Structural-group quantitation by CP/MAS 13C NMR measurements of dissolved organic matter from natural waters
No abstract available.
Book chapter↗
Geology topics
George R. Aiken
Publications and source records attributed to George R. Aiken.
Surface-water-quality assessment of the Yakima River basin, Washington. Distribution of pesticides and other organic compounds in water, sediment, and aquatic biota, 1987-91: With a section on dissolved organic carbon in the Yakima River basin
During 1987-91, chemical data were collected for pesticides and other organic compounds in surface water, streambed sediment, suspended sediment, agricultural soil, and aquatic biota to determine the occurrence, distribution, transport, and fate of organic compounds in the Yakima River basin in Washington. The report describes the chemical and physical properties of the compounds most frequently detected in the water column; organochlorine compounds including DDT, organophosphorus compounds, thiocarbamate and sulfite compounds, acetamide and triazine compounds, and chlorophenoxy-acetic acid and benzoic compounds. Concentrations are evaluated relative to chronic-toxicity water quality criteria and guidelines for the protection of human health and freshwater aquatic life.
Washington↗
Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades
Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca 2+ . Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13 C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pH pzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.
Florida↗
Sources and age of aquatic humus
As aquatic scientists have recognized the diversity of processes controlled by or dependent upon aquatic humus, it has become important to learn more about the genesis, chemical properties, and concentration of humic substances in aquatic ecosystems. There are three classes of aquatic humus (fulvic acids, humic acids, and humin), all of which share the characteristics of being heterogeneous biomolecules which are yellow to brown or black in color, high to moderate molecular weight, and biologically recalcitrant. Fulvic acids are organic acids which are soluble at any pH; humic acids are soluble above pH 2; and humin is insoluble under the full range of pH. Aquatic humus occurs in both dissolved and solid phases, with molecular weights ranging from about 500 D for dissolved fulvic acid to greater than 100,000 D for humic acids in sediments. Although the heterogeneity of these humic fractions makes rigorous chemical studies challenging, there are sufficient analytical methods at hand to make progress toward understanding the sources, formation pathways, and fate of aquatic humus.
Book chapter↗
Dissolved organic carbon concentrations and compositions, and trihalomethane formation potentials in waters from agricultural peat soils, Sacramento-San Joaquin Delta, California; implications for drinking-water quality
Water exported from the Sacramento-San Joaquin River delta (Delta) is an important drinking-water source for more than 20 million people in California. At times, this water contains elevated concentrations of dissolved organic carbon and bromide, and exceeds the U.S. Environmental Protection Agency's maximum contaminant level for trihalomethanes of 0.100 milligrams per liter if chlorinated for drinking water. About 20 to 50 percent of the trihalomethane precursors to Delta waters originates from drainage water from peat soils on Delta islands. This report elucidates some of the factors and processes controlling and affecting the concentration and quality of dissolved organic carbon released from peat soils and relates the propensity of dissolved organic carbon to form trihalomethanes to its chemical composition. Soil water was sampled from near-surface, oxidized, well-decomposed peat soil (upper soil zone) and deeper, reduced, fibrous peat soil (lower soil zone) from one agricultural field in the west central Delta over 1 year. Concentrations of dissolved organic carbon in the upper soil zone were highly variable, with median concentrations ranging from 46.4 to 83.2 milligrams per liter. Concentrations of dissolved organic carbon in samples from the lower soil zone were much less variable and generally slightly higher than samples from the upper soil zone, with median concentrations ranging from 49.3 to 82.3 milligrams per liter. The dissolved organic carbon from the lower soil zone had significantly higher aromaticity (as measured by specific ultraviolet absorbance) and contained significantly greater amounts of aromatic humic substances (as measured by XAD resin fractionation and carbon-13 nuclear magnetic resonance analysis of XAD isolates) than the dissolved organic carbon from the upper soil zone. These results support the conclusion that more aromatic forms of dissolved organic carbon are produced under anaerobic conditions compared to aerobic conditions. Dissolved organic carbon concentration, trihalomethane formation potential, and ultraviolet absorbance were all highly correlated, showing that trihalomethane precursors increased with increasing dissolved organic carbon and ultraviolet absorbance for whole water samples. Contrary to the generally accepted conceptual model for trihalomethane formation that assumes that aromatic forms of carbon are primary precursors to trihalomethanes, results from this study indicate that dissolved organic carbon aromaticity appears unrelated to trihalomethane formation on a carbon-normalized basis. Thus, dissolved organic carbon aromaticity alone cannot fully explain or predict trihalomethane precursor content, and further investigation of aromatic and nonaromatic forms of carbon will be needed to better identify trihalomethane precursors.
