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M.M. Reddy

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

At least 37 records · Page 2Linked to original sources

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↗

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↗

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↗

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↗

Limestone characterization to model damage from acidic precipitation: Effect of pore structure on mass transfer

The pore structure of Salem limestone is investigated, and conclusions regarding the effect of the pore geometry on modeling moisture and contaminant transport are discussed based on thin section petrography, scanning electron microscopy, mercury intrusion porosimetry, and nitrogen adsorption analyses. These investigations are compared to and shown to compliment permeability and capillary pressure measurements for this common building stone. Salem limestone exhibits a bimodal pore size distribution in which the larger pores provide routes for convective mass transfer of contaminants into the material and the smaller pores lead to high surface area adsorption and reaction sites. Relative permeability and capillary pressure measurements of the air/water system indicate that Salem limestone exhibits high capillarity end low effective permeability to water. Based on stone characterization, aqueous diffusion and convection are believed to be the primary transport mechanisms for pollutants in this stone. The extent of contaminant accumulation in the stone depends on the mechanism of partitioning between the aqueous and solid phases. The described characterization techniques and modeling approach can be applied to many systems of interest such as acidic damage to limestone, mass transfer of contaminants in concrete and other porous building materials, and modeling pollutant transport in subsurface moisture zones.

Environmental Science & Technology↗

The effect of iron content and dissolved O 2 on dissolution rates of clinopyroxene at pH 5.8 and 25°C: Preliminary results

Dissolution experiments using augite (Mg 0.87 Ca 0.85 Fe 0.19 Na 0.09 Al 0.03 Si 2 O 6 ) and diopside (Mg 0.91 Ca 0.93 Fe 0.07 Na 0.03 Al 0.03 Si 2 O 6 ) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO 2 through a solution of 0.01 M KHCO 3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O 2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O 2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O 2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O 2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.

Chemical Geology↗

Computational scheme for the prediction of metal ion binding by a soil fulvic acid

The dissociation and metal ion binding properties of a soil fulvic acid have been characterized. Information thus gained was used to compensate for salt and site heterogeneity effects in metal ion complexation by the fulvic acid. An earlier computational scheme has been modified by incorporating an additional step which improves the accuracy of metal ion speciation estimates. An algorithm is employed for the prediction of metal ion binding by organic acid constituents of natural waters (once the organic acid is characterized in terms of functional group identity and abundance). The approach discussed here, currently used with a spreadsheet program on a personal computer, is conceptually envisaged to be compatible with computer programs available for ion binding by inorganic ligands in natural waters.

Analytica Chimica Acta↗

Specific surface area of a crushed welded tuff before and after aqueous dissolution

Specific surface areas were measured for several reference minerals (anorthoclase, labradorite and augite), welded tuff and stream sediments from Snowshoe Mountain, near Creede, Colorado. Crushed and sieved tuff had an unexpectedly small variation in specific surface area over a range of size fractions. Replicate surface area measurements of the largest and smallest tuff particle size fractions examined (1−0.3mm and<0.212mm) were 2.3 ± 0.2m 2 /g for each size fraction. Reference minerals prepared in the same way as the tuff had smaller specific surface areas than that of the tuff of the same size fraction. Higher than expected tuff specific surface areas appear to be due to porous matrix. Tuff, reacted in solutions with pH values from 2 to 6, had little change in specific surface area in comparison with unreacted tuff. Tuff, reacted with solutions having high acid concentrations (0.1 M hydrochloric acid or sulfuric-hydrofluoric acid), exhibited a marked increase in specific surface area compared to unreacted tuff.

Colorado↗

Welded tuff porosity characterization using mercury intrusion, nitrogen and ethylene glycol monoethyl ether sorption and epifluorescence microscopy

Porosity of welded tuff from Snowshoe Mountain, Colorado, was characterized by mercury intrusion porosimetry (MIP), nitrogen sorption porosimetry, ethylene glycol monoethyl ether (EGME) gas phase sorption and epifluorescence optical microscopy. Crushed tuff of two particle-size fractions (1-0.3 mm and less than 0.212 mm), sawed sections of whole rock and crushed tuff that had been reacted with 0.1 N hydrochloric acid were examined. Average MIP pore diameter values were in the range of 0.01–0.02μm. Intrusion volume was greatest for tuff reacted with 0.1 N hydrochloric acid and least for sawed tuff. Cut rock had the smallest porosity (4.72%) and crushed tuff reacted in hydrochloric acid had the largest porosity (6.56%). Mean pore diameters from nitrogen sorption measurements were 0.0075–0.0187 μm. Nitrogen adsorption pore volumes (from 0.005 to 0.013 cm 3 /g) and porosity values (from 1.34 to 3.21%) were less than the corresponding values obtained by MIP. More than half of the total tuff pore volume was associated with pore diameters < 0.05μm. Vapor sorption of EGME demonstrated that tuff pores contain a clay-like material. Epifluorescence microscopy indicated that connected porosity is heterogeneously distributed within the tuff matix; mineral grains had little porosity. Tuff porosity may have important consequences for contaminant disposal in this host rock.

