Geology topics

G. R. Aiken

Publications and source records attributed to G. R. Aiken.

At least 19 recordsLinked to original sources

USGS2012

Landscape controls on total and methyl Hg in the Upper Hudson River basin, New York, USA

Approaches are needed to better predict spatial variation in riverine Hg concentrations across heterogeneous landscapes that include mountains, wetlands, and open waters. We applied multivariate linear regression to determine the landscape factors and chemical variables that best account for the spatial variation of total Hg (THg) and methyl Hg (MeHg) concentrations in 27 sub-basins across the 493 km 2 upper Hudson River basin in the Adirondack Mountains of New York. THg concentrations varied by sixfold, and those of MeHg by 40-fold in synoptic samples collected at low-to-moderate flow, during spring and summer of 2006 and 2008. Bivariate linear regression relations of THg and MeHg concentrations with either percent wetland area or DOC concentrations were significant but could account for only about 1/3 of the variation in these Hg forms in summer. In contrast, multivariate linear regression relations that included metrics of (1) hydrogeomorphology, (2) riparian/wetland area, and (3) open water, explained about 66% to >90% of spatial variation in each Hg form in spring and summer samples. These metrics reflect the influence of basin morphometry and riparian soils on Hg source and transport, and the role of open water as a Hg sink. Multivariate models based solely on these landscape metrics generally accounted for as much or more of the variation in Hg concentrations than models based on chemical and physical metrics, and show great promise for identifying waters with expected high Hg concentrations in the Adirondack region and similar glaciated riverine ecosystems.

New York↗

USGS2012

Mercury species and other selected constituent concentrations in water, sediment, and biota of Sinclair Inlet, Kitsap County, Washington, 2007-10

This report presents data collected for two U.S. Geological Survey field sampling projects related to mercury (Hg) in Sinclair Inlet: (1) the Watersheds Sources Project that evaluated the sources of mercury to Sinclair Inlet during December 2007 to March 2010, and (2) the Methylation and Bioaccumulation Project, a comprehensive examination of mercury biogeochemistry in sediment, water, and zooplankton during August 2008–February 2010. For the Watershed Sources project, nonpoint and point sources of mercury to Sinclair Inlet from the Bremerton naval complex (BNC) were evaluated by using filtered total mercury and particulate total mercury measured in water samples collected from 11 wells, 2 dry dock sump discharges, and a steam plant's effluent at the BNC. Methylmercury sources to the inlet were examined by determining filtered methylmercury concentrations in water samples collected from five wells, two dry dock sump discharges, a steam plant's effluent, five intertidal piezometers, and three stormwater drains on the BNC, as well as in samples from five creeks, two wastewater treatment facilities, and three stormwater drains in the Sinclair Inlet watershed outside of the BNC. An improved understanding of tidally modulated mercury migration to Sinclair Inlet from the BNC was gained through three intensive nearshore (tidal) sampling events of mercury species in groundwater and a nearby stormwater drain. The Methylation and Bioaccumulation Project included a comprehensive field study of mercury biogeochemistry in marine sediment, water, and zooplankton in Sinclair Inlet. Mercury, iron, and sulfur species in sediment porewater from six sites within and three sites outside of Sinclair Inlet were measured to provide insight into the processes that produce methylmercury in the sediments. Total mercury, methylmercury, dissolved organic carbon, and redox-sensitive species were measured in porewaters in the top 2 centimeters of sediment, and these data were paired with sedimentary flux measurements from core incubation experiments to connect sedimentary processes to the water column. A broad-scale study of mercury methylation potential and mercury species at 20-plus stations in Sinclair Inlet was conducted in February 2009 and 2010, June 2009, and August 2009. Sedimentary flux measurements and analysis of mercury and biogeochemicals in sediment porewater and bottom water were made at six of the broad-scale stations. Bioaccumulation processes in the water column in the context of the sedimentary flux of methylmercury were examined using monthly survey data collected between August 2008 and August 2009. The survey data included concentrations of methylmercury and isotope ratios of carbon and nitrogen in bulk zooplankton measured at four stations in Sinclair Inlet in the context of the population of bulk zooplankton ascertained by taxonomical identification. The analysis of filtered total mercury, total particulate mercury, filtered methylmercury, particulate methylmercury, chlorophyll a, isotopes of carbon and nitrogen in suspended matter, and other biogeochemical data will facilitate the examination of the biogeochemistry of mercury in Sinclair Inlet.

