Nitrogen Enrichment during Soil Organic Matter Burning and Molecular Evidence of Maillard Reactions.

Wildfires in forested watersheds dramatically alter stored and labile soil organic matter (SOM) pools and the export of dissolved organic matter (DOM). Ecosystem recovery after wildfires depends on soil microbial communities and revegetation and therefore is limited by the availability of nutrients, such as nitrogen-containing and labile, water-soluble compounds. However, SOM byproducts produced at different wildfire intensities are poorly understood, leading to difficulties in assessing wildfire severity and predicting ecosystem recovery.

Molecular Identification of Water-Extractable Organic Carbon from Thermally Heated Soils: C-13 NMR and Accurate Mass Analyses Find Benzene and Pyridine Carboxylic Acids.

To simulate the effects of wildfire on the combustion process in soils and their potential to leach organic compounds into streams and groundwater, mineral soil samples were heated at temperatures of 150-550 °C. Then, the soils were leached with deionized water, filtered, and analyzed for dissolved organic carbon. The water extract was concentrated by both XAD-8 and XAD-4 resins and analyzed by C-13 nuclear magnetic resonance and liquid chromatography time-of-flight mass spectrometry.

13C and 15N NMR identification of product compound classes from aqueous and solid phase photodegradation of 2,4,6-trinitrotoluene.

Photolysis is one of the main transformation pathways for 2,4,6-trinitrotoluene (TNT) released into the environment. Upon exposure to sunlight, TNT is known to undergo both oxidation and reduction reactions with release of nitrite, nitrate, and ammonium ions, followed by condensation reactions of the oxidation and reduction products. In this study, compound classes of transformation products from the aqueous and solid phase photodegradation of 2,4,6-trinitrotoluene (TNT) have been identified by liquid and solid state 13C and 15N NMR.

Crude Oil Metabolites in Groundwater at Two Spill Sites.

Two groundwater plumes in north central Minnesota with residual crude oil sources have 20 to 50 mg/L of nonvolatile dissolved organic carbon (NVDOC). These values are over 10 times higher than benzene and two to three times higher than Diesel Range Organics in the same wells. On the basis of previous work, most of the NVDOC consists of partial transformation products from the crude oil.

Nitrosation and Nitration of Fulvic Acid, Peat and Coal with Nitric Acid.

Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM) in general, in the context of a variety of environmental and biogeochemical processes.

Probing the Carbonyl Functionality of a Petroleum Resin and Asphaltene through Oximation and Schiff Base Formation in Conjunction with N-15 NMR.

Despite recent advances in spectroscopic techniques, there is uncertainty regarding the nature of the carbonyl groups in the asphaltene and resin fractions of crude oil, information necessary for an understanding of the physical properties and environmental fate of these materials. Carbonyl and hydroxyl group functionalities are not observed in natural abundance 13C nuclear magnetic resonance (NMR) spectra of asphaltenes and resins and therefore require spin labeling techniques for detection. In this study, the carbonyl functionalities of the resin and asphaltene fractions from a light aliphatic crude oil that is the source of groundwater contamination at the long term USGS study site near Bemidji, Minnesota, have been examined through reaction with 15N-labeled hydroxylamine and aniline in conjunction with analysis by solid and liquid state 15N NMR.

Ultraviolet irradiation effects incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter.

One of the concerns regarding the safety and efficacy of ultraviolet radiation for treatment of drinking water and wastewater is the fate of nitrate, particularly its photolysis to nitrite. In this study, N NMR was used to establish for the first time that UV irradiation effects the incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter (NOM). Irradiation of (15)N-labeled nitrate in aqueous solution with an unfiltered medium pressure mercury lamp resulted in the incorporation of nitrogen into Suwannee River NOM (SRNOM) via nitrosation and other reactions over a range of pH from approximately 3.

Order of functionality loss during photodegradation of aquatic humic substances.

The time course photodegradation of the Nordic aquatic fulvic and humic acids and Suwannee River XAD-4 acids subjected to UV irradiation with an unfiltered medium pressure mercury lamp was studied by liquid-state 13C nuclear magnetic resonance. Photodecarboxylation was a significant pathway in all cases. Decreases in ketone, aromatic, and O-alkyl carbons were observed throughout the course of the irradiations, whereas C-alkyl carbons resisted photodegradation.

N-15 NMR study of the immobilization of 2,4- and 2,6-dinitrotoluene in aerobic compost.

Large-scale aerobic windrow composting has been used to bioremediate washout lagoon soils contaminated with the explosives TNT (2,4,6-trinitrotoluene) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) at several sites within the United States. We previously used 15N NMR to investigate the reduction and binding of T15NT in aerobic bench-scale reactors simulating the conditions of windrow composting. These studies have been extended to 2,4-dinitrotoluene (2,4DNT) and 2,6-dinitrotoluene (2,6DNT), which, as impurities in TNT, are usually presentwherever soils have been contaminated with TNT.

Alkaline hydrolysis/polymerization of 2,4,6-trinitrotoluene: characterization of products by 13C and 15N NMR.

Alkaline hydrolysis has been investigated as a nonbiological procedure for the destruction of 2,4,6-trinitrotoluene (TNT) in explosives contaminated soils and munitions scrap. Nucleophilic substitutions of the nitro and methyl groups of TNT by hydroxide ion are the initial steps in the alkaline degradation of TNT. Potential applications of the technique include both in situ surface liming and ex situ alkaline treatment of contaminated soils.

Development and application of pyrolysis gas chromatography/mass spectrometry for the analysis of bound trinitrotoluene residues in soil.

TNT (trinitrotoluene) is a contaminant of global environmental significance, yet determining its environmental fate has posed longstanding challenges. To date, only differential extraction-based approaches have been able to determine the presence of covalently bound, reduced forms of TNT in field soils. Here, we employed thermal elution, pyrolysis, and gas chromatography/mass spectrometry (GC/MS) to distinguish between covalently bound and noncovalently bound reduced forms of TNT in soil.