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G. Aiken

Publications and source records attributed to G. Aiken.

9 recordsLinked to original sources

Mercury on the move during snowmelt in Vermont

Although mercury (Hg) emissions peaked in the United States over the last 20 to 40 years and are now declining, they remain well above natural background levels in soils and sediments. Only a small fraction of the Hg deposited from the atmosphere to the terrestrial landscape runs off in streamflow. However, some of this Hg is methylated in the environment and can potentially bioaccumulate to the top of food webs, posing a hazard to people who eat fish, especially children and pregnant women. What factors determine the amount of Hg that runs off in streams? During the 2000 snowmelt at Sleepers River in Vermont, strong correlations were found between dissolved and particulate mercury and the respective dissolved and particulate organic carbon fractions, even when data were pooled from 10 streams of diverse watershed size and land cover. Episodic export of particulate Hg during the highest flows appears to be the dominant mechanism of Hg movement.

Vermont

Using optical proxies for biogeochemical properties to study land coverage and terrestrial inputs of organic carbon into coastal waters from the Penobscot Watershed to the Gulf of Maine

Coastal waters are physically, biogeochemically, and therefore optically complex as a result of the commingling of waters arising from terrestrial, freshwater and marine ecosystems. Separating the influences of these three ecosystems on the optical properties of the resulting mixture is challenging, particularly given the variability within each. The longterm goals of this project are twofold: (1) to investigate the feasibility of identifying landuse changes using inwater optical observations, (2) to quantify the input of terrestrial organic carbon into the coastal marine environment. Our approach is to study the Penobscot River Watershed in Maine, from its many tributaries and subwatersheds into the main branch of the Penobscot River, Penobscot Bay and ultimately into the coastal waters of the Eastern Maine Coastal Current. The first step towards this goal is to define optical signatures associated with specific watershed land coverages measured at the source (optical proxies). The next step is to track those proxies from their respective sources to the coast, characterizing the dilution and transformative processes. Using analyses of discrete samples collected monthly from the subwatersheds, we have quantified optical proxies for both dissolved and particulate organic carbon, particulate carbon to nitrogen ratios and fluorophores unique to certain land coverages (e.g. wetlands, residence ponds, lumber mills, agriculture). We apply these proxies to in situ optical observations retrieved from sensors moored within the lower river and upper estuary to quantify the temporal patterns in the biogeochemical properties. To date we have approximately 2 years of observations, including the wettest year on record for the last century in this region. The proxies associated with the dissolved fraction are the most robust and provide signatures for both land coverage and for organic carbon concentration. Those associated with particles are robust proxies for carbon but are less informative about land coverage.

Maine

Interactions between dissolved organic matter and mercury in the Florida Everglades

Experiments were conducted using organic matter isolated from various surface waters in the Florida Everglades to study the interactions between dissolved organic matter (DOM) and Hg (II). Conditional distribution coefficients ( ), obtained using an equilibriurn dialysis ligand exchange method, were strongly affected by the Hg/DOM concentration ratio. Very strong interactions ( = 10 L kg -1 ), indicative of Hg-thiol bonds, were observed at Hg/DOM ratios below approximately 1 g Hg per mg DOM. Above approximately 10 g Hg per mg DOM much lower values ( L kg -1 ) were obtained. DOM-Hg interactions were also studied by HgS (log K ) dissolution and precipitation experiments. In the dissolution experiments, a significant amount of Hg was released from cinnabar in the presence of DOM, suggesting strong interactions. Conversely, precipitation of HgS was strongly inhibited in the presence of low concentrations ( 3 mg C/L) of DOM. In both the dissolution and precipitation experiments, organic matter rich in aromatic moities was more reactive with HgS than less aromatic fractions and sulfur-containing model compounds. These results suggest that DOM can influence the geochemistry of inorganic complexes of Hg in the Everglades, especially HgS, by strong Hg-DOM binding and colloidal stabilization.