Washington↗

USGS2011

Mercury export from the Yukon River Basin and potential response to a changing climate

We measured mercury (Hg) concentrations and calculated export and yield from the Yukon River Basin (YRB) to quantify Hg flux from a large, permafrost-dominated, high-latitude watershed. Exports of Hg averaged 4400 kg Hg yr -1 . The average annual yield for the YRB during the study period was 5.17 μg m -2 yr -1 , which is 3–32 times more than Hg yields reported for 8 other major northern hemisphere river basins. The vast majority (90%) of Hg export is associated with particulates. Half of the annual export of Hg occurred during the spring with about 80% of 34 samples exceeding the U.S. EPA Hg standard for adverse chronic effects to biota. Dissolved and particulate organic carbon exports explained 81% and 50%, respectively, of the variance in Hg exports, and both were significantly ( p < 0.001) correlated with water discharge. Recent measurements indicate that permafrost contains a substantial reservoir of Hg. Consequently, climate warming will likely accelerate the mobilization of Hg from thawing permafrost increasing the export of organic carbon associated Hg and thus potentially exacerbating the production of bioavailable methylmercury from permafrost-dominated northern river basins.

Alaska↗

USGS2011

Metallothionein-like multinuclear clusters of mercury(II) and sulfur in peat

Strong mercury(II)–sulfur (Hg-SR) bonds in natural organic matter, which influence mercury bioavailability, are difficult to characterize. We report evidence for two new Hg-SR structures using X-ray absorption spectroscopy in peats from the Florida Everglades with added Hg. The first, observed at a mole ratio of organic reduced S to Hg (S red /Hg) between 220 and 1140, is a Hg 4 S x type of cluster with each Hg atom bonded to two S atoms at 2.34 Å and one S at 2.53 Å, and all Hg atoms 4.12 Å apart. This model structure matches those of metal–thiolate clusters in metallothioneins, but not those of HgS minerals. The second, with one S atom at 2.34 Å and about six C atoms at 2.97 to 3.28 Å, occurred at S red /Hg between 0.80 and 4.3 and suggests Hg binding to a thiolated aromatic unit. The multinuclear Hg cluster indicates a strong binding environment to cysteinyl sulfur that might impede methylation. Along with a linear Hg(SR) 2 unit with Hg—S bond lengths of 2.34 Å at S red /Hg of about 10 to 20, the new structures support a continuum in Hg-SR binding strength in natural organic matter.

Environmental Science & Technology↗

USGS2011

Effects of sediment-associated extractable metals, degree of sediment grain sorting, and dissolved organic carbon upon Cryptosporidium parvum removal and transport within riverbank filtration sediments, Sonoma County, California

Oocysts of the protozoan pathogen Cryptosporidium parvum are of particular concern for riverbank filtration (RBF) operations because of their persistence, ubiquity, and resistance to chlorine disinfection. At the Russian River RBF site (Sonoma County, CA), transport of C. parvum oocysts and oocyst-sized (3 μm) carboxylate-modified microspheres through poorly sorted (sorting indices, σ 1 , up to 3.0) and geochemically heterogeneous sediments collected between 2 and 25 m below land surface (bls) were assessed. Removal was highly sensitive to variations in both the quantity of extractable metals (mainly Fe and Al) and degree of grain sorting. In flow-through columns, there was a log–linear relationship ( r 2 = 0.82 at p < 0.002) between collision efficiency (α, the probability that colloidal collisions with grain surfaces would result in attachment) and extractable metals, and a linear relationship ( r 2 = 0.99 at p < 0.002) between α and σ 1 . Collectively, variability in extractable metals and grain sorting accounted for ∼83% of the variability in α (at p < 0.0002) along the depth profiles. Amendments of 2.2 mg L –1 of Russian River dissolved organic carbon (DOC) reduced α for oocysts by 4–5 fold. The highly reactive hydrophobic organic acid (HPOA) fraction was particularly effective in re-entraining sediment-attached microspheres. However, the transport-enhancing effects of the riverine DOC did not appear to penetrate very deeply into the underlying sediments, judging from high α values (∼1.0) observed for oocysts being advected through unamended sediments collected at ∼2 m bls. This study suggests that in evaluating the efficacy of RBF operations to remove oocysts, it may be necessary to consider not only the geochemical nature and size distribution of the sediment grains, but also the degrees of sediment sorting and the concentration, reactivity, and penetration of the source water DOC.