Applied Geochemistry↗

Assessment of spatial variability of major-ion concentrations and del oxygen-18 values in surface snow, Upper Fremont Glacier, Wyoming, USA

One hundred samples were collected from the surface of the Upper Fremont Glacier at equally spaced intervals defined by an 8,100 m 2 snow grid to assess the significance of lateral variability in major-ion concentrations and del oxygen-18 values. For the major ions, the largest concentration range within the snow grid was sodium (0.5056 mg/l) and the smallest concentration range was sulfate (0.125 mg/l). Del oxygen-18 values showed a range of 7.45 per mil. Comparison of the observed variability of each chemical constituent to the variability expected by measurement error indicated substantial lateral variability within the surface-snow layer. Results of the nested ANOVA indicate most of the variance for every constituent is in the values grouped at the two smaller geographic scales (between 506 m 2 and within 506 m 2 sections). Calcium and sodium concentrations and del oxygen-18 values displayed the largest amount of variance at the largest geographic scale (between 2,025 m 2 sections) within the grid and ranged from 14 to 26 per cent of the total variance. The variance data from the snow grid were used to develop equations to evaluate the significance of both positive and negative concentration/value peaks of nitrate and del oxygen-18 with depth, in a 160 m ice core. Solving the equations indicates that both the nitrate and del oxygen-18 ice-core profiles have concentration/value trends that exceed the limits expected from lateral variability. Values of del oxygen-18 in the section from 110-150 m below the surface consistently vary outside the expected limits and possibly represents cooler temperatures during the Little Ice Age from about 1810 to 1725 A.D.

Wyoming↗

The erosion of carbonate stone by acid rain: Laboratory and field investigations

One of the goals of research on the effects of acidic deposition on carbonate stone surfaces is to define the incremental impact of acidic deposition relative to natural weathering processes on the rate of carbonate stone erosion. If rain that impacts carbonate stone surfaces is resident on the surface long enough to approach chemical equilibrium, the incremental effect of hydrogen ion is expected to be small (i.e., 6% for a rain of pH 4.0). Under nonequilibrium (i.e., high flow rate) conditions, kinetic considerations suggest that the incremental effect of hydrogen ion deposition could be quite significant. Field run-off experiments involving the chemical analysis of rain collected from inclined stone slabs have been used to evaluate stone dissolution processes under ambient conditions of wet and dry deposition of acidic species. The stoichiometry of the reaction of stone with hydrogen ion is difficult to define from the field data due to scatter in the data attributed to hydrodynamic effects. Laboratory run-off experiments show that the stoichiometry is best defined by a reaction with H+ in which CO2 is released from the system. The baseline effect caused by water in equilibrium with atmospheric CO2 is identical in the field and in laboratory simulation. The experiments show that the solutions are close enough to equilibrium for the incremental effect of hydrogen ion to be minor (i.e., 24% for marble for a rain of pH 4.0) relative to dissolution due to water and carbonic acid reactions. Stone erosion rates based on physical measurement are approximately double the recession rates that are due to dissolution (estimated from the observed calcium content of the run-off solutions). The difference may reflect the loss of granular material not included in recession estimates based on the run-off data. Neither the field nor the laboratory run-off experiments indicate a pH dependence for the grain-removal process.

