Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

Using Regression Tree Analysis to Improve Predictions of Low-Flow Nitrate and Chloride in Willamette River Basin Watersheds

The use of regression tree analysis is examined as a tool to evaluate hydrologic and land use factors that affect nitrate and chloride stream concentrations during low-flow conditions. Although this data mining technique has been used to assess a range of ecological parameters, it has not previously been used for stream water quality analysis. Regression tree analysis was conducted on nitrate and chloride data from 71 watersheds in the Willamette River Basin to determine whether this method provides a greater predictive ability compared to standard multiple linear regression, and to elucidate the potential roles of controlling mechanisms. Metrics used in the models included a variety of watershed-scale landscape indices and land use classifications. Regression tree analysis significantly enhanced model accuracy over multiple linear regression, increasing nitrate R ² values from 0.38 to 0.75 and chloride R ² values from 0.64 to 0.85 and as indicated by the ΔAIC value. These improvements are primarily attributed to the ability for regression trees to more effectively handle interactions and manage non-linear functions associated with watershed heterogeneity within the basin. Whereas hydrologic factors governed the conservative chloride tracer in the model, land use dominated control of nitrate concentrations. Watersheds containing higher agricultural activity did not necessarily yield high nitrate concentrations, but agricultural areas combined with either small proportions of forested land or greater urbanization generated nitrate levels far exceeding water quality standards. Although further refinements are recommended, we conclude that regression tree analysis presents water resource managers a promising tool that improves on the predictive ability of standard statistical methods, provides insight into controlling mechanisms, and helps identify catchment characteristics associated with water quality impairment.     

Investigation of the ultraviolet photolysis method for the determination of organic nitrogen in aerosol samples

The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.     

The contingent behavior of charter fishing participants on the Chesapeake Bay: Welfare estimates associated with water quality improvements

Water quality in the Chesapeake Bay has deteriorated over recent years. Historically, fishing has contributed to the region's local economy in terms of commercial and recreational harvests. A contingent behavior model is used to estimate welfare measures for charter fishing participants with regard to a hypothetical improvement in water quality. Using a truncated Poisson count model corrected for endogenous stratification, it was found that charter fishers not only contribute to the local market economy, but they also place positive non-market value on preserving the Bay's water quality. Using two estimates for travels costs it is estimated that the individual consumer surplus is $200 and $117 per trip, and the average individual consumer surplus values for an improvement in water quality is $75 and $44 for two models estimated.     

Testing the Hydrological Landscape Unit Classification System and Other Terrain Analysis Measures for Predicting Low-Flow Nitrate and Chloride in Watersheds

Elevated nitrate concentrations in streamwater are a major environmental management problem. While land use exerts a large control on stream nitrate, hydrology often plays an equally important role. To date, predictions of low-flow nitrate in ungauged watersheds have been poor because of the difficulty in describing the uniqueness of watershed hydrology over large areas. Clearly, hydrologic response varies depending on the states and stocks of water, flow pathways, and residence times. How to capture the dominant hydrological controls that combine with land use to define streamwater nitrate concentration is a major research challenge. This paper tests the new Hydrologic Landscape Regions (HLRs) watershed classification scheme of Wolock and others (Environmental Management 34:S71-S88, 2004) to address the question: Can HLRs be used as a way to predict low-flow nitrate? We also test a number of other indexes including inverse-distance weighting of land use and the well-known topographic index (TI) to address the question: How do other terrain and land use measures compare to HLR in terms of their ability to predict low-flow nitrate concentration? We test this for 76 watersheds in western Oregon using the U.S. Environmental Protection Agency’s Environmental Monitoring and Assessment Program and Regional Environmental Monitoring and Assessment Program data. We found that HLRs did not significantly improve nitrate predictions beyond the standard TI and land-use metrics. Using TI and inverse-distance weighting did not improve nitrate predictions; the best models were the percentage land use—elevation models. We did, however, see an improvement of chloride predictions using HLRs, TI, and inverse-distance weighting; adding HLRs and TI significantly improved model predictions and the best models used inverse-distance weighting and elevation. One interesting result of this study is elevation consistently predicted nitrate better than TI or the hydrologic classification scheme.