California↗

USGS2010

Influence of organic carbon loading, sediment associated metal oxide content and sediment grain size distributions upon Cryptosporidium parvum removal during riverbank filtration operations, Sonoma County, CA

This study assessed the efficacy for removing Cryptosporidium parvum oocysts of poorly sorted, Fe- and Al-rich, subsurface sediments collected from 0.9 to 4.9 and 1.7–13.9 m below land surface at an operating riverbank filtration (RBF) site (Russian River, Sonoma County, CA). Both formaldehyde-killed oocysts and oocyst-sized (3 μm) microspheres were employed in sediment-packed flow-through and static columns. The degree of surface coverage of metal oxides on sediment grain surfaces correlated strongly with the degrees of oocyst and microsphere removals. In contrast, average grain size ( D 50 ) was not a good indicator of either microsphere or oocyst removal, suggesting that the primary mechanism of immobilization within these sediments is sorptive filtration rather than physical straining. A low specific UV absorbance (SUVA) for organic matter isolated from the Russian River, suggested that the modest concentration of the SUVA component (0.8 mg L −1 ) of the 2.2 mg L −1 dissolved organic carbon (DOC) is relatively unreactive. Nevertheless, an amendment of 2.2 mg L −1 of isolated river DOC to column sediments resulted in up to a 35.7% decrease in sorption of oocysts and (or) oocyst-sized microspheres. Amendments (3.2 μM) of the anionic surfactant, sodium dodecyl benzene sulfonate (SDBS) also caused substantive decreases (up to 31.9 times) in colloid filtration. Although the grain-surface metal oxides were found to have a high colloid-removal capacity, our study suggested that any major changes within the watershed that would result in long-term alterations in either the quantity and (or) the character of the river's DOC could alter the effectiveness of pathogen removal during RBF operations.

Water Research↗

USGS2009

Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

[1] The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long‐term DOC monitoring data. Intensive sampling across the historically under‐sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean.

Geophysical Research Letters↗

USGS2009

Mercury cycling in stream ecosystems. 3. Trophic dynamics and methylmercury bioaccumulation

Trophic dynamics (community composition and feeding relationships) have been identified as important drivers of methylmercury (MeHg) bioaccumulation in lakes, reservoirs, and marine ecosystems. The relative importance of trophic dynamics and geochemical controls on MeHg bioaccumulation in streams, however, remains poorly characterized. MeHg bioaccumulation was evaluated in eight stream ecosystems across the United States (Oregon, Wisconsin, and Florida) spanning large ranges in climate, landscape characteristics, atmospheric Hg deposition, and stream chemistry. Across all geographic regions and all streams, concentrations of total Hg (THg) in top predator fish and forage fish, and MeHg in invertebrates, were strongly positively correlated to concentrations of filtered THg (FTHg), filtered MeHg (FMeHg), and dissolved organic carbon (DOC); to DOC complexity (as measured by specific ultraviolet absorbance); and to percent wetland in the stream basins. Correlations were strongest for nonurban streams. Although regressions of log[Hg] versus δ 15 N indicate that Hg in biota increased significantly with increasing trophic position within seven of eight individual streams, Hg concentrations in top predator fish (including cutthroat, rainbow, and brown trout; green sunfish; and largemouth bass) were not strongly influenced by differences in relative trophic position. Slopes of log[Hg] versus δ 15 N, an indicator of the efficiency of trophic enrichment, ranged from 0.14 to 0.27 for all streams. These data suggest that, across the large ranges in FTHg (0.14−14.2 ng L −1 ), FMeHg (0.023−1.03 ng L −1 ), and DOC (0.50−61.0 mg L −1 ) found in this study, Hg contamination in top predator fish in streams likely is dominated by the amount of MeHg available for uptake at the base of the food web rather than by differences in the trophic position of top predator fish.

