the local ground‐water district, could yield an effective strategy that is ecologically and hydrologicaly sound, and that allows rural provision of water supply to urban consumers.