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M.M. Reddy

Publications and source records attributed to M.M. Reddy.

At least 19 recordsLinked to original sources
USGS2011

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↗
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

Peat porewater chloride concentration profiles in the Everglades during wet/dry cycles from January 1996 to June 1998: Field measurements and theoretical analysis

Water quality is a key aspect of the Everglades Restoration Project, the largest water reclamation and ecosystem management project proposed in the United States. Movement of nutrients and contaminants to and from Everglades peat porewater could have important consequences for Everglades water quality and ecosystem restoration activities. In a study of Everglades porewater, we observed complex, seasonally variable peat porewater chloride concentration profiles at several locations. Analyses and interpretation of these changing peat porewater chloride concentration profiles identifies processes controlling conservative solute movement at the peat–surface water interface, that is, solutes whose transport is minimally affected by chemical and biological reactions. We examine, with an advection–diffusion model, how alternating wet and dry climatic conditions in the Florida Everglades mediate movement of chloride between peat porewater and marsh surface water. Changing surface water–chloride concentrations alter gradients at the interface between peat and overlying water and hence alter chloride flux across that interface. Surface water chloride concentrations at two frequently monitored sites vary with marsh water depth, and a transfer function was developed to describe daily marsh surface water chloride concentration as a function of marsh water depth. Model results demonstrate that porewater chloride concentrations are driven by changing surface water chloride concentrations, and a sensitivity analysis suggests that inclusion of advective transport in the model improves the agreement between the calculated and the observed chloride concentration profiles.

Hydrological Processes↗
USGS2006

Acid rain damage to carbonate stone: a quantitative assessment based on the aqueous geochemistry of rainfall runoff from stone

An onsite experimental procedure was used to identify and quantify acid rain damage to carbonate stone, based on the change in rain runoff chemical composition. Onsite data obtained during the summer and fall of 1984 at three locations in the northeastern United States indicate that carbonate stone surface recession is related to acid deposition. -from Author

Earth Surface Processes and Landforms↗
USGS2003

Characterization and diagenesis of strong-acid carboxyl groups in humic substances

A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

Applied Geochemistry↗
USGS2002

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 1. Minor structures

An investigation of the strong-acid characteristics (pKa 3.0 or less) of fulvic acid from the Suwannee River, Georgia, was conducted. Quantitative determinations were made for amino acid and sulfur-containing acid structures, oxalate half-ester structures, malonic acid structures, keto acid structures, and aromatic carboxyl-group structures. These determinations were made by using a variety of spectrometric (13C-nuclear magnetic resonance, infrared, and ultraviolet spectrometry) and titrimetric characterizations on fulvic acid or fulvic acid samples that were chemically derivatized to indicate certain functional groups. Only keto acid and aromatic carboxyl-group structures contributed significantly to the strong-acid characteristics of the fulvic acid; these structures accounted for 43% of the strong-acid acidity. The remaining 57% of the strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

Environmental Science & Technology↗
USGS2002

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures

Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the a-ether or a-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic a-ether and a-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

Environmental Science & Technology↗
USGS2002

Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions

Earlier research has shown that the acid dissociation and metal ion complexation equilibria of linear, weak-acid polyelectrolytes and their cross-linked gel analogues are similarly sensitive to the counterion concentration levels of their solutions. Gibbs-Donnan-based concepts, applicable to the gel, are equally applicable to the linear polyelectrolyte for the accommodation of this sensitivity to ionic strength. This result is presumed to indicate that the linear polyelectrolyte in solution develops counterion-concentrating regions that closely resemble the gel phase of their analogues. Advantage has been taken of this description of linear polyelectrolytes to estimate the solvent uptake by these regions. ?? 1991 American Chemical Society.

Journal of Physical Chemistry↗
USGS2001

Water chemistry at Snowshoe Mountain, Colorado: mixed processes in a common bedrock

At Snowshoe Mountain the primary bedrock is quite homogeneous, but weathering processes vary as waters moves through the soils, vadose zone and phreatic zone of the subsurface. In the thin soil, physical degradation of tuff facilitates preferential dissolution of potassium ion from glass within the rock matrix, while other silicate minerals remain unaltered. In the vadose zone, in the upper few meters of fractured bedrock, dilute water infiltrates during spring snowmelt and summer storms, leading to preferential dissolution of augite exposed on fracture surfaces. Deeper yet, in the phreatic zone of the fractured bedrock, Pleistocene calcite fracture fillings dissolve, and dioctahedral and trioctahedral clays form as penetrative weathering alters feldspar and pyroxene. Alkalinity is generated and silica concentrations are buffered by mineral alteration reactions.

Colorado↗
USGS2000

Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO 3 ). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (Ω = 4.5), P CO 2 (10 −3.5 atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not.