Environmental Science & Technology↗

USGS2009

Hydrologic support of carbon dioxide flux revealed by whole-lake carbon budgets

Freshwater lakes are an important component of the global carbon cycle through both organic carbon (OC) sequestration and carbon dioxide (CO 2 ) emission. Most lakes have a net annual loss of CO 2 to the atmosphere and substantial current evidence suggests that biologic mineralization of allochthonous OC maintains this flux. Because net CO 2 flux to the atmosphere implies net mineralization of OC within the lake ecosystem, it is also commonly assumed that net annual CO 2 emission indicates negative net ecosystem production (NEP). We explored the relationship between atmospheric CO 2 emission and NEP in two lakes known to have contrasting hydrologie characteristics and net CO 2 emission. We calculated NEP for calendar year 2004 using whole-lake OC and inorganic carbon (IC) budgets, NEP oc and NEP IC , respectively, and compared the resulting values to measured annual CO 2 flux from the lakes. In both lakes, NEP Ic and NEP Ic were positive, indicating net autotrophy. Therefore CO 2 emission from these lakes was apparently not supported by mineralization of allochthonous organic material. In both lakes, hydrologie CO 2 inputs, as well as CO 2 evolved from netcalcite precipitation, could account for the net CO 2 emission. NEP calculated from diel CO 2 measurements was also affected by hydrologie inputs of CO 2 . These results indicate that CO 2 emission and positive NEP may coincide in lakes, especially in carbonate terrain, and that all potential geologic, biogeochemical, and hydrologie sources of CO 2 need to be accounted for when using CO 2 concentrations to infer lake NEP. Copyright 2009 by the American Geophysical Union.

Journal of Geophysical Research G: Biogeosciences↗

USGS2009

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg d ), DOC concentration and DOC composition, and UV 254 absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg d to DOC (r 2 = 0.87), but progressively stronger correlations of THg d with the hydrophobic acid fraction (HPOA) of DOC (r 2 = 0.91) and with UV 254 absorbance (r 2 = 0.92). The strength of the UV 254 absorbance-THg d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg d flux in drainage waters.

Environmental Pollution↗

USGS2008

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1 ng L −1 and MeHg was less than 0.2 ng L −1 . THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56) ng L −1 at Sleepers River, Vermont; 112 (0.75) ng L −1 at Rio Icacos, Puerto Rico; and 55 (0.80) ng L −1 at Panola Mt., Georgia. Filtered (<0.7 μm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5 ng L −1 at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.

Environmental Pollution↗

USGS2007

Flux and age of dissolved organic carbon exported to the Arctic Ocean: A carbon isotopic study of the five largest arctic rivers

The export and Δ 14 C-age of dissolved organic carbon (DOC) was determined for the Yenisey, Lena, Ob', Mackenzie, and Yukon rivers for 2004–2005. Concentrations of DOC elevate significantly with increasing discharge in these rivers, causing approximately 60% of the annual export to occur during a 2-month period following spring ice breakup. We present a total annual flux from the five rivers of ∼16 teragrams (Tg), and conservatively estimate that the total input of DOC to the Arctic Ocean is 25–36 Tg, which is ∼5–20% greater than previous fluxes. These fluxes are also ∼2.5× greater than temperate rivers with similar watershed sizes and water discharge. Δ 14 C-DOC shows a clear relationship with hydrology. A small pool of DOC slightly depleted in Δ 14 C is exported with base flow. The large pool exported with spring thaw is enriched in Δ 14 C with respect to current-day atmospheric Δ 14 C-CO 2 values. A simple model predicts that ∼50% of DOC exported during the arctic spring thaw is 1–5 years old, ∼25% is 6–10 years in age, and 15% is 11–20 years old. The dominant spring melt period, a historically undersampled period, exports a large amount of young and presumably semilabile DOC to the Arctic Ocean.

Global Biogeochemical Cycles↗

USGS2007

Mercury and organic carbon dynamics during runoff episodes from a northeastern USA watershed