Journal of Chemical Education↗

Effects of acidic deposition on the erosion of carbonate stone - experimental results from the U.S. National Acid Precipitation Assessment Program (NAPAP)

One of the goals of NAPAP-sponsored research on the effects of acidic deposition on carbonate stone has been to quantify the incremental effects of wet and dry deposition of hydrogen ion, sulfur dioxide and nitrogen oxides on stone erosion. Test briquettes and slabs of freshly quarried Indiana limestone and Vermont marble have been exposed to ambient environmental conditions in a long-term exposure program. Physical measurements of the recession of test stones exposed to ambient conditions at an angle of 30?? to horizontal at the five NAPAP materials exposure sites range from ~15 to ~30?? ??m yr-1 for marble, and from ~25 to ~45 ??m yr -1 for limestone, and are approximately double the recession estimates based on the observed calcium content of run-off solutions from test slabs. The difference between the physical and chemical recession measurements is attributed to the loss of mineral grains from the stone surfaces that are not measured in the run-off experiments. The erosion due to grain loss does not appear to be influenced by rainfall acidity, however, preliminary evidence suggests that grain loss may be influenced by dry deposition of sulfur dioxide between rainfall events. Chemical analyses of the run-off solutions and associated rainfall blanks suggest that ~30% of erosion by dissolution can be attributed to the wet deposition of hydrogen ion and the dry deposition of sulfur dioxide and nitric acid between rain events. The remaining ~70% of erosion by dissolution is accounted for by the solubility of carbonate stone in rain that is in equilibrium with atmospheric carbon dioxide ('clean rain'). These results are for marble and limestone slabs exposed at an angle of 30?? from horizontal. The relative contribution of sulfur dioxide to chemical erosion is significantly enhanced for stone slabs having an inclination of 60?? or 85??. The dry deposition of alkaline particulate material has a mitigating effect at the two urban field exposure sites at Washington, DC, and Steubenville, OH.

Conference Paper↗

A monitor for continuous measurement of temperature, pH, and conductance of wet precipitation: Preliminary results from the Adirondack Mountains, New York

This report describes a continuous wet-only precipitation monitor designed by the U.S. Geological Survey to record variations in rainfall temperature, pH, and specific conductance at 1-min intervals over the course of storms. Initial sampling in the Adirondack Mountains showed that rainfall acidity varied over the course of summer storms, with low initial pH values increasing as storm intensity increased.

New York↗

Vapor-pressure osmometric study of the molecular weight and aggregation tendency of a reference-soil fulvic acid

The molecular weight and aggregation tendency of a reference-soil fulvic acid in Armadale horizon Bh were determined by vapor-pressure osmometry using tetrahydrofuran and water as solvents. With tetrahydrofuran, number-average molecular weight values of 767 ?? 34 and 699 ?? 8 daltons were obtained from two separate sets of measurements. Two sets of measurements with water also yielded values within this range (754 ?? 70 daltons) provided that the fulvic acid concentration in water did not exceed 7 mg ml-1; at higher concentrations (9.1-13.7 mg ml-1) a number-average molecular weight of 956 ?? 25 daltons was resolved, providing evidence of molecular aggregation. Extension of these studies to 80% neutralized fulvic acid showed that a sizeable fraction of the sodium counter ion is not osmotically active.

Analytica Chimica Acta↗

Description and testing of three moisture sensors for measuring surface wetness on carbonate building stones

Three moisture sensors were tested as a means for determining the surface wetness on carbonate building stones exposed to conditions that produce deposition of moisture. A relative-humidity probe, a gypsum-coated circuit grid, and a limestone-block resistor were tested as sensors for determining surface wetness. Sensors were tested under laboratory conditions of constant relative humidity and temperature and also under on-site conditions of variable relative humidity and temperature for eight weeks at Newcomb, NY. Laboratory tests indicated that relative humidity alone did not cause sensors to become saturated with water. However, the rates of drying indicated by the sensors after an initial saturation were inversely related to the relative humidity. On-site testing of the relative-humidity probe and the gypsum-coated ciruit grid indicated that they respond to a diurnal wetting and drying cycle; the limestone-block resistor responded only to rainfall.

Review of Scientific Instruments↗

Cadmium, copper, lead, and zinc determination in precipitation: A comparison of inductively coupled plasma atomic emission spectrometry and graphite furnace atomization atomic absorption spectrometry

Selected trace element analysis for cadmium, copper, lead, and zinc in precipitation samples by inductively coupled plasma atomic emission Spectrometry (ICP) and by atomic absorption spectrometry with graphite furnace atomization (AAGF) have been evaluated. This task was conducted in conjunction with a longterm study of precipitation chemistry at high altitude sites located in remote areas of the southwestern United States. Coefficients of variation and recovery values were determined for a standard reference water sample for all metals examined for both techniques. At concentration levels less than 10 micrograms per liter AAGF analyses exhibited better precision and accuracy than ICP. Both methods appear to offer the potential for cost-effective analysis of trace metal ions in precipitation. ?? 1987 Springer-Verlag.

Mikrochimica Acta↗