Florida

Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances

The number- and weight-averaged molecular weights of a number of aquatic fulvic acids, a commercial humic acid, and unfractionated organic matter from four natural water samples were measured by high-pressure size exclusion chromatography (HPSEC). Molecular weights determined in this manner compared favorably with those values reported in the literature. Both recent literature values and our data indicate that these substances are smaller and less polydisperse than previously believed. Moreover, the molecular weights of the organic matter from three of the four natural water samples compared favorably to the fulvic acid samples extracted from similar environments. Bulk spectroscopic properties of the fulvic substances such as molar absorptivity at 280 nm and the E4/E6 ratio were also measured. A strong correlation was observed between molar absorptivity, total aromaticity, and the weight average molecular weights of all the humic substances. This observation suggests that bulk spectroscopic properties can be used to quickly estimate the size of humic substances and their aromatic contents. Both parameters are important with respect to understanding humic substance mobility and their propensity to react with both organic and inorganic pollutants.

Environmental Science & Technology

Assessment of relative accuracy in the determination of organic matter concentrations in aquatic systems

Accurate determinations of total (TOC), dissolved (DOC) and particulate (POC) organic carbon concentrations are critical for understanding the geochemical, environmental, and ecological roles of aquatic organic matter. Of particular significance for the drinking water industry, TOC measurements are the basis for compliance with US EPA regulations. The results of an interlaboratory comparison designed to identify problems associated with the determination of organic matter concentrations in drinking water supplies are presented. The study involved 31 laboratories and a variety of commercially available analytical instruments. All participating laboratories performed well on samples of potassium hydrogen phthalate (KHP), a compound commonly used as a standard in carbon analysis. However, problems associated with the oxidation of difficult to oxidize compounds, such as dodecylbenzene sulfonic acid and caffeine, were noted. Humic substances posed fewer problems for analysts. Particulate organic matter (POM) in the form of polystyrene beads, freeze-dried bacteria and pulverized leaf material were the most difficult for all analysts, with a wide range of performances reported. The POM results indicate that the methods surveyed in this study are inappropriate for the accurate determination of POC and TOC concentration. Finally, several analysts had difficulty in efficiently separating inorganic carbon from KHP solutions, thereby biasing DOC results.

Journal of Environmental Monitoring

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

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

Geochemistry of aquatic humic substances in the Lake Fryxell basin, Antarctica

Dissolved organic carbon (DOC) in Lake Fryxell, 10 streams flowing into the lake, and the moat surrounding the lake was studied to determine the influence of sources and biogeochemical processes on its distribution and chemical nature. Lake Fryxell is an amictic, permanently ice-covered lake in the McMurdo Dry Valleys which contains benthic and planktonic microbial populations, but receives essentially no input of organic material from the ahumic soils of the watershed. Biological activity in the water column does not appear to influence the DOC depth profile, which is similar to the profiles for conservative inorganic constituents. DOC values for the streams varied with biomass in the stream channel, and ranged from 0.2 to 9.7 mg C/L. Fulvic acids in the streams were a lower percentage of the total DOC than in the lake. These samples contain recent carbon and appear to be simpler mixtures of compounds than the lake samples, indicating that they have undergone less humification. The fulvic acids from just above the sediments of the lake have a high sulfur content and are highly aliphatic. The main transformations occurring as these fractions diffuse upward in the water column are 1) loss of sulfur groups through the oxycline and 2) decrease in aliphatic carbon and increase in the heterogeneity of aliphatic moieties. The fraction of modem 14C content of the lake fulvic acids range from a minimum of 0.68 (approximately 3000 years old) at 15m depth to 0.997 (recent material) just under the ice. The major processes controlling the DOC in the lake appear to be: 1) The transport of organic matter by the inflow streams resulting in the addition of recent organic material to the moat and upper waters of the lake; 2) The diffusion of organic matter composed of relict organic material and organic carbon resulting from the degradation of algae and bacteria from the bottom waters or sediments of the lake into overlying glacial melt water; 3) The addition of recent organic matter to the bottom waters of the lake from the moat.

Biogeochemistry