California↗
Sequestration of hydrophobic organic contaminants by geosorbents
The chemical interactions of hydrophobic organic contaminants (HOCs) with soils and sediments (geosorbents) may result in strong binding and slow subsequent release rates that significantly affect remediation rates and endpoints. The underlying physical and chemical phenomena potentially responsible for this apparent sequestration of HOCs by geosorbents are not well understood. This challenges our concepts for assessing exposure and toxicity and for setting environmental quality criteria. Currently there are no direct observational data revealing the molecular-scale locations in which nonpolar organic compounds accumulate when associated with natural soils or sediments. Hence macroscopic observations are used to make inferences about sorption mechanisms and the chemical factors affecting the sequestration of HOCs by geosorbents. Recent observations suggest that HOC interactions with geosorbents comprise different inorganic and organic surfaces and matrices, and distinctions may be drawn along these lines, particularly with regard to the roles of inorganic micropores, natural sorbent organic matter components, combustion residue particulate carbon, and spilled organic liquids. Certain manipulations of sorbates or sorbent media may help reveal sorption mechanisms, but mixed sorption phenomena complicate the interpretation of macroscopic data regarding diffusion of HOCs into and out of different matrices and the hysteretic sorption and aging effects commonly observed for geosorbents. Analytical characterizations at the microscale, and mechanistic models derived therefrom, are needed to advance scientific knowledge of HOC sequestration, release, and environmental risk.
Environmental Science & Technology↗
Hydrological and chemical estimates of the water balance of a closed-basin lake in north central Minnesota
Chemical mass balances for sodium, magnesium, chloride, dissolved organic carbon, and oxygen 18 were used to estimate groundwater seepage to and from Williams Lake, Minnesota, over a 15-month period, from April 1991 through June 1992. Groundwater seepage to the lake and seepage from the lake to groundwater were determined independently using a flow net approach using data from water table wells installed as part of the study. Hydrogeological analysis indicated groundwater seepage to the lake accounted for 74% of annual water input to the lake; the remainder came from atmospheric precipitation, as determined from a gage in the watershed and from nearby National Weather Service gages. Seepage from the lake accounted for 69% of annual water losses from the lake; the remainder was removed by evaporation, as determined by the energy budget method. Calculated annual water loss exceeded calculated annual water gain, and this imbalance was double the value of the independently measured decrease in lake volume. Seepage to the lake determined from oxygen 18 was larger (79% of annual water input) than that determined from the flow net approach and made the difference between calculated annual water gain and loss consistent with the independently measured decrease in lake volume. Although the net difference between volume of seepage to the lake and volume of seepage from the lake was 1% of average lake volume, movement of water into and out of the lake by seepage represented an annual exchange of groundwater with the lake equal to 26–27% of lake volume. Estimates of seepage to the lake from sodium, magnesium, chloride, and dissolved organic carbon did not agree with the values determined from flow net approach or oxygen 18. These results indicated the importance of using a combination of hydrogeological and chemical approaches to define volume of seepage to and from Williams Lake and identify uncertainties in chemical fluxes.
Minnesota↗
Interactions of mercury with dissolved organic carbon in the Florida Everglades
There has been increased awareness by both public and scientific communities over mercury contamination of game fish in South Florida. Effective management strategies for dealing with this problem will require a more thorough understanding of the factors and processes that result in the generation and transport of mercury, and control its reactivity in the Everglades. The role of mercury complexation by dissolved organic carbon (DOC) has been proposed by several investigators as a primary mechanism for the transport of mercury in aquatic systems. However, this relationship has been simply proposed based on a strong correlation between dissolved mercury and DOC concentrations in ground, lake and stream waters. Interactions with DOC may be an important process for controlling the transport and bioavailability of mercury. The issue of carbon reactivity in South Florida is especially relevant due to the high natural production of organic carbon in the peat soils and wetlands, the relatively high carbon content of shallow ground water systems in the region, the interactions of organic matter with mercury, other trace metals, and anthropogenic compounds, accumulation of organic carbon in corals and carbonate precipitates, and the potential changes in the quality and reactivity of dissolved organic carbon (DOC) resulting from land use practices. This study will attempt to meet the need to more clearly understand the dynamics of organic matter mercury interactions in the Florida Everglades by focusing research on the effect of dissolved organic carbon (DOC) on the transport and reactivity of Hg in the Everglades.
Florida↗
The aqueous photolysis of α-pinene in solution with humic acid
Terpenes are produced abundantly by environmental processes but are found in very low concentrations in natural waters. Aqueous photolysis of solutions containing α-pinene, a representative terpene, in the presence of humic acid resulted in degradation of the pinene. Comparison of this reaction to photolysis of α-pinene in the presence of methylene blue leads to the conclusion that the reactive pathway for the abiotic degradation of α-pinene is due to reaction with singlet oxygen produced by irradiation of the humic material. The initial product of single oxygen and α-pinene is a hydroperoxide. Since humic materials are prevalent in most natural waters, this mechanism of photodecomposition for α-pinene probably also applies to other terpenes in surface waters and may be reasonably considered to contribute to their low environmental concentration.
Journal of Contaminant Hydrology↗