Mercury and organic carbon concentrations vary dynamically in streamwater at the Sleepers River Research Watershed in Vermont, USA. Total mercury (THg) concentrations ranged from 0.53 to 93.8 ng/L during a 3-year period of study. The highest mercury (Hg) concentrations occurred slightly before peak flows and were associated with the highest organic carbon (OC) concentrations. Dissolved Hg (DHg) was the dominant form in the upland catchments; particulate Hg (PHg) dominated in the lowland catchments. The concentration of hydrophobic acid (HPOA), the major component of dissolved organic carbon (DOC), explained 41–98% of the variability of DHg concentration while DOC flux explained 68–85% of the variability in DHg flux, indicating both quality and quantity of the DOC substantially influenced the transport and fate of DHg. Particulate organic carbon (POC) concentrations explained 50% of the PHg variability, indicating that POC is an important transport mechanism for PHg. Despite available sources of DHg and wetlands in the upland catchments, dissolved methylmercury (DmeHg) concentrations in streamwaters were below detection limit (0.04 ng/L). PHg and particulate methylmercury (PmeHg) had a strong positive correlation ( r 2 = 0.84, p < 0.0001), suggesting a common source; likely in-stream or near-stream POC eroded or re-suspended during spring snowmelt and summer storms. Ratios of PmeHg to THg were low and fairly constant despite an apparent higher methylmercury (meHg) production potential in the summer. Methylmercury production in soils and stream sediments was below detection during snowmelt in April and highest in stream sediments (compared to forest and wetland soils) sampled in July. Using the watershed approach, the correlation of the percent of wetland cover to TmeHg concentrations in streamwater indicates that poorly drained wetland soils are a source of meHg and the relatively high concentrations found in stream surface sediments in July indicate these zones are a meHg sink.

Water, Air, & Soil Pollution↗

USGS2007

DOM in recharge waters of the Santa Ana River Basin

Assessment of the composition, reactivity, and potential health effects of dissolved organic matter (DOM) is an important issue in the regulation and operation of groundwater recharge projects. The composition of DOM in various natural surface waters and reclaimed waters used to recharge the alluvial aquifers of the lower Santa Ana River Basin in California was derived primarily from terpenoid hydrocarbons and amino sugars. Lesser amounts of aromatic sulfonate and alkylphenol polyethoxylate metabolites of anionic and neutral surfactants were detected in reclaimed water, and these metabolites persisted in waters of the Santa Ana River, the Prado Wetland, and the recharge basins. Only small amounts of humic substances derived from tannins and lignins were deposited during storm flow periods in the Prado Wetland, but these amounts were responsible for significant increases in disinfection by-product formation potential in these waters. Colloids composed of bacterial cell wall fragments showed large percentage increases in all waters during storm flow periods.

California↗

USGS2006

Evidence for the aquatic binding of arsenate by natural organic matter-suspended Fe(III)

Dialysis experiments with arsenate and three different NOM samples amended with Fe(III) showed evidence confirming the formation of aquatic arsenate-Fe(III)-NOM associations. A linear relationship was observed between the amount of complexed arsenate and the Fe(III) content of the NOM. The dialysis results were consistent with complex formation through ferric iron cations acting as bridges between the negatively charged arsenate and NOM functional groups and/or a more colloidal association, in which the arsenate is bound by suspended Fe(III)-NOM colloids. Sequential filtration experiments confirmed that a significant proportion of the iron present at all Fe/C ratios used in the dialysis experiments was colloidal in nature. These colloids may include larger NOM species that are coagulated by the presence of chelated Fe(III) and/or NOM-stabilized ferric (oxy)hydroxide colloids, and thus, the solution-phase arsenate-Fe(III)-NOM associations are at least partially colloidal in nature. ?? 2006 American Chemical Society.

Environmental Science & Technology↗

USGS2005

A decrease in discharge-normalized DOC export by the Yukon River during summer through autumn

Climate warming is having a dramatic effect on the vegetation distribution and carbon cycling of terrestrial subarctic and arctic ecosystems. Here, we present hydrologic evidence that warming is also affecting the export of dissolved organic carbon and bicarbonate (DOC and HCO 3 − ) at the large basin scale. In the 831,400 km 2 Yukon River basin, water discharge (Q) corrected DOC export significantly decreased during the growing season from 1978–80 to 2001–03, indicating a major shift in terrestrial to aquatic C transfer. We conclude that decreased DOC export, relative to total summer through autumn Q, results from increased flow path, residence time, and microbial mineralization of DOC in the soil active layer and groundwater. Counter to current predictions, we argue that continued warming could result in decreased DOC export to the Bering Sea and Arctic Ocean by major subarctic and arctic rivers, due to increased respiration of organic C on land.

Geophysical Research Letters↗

USGS2005

Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

Environmental Science & Technology↗

USGS2005

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10 −13 to 7.16 × 10 −12 mol Hg (mg C) −1 m −2 s −1 . Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R 2 = 0.88), aromaticity (R 2 = 0.80), and molecular weight (R 2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.

Geochimica et Cosmochimica Acta↗