P. Westerhoff | Geology Reports

USGS2000

Concentrations and characteristics of organic carbon in surface water in Arizona: Influence of urbanization

Dissolved (DOC) and total (TOC) organic carbon concentrations and compositions were studied for several river systems in Arizona, USA. DOC composition was characterized by ultraviolet and visible absorption and fluorescence emission (excitation wavelength of 370 nm) spectra characteristics. Ephemeral sites had the highest DOC concentrations, and unregulated perennial sites had lower concentrations than unregulated intermittent sites, regulated sites, and sites downstream from wastewater-treatment plants (p < 0.05). Reservoir outflows and wastewater-treatment plant effluent were higher in DOC concentration (p < 0.05) and exhibited less variability in concentration than inflows to the reservoirs. Specific ultraviolet absorbance values at 254 nm were typically less than 2 m-1(milligram DOC per liter)-1 and lower than values found in most temperate-region rivers, but specific ultraviolet absorbance values increased during runoff events. Fluorescence measurements indicated that DOC in desert streams typically exhibit characteristics of autochthonous sources; however, DOC in unregulated upland rivers and desert streams experienced sudden shifts from autochthonous to allochthonous sources during runoff events. The urban water system (reservoir systems and wastewater-treatment plants) was found to affect temporal variability in DOC concentration and composition. (C) 2000 Elsevier Science B.V.Dissolved (DOC) and total (TOC) organic carbon concentrations and compositions were studied for several river systems in Arizona, USA. DOC composition was characterized by ultraviolet and visible absorption and fluorescence emission (excitation wavelength of 370 nm) spectra characteristics. Ephemeral sites had the highest DOC concentrations, and unregulated perennial sites had lower concentrations than unregulated intermittent sites, regulated sites, and sites downstream from wastewater-treatment plants (p<0.05). Reservoir outflows and wastewater-treatment plant effluent were higher in DOC concentration (p<0.05) and exhibited less variability in concentration than inflows to the reservoirs. Specific ultraviolet absorbance values at 254 nm were typically less than 2 m-1(milligram DOC per liter)-1 and lower than values found in most temperate-region rivers, but specific ultraviolet absorbance values increased during runoff events. Fluorescence measurements indicated that DOC in desert streams typically exhibit characteristics of autochthonous sources; however, DOC in unregulated upland rivers and desert streams experienced sudden shifts from autochthonous to allochthonous sources during runoff events. The urban water system (reservoir systems and wastewater-treatment plants) was found to affect temporal variability in DOC concentration and composition.The influence of urbanization, becoming increasingly common in arid regions, on dissolved organic carbon (DOC) concentrations in surface water resources was studied. DOC concentration and composition, seasonal watershed runoff events, streamflow variations, water management practices, and urban infrastructure in several Arizona watersheds were monitored. Ephemeral sites had the highest DOC levels, and unregulated perennial sites and lower concentrations than unregulated intermittent sites, regulated sites, and sites downstream from wastewater treatment plants. Reservoir outflows and wastewater treatment plant effluent had higher and less variable DOC concentrations than inflows to reservoirs. UV absorbance values, fluorescence measurements, and other indicators suggest that urban water systems (reservoirs and wastewater treatment plants) affect temporal variability in DOC concentration and composition.

Journal of Hydrology↗

USGS1999

Relationships between the structure of natural organic matter and its reactivity towards molecular ozone and hydroxyl radicals

Oxidation reaction rate parameters for molecular ozone (O3) and hydroxyl (HO) radicals with a variety of hydrophobic organic acids (HOAs) isolated from different geographic locations were determined from batch ozonation studies. Rate parameter values, obtained under equivalent dissolved organic carbon concentrations in both the presence and absence of non-NOM HO radical scavengers, varied as a function of NOM structure. First-order rate constants for O3 consumption (k(O3)) averaged 8.8 x 10-3 s-1, ranging from 3.9 x 10-3 s-1 for a groundwater HOA to > 16 x 10-3 s-1 for river HOAs with large terrestrial carbon inputs. The average second-order rate constant (k(HO,DOC) between HO radicals and NOM was 3.6 x 108 l (mol C)-1 s-1; a mass of 12 g C per mole C was used in all calculations. Specific ultraviolet absorbance (SUVA) at 254 or 280 nm of the HOAs correlated well (r > 0.9) with O3 consumption rate parameters, implying that organic ??-electrons strongly and selectively influence oxidative reactivity. HO radical reactions with NOM were less selective, although correlation between k(HO,DOC) and SUVA existed. Other physical-chemical properties of NOM, such as aromatic and aliphatic carbon content from 13C-NMR spectroscopy, proved less sensitive for predicting oxidation reactivity than SUVA. The implication of this study is that the structural nature of NOM varies temporally and spatially in a water source, and both the nature and amount of NOM will influence oxidation rates.

Water Research↗

USGS1999

Ozone-induced changes in natural organic matter (NOM) structure

Hydrophobic organic acids (combined humic and fulvic acids), obtained from an Antarctic Lake with predominantly microbially derived organic carbon sources and two US river systems with terrestrial organic carbon sources, were ozonated. Several analyses, including 13 C‐NMR, UV absorbance, fluorescence, hydrophobic/transphilic classification, and potentiometric titrations, were performed before and after ozonation. Ozonation reduced aromatic carbon content, selectively reducing phenolic carbon content. Ozonation of the samples resulted in increased aliphatic, carboxyl, plus acetal and ketal anomeric carbon content and shifted towards less hydrophobic compounds.

Ozone: Science and Engineering↗