Florida↗
USGS2000

Transient calcite fracture fillings in a welded tuff, Snowshoe Mountain, Colorado

The core from two boreholes (13.1 and 19.2 m depth) drilled 500 m apart in the fractured, welded tuff near the summit of the Snowshoe Mountain, Colorado (47??30'N, 106??55'W) had unique petrographic and hydrodynamic properties. Borehole SM-4 had highly variable annual water levels, in contrast to SM-1a, whose water level remained near the land surface. Core samples from both boreholes (n = 10 and 11) were examined petrographically in thin sections impregnated with epoxy containing rhodamine to mark the pore system features, and were analyzed for matrix porosity and permeability. Core from the borehole sampling the vadose zone was characterized by open fractures with enhanced porosity around phenocrysts due to chemical weathering. Fractures within the borehole sampling the phreatic zone were mineralized with calcite and had porosity characteristics similar to Unweathered and unfractured rock. At the top of the phreatic zone petrography indicates that calcite is dissolving, thereby changing the hydrogeochemical character of the rock (i.e. permeability, porosity, reactive surface area, and mineralogy). Radiocarbon ages and C and O stable isotopes indicate that calcite mineralization occurred about 30 to 40 ka ago and that there was more than one mineralization event. Results of this study also provide some relationships between primary porosity development from 3 types of fracture in a welded tuff. (C) 2000 Elsevier Science Ltd.

Applied Geochemistry↗
USGS1999

Calcium ion binding to a soil fulvic acid using a donnan potential model

Calcium ion binding to a soil fulvic acid (Armadale Bh Horizon) was evaluated over a range of calcium ion concentrations, from pH 3.8 to 7.3, using potentiometric titrations and calcium ion electrode measurements. Fulvic acid concentration was constant (100 milligrams per liter) and calcium ion concentration varied up to 8 X 10 -4 moles per liter. Experiments discussed here included: (1) titrations of fulvic acid-calcium ion containing solutions with sodium hydroxide; and (2) titrations of fully neutralized fulvic acid with calcium chloride solutions. Apparent binding constants (expressed as the logarithm of the value, log β app ) vary with solution pH, calcium ion concentration, degree of acid dissociation, and ionic strength (from log β app = 2.5 to 3.9) and are similar to those reported by others. Fulvic acid charge, and the associated Donnan Potential, influences calcium ion-fulvic acid ion pair formation. A Donnan Potential corrrection term allowed calculation of intrinsic calcium ion-fulvic acid binding constants. Intrinsic binding constants vary from 1.2 to 2.5 (the average value is about log β = 1.6) and are similar to, but somewhat higher than, stability constants for calcium ion-carboxylic acid monodentate complexes.

Radiochimica Acta↗
USGS1999

Inhibition of precipitation and aggregation of metacinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

Precipitation and aggregation of metacinnabar (black HgS) was inhibited in the presence of low concentrations (≥3 mg C/L) of humic fractions of dissolved organic matter (DOM) isolated from the Florida Everglades. At low Hg concentrations (≤5 × 10 - 8 M), DOM prevented the precipitation of metacinnabar. At moderate Hg concentrations (5 × 10 - 5 M), DOM inhibited the aggregation of colloidal metacinnabar (Hg passed through a 0.1 μm filter but was removed by centrifugation). At Hg concentrations greater than 5 × 10 - 4 M, mercury formed solid metacinnabar particles that were removed from solution by a 0.1 μm filter. Organic matter rich in aromatic moieties was preferentially removed with the solid. Hydrophobic organic acids (humic and fulvic acids) inhibited aggregation better than hydrophilic organic acids. The presence of chloride, acetate, salicylate, EDTA, and cysteine did not inhibit the precipitation or aggregation of metacinnabar. Calcium enhanced metacinnabar aggregation even in the presence of DOM, but the magnitude of the effect was dependent on the concentrations of DOM, Hg, and Ca. Inhibition of metacinnabar precipitation appears to be a result of strong DOM-Hg binding. Prevention of aggregation of colloidal particles appears to be caused by adsorption of DOM and electrostatic repulsion.

Environmental Science & Technology↗
USGS1999

Importance of mechanical disaggregation in chemical weathering in a cold alpine environment, San Juan Mountains, Colorado

Weathering of welded tuff near the summit of Snowshoe Mountain (3660 m) in southwestern Colorado was studied by analyzing infiltrating waters in the soil and associated solid phases. Infiltrating waters exhibit anomalously high potassium to silica ratios resulting from dissolution of a potassium-rich glass that occurs as a trace phase in the rock. In laboratory experiments using rock from the field site, initial dissolution generated potassium-rich solutions similar to those observed in the field. The anomalous potassium release decreased over time (about 1 month), after which the dominant cation was calcium, with a much lower potassium to silica ratio.

Colorado↗
USGS1999

Pollution damage to the Powell Building, Reston, Virginia

Concrete column segments of the Powell Building (Reston, VA) exposed to the elements and wetted by precipitation were `cleaned' and roughened, but sheltered portions of the columns retained their smoothness and pollution accumulates, similar to observations for limestone, marble, and sandstone. Weathering effects on the columns were dominated by precipitation run-off and not the acidity of the precipitation. The process may be dry deposition of sulfur dioxide (SO2) and nitric oxides (NOx) that formed soluble salts in the presence of humid air or dew, salts that were removed by precipitation run-off.

Materials Performance↗