Michael M. Reddy

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 (CaCO3). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (Ω = 4.5), PCO2 (10−3.5atm), 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.

Hydrological and chemical estimates of the water balance of a closed-basin lake in north central Minnesota

Chemical mass balances for sodium, magnesium, chloride, dissolved organic carbon, and oxygen 18 were used to estimate groundwater seepage to and from Williams Lake, Minnesota, over a 15-month period, from April 1991 through June 1992. Groundwater seepage to the lake and seepage from the lake to groundwater were determined independently using a flow net approach using data from water table wells installed as part of the study. Hydrogeological analysis indicated groundwater seepage to the lake accounted for 74% of annual water input to the lake; the remainder came from atmospheric precipitation, as determined from a gage in the watershed and from nearby National Weather Service gages. Seepage from the lake accounted for 69% of annual water losses from the lake; the remainder was removed by evaporation, as determined by the energy budget method. Calculated annual water loss exceeded calculated annual water gain, and this imbalance was double the value of the independently measured decrease in lake volume. Seepage to the lake determined from oxygen 18 was larger (79% of annual water input) than that determined from the flow net approach and made the difference between calculated annual water gain and loss consistent with the independently measured decrease in lake volume. Although the net difference between volume of seepage to the lake and volume of seepage from the lake was 1% of average lake volume, movement of water into and out of the lake by seepage represented an annual exchange of groundwater with the lake equal to 26–27% of lake volume. Estimates of seepage to the lake from sodium, magnesium, chloride, and dissolved organic carbon did not agree with the values determined from flow net approach or oxygen 18. These results indicated the importance of using a combination of hydrogeological and chemical approaches to define volume of seepage to and from Williams Lake and identify uncertainties in chemical fluxes.

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.

Use of the chloride ion in determining hydrologic-basin water budgets - A 3-year case study in the San Juan Mountains, Colorado, U.S.A.

Abstract Measurement of chloride concentration and water equivalent in precipitation and recharge at a site can be extrapolated to determine available moisture in a nearby basin. This method also may be extrapolated to a basin with similar climatic characteristics if precipitation, vegetation, and topographic data are available. The average accuracy of the total of evaporation, recharge, and runoff (assuming no storage) was about 10% of total precipitation. Soil-moisture measurements indicate the entire 10% error in moisture balance can be attributed to annual changes in storage. Data requirements for the method are considerably less than data requirements for energy-budget methods to determine available moisture. Potential applications of the method to hydrologic problem-solving are: 1. (1) Estimating total available moisture from chloride concentrations in groundwater or surface water or both. 2. (2) Modeling paleoclimate scenarios and evaluating their correctness by comparison with paleo-groundwater chloride concentrations. 3. (3) Providing an independent comparison for water budgets obtained by energy-budget methods. Obviously the method cannot be applied readily to systems with a lithologic source of chloride. Most systems primarily consisting of tuff, intrusive volcanic rock, nonmarine sediments, quartzite, and other metamorphic rocks will be suitable for application of the model.

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. The anomalous potassium concentrations observed in the infiltrating soil solutions result from weathering of freshly exposed rock surfaces. Continual mechanical disaggregation of the rock due to segregation freezing exposes fresh glass to weathering and thus maintains the source of potassium for the infiltrating water. The ongoing process of creation of fresh surfaces by physical processes is an important influence on the composition of infiltrating waters in the vadose zone.

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

Abstract 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 μm yr−1 for marble, and from ∼ 25 to ∼ 45 μm 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.

Estimates of average major ion concentrations in bulk precipitation at two high-altitude sites near the continental divide in Southwestern Colorado

Abstract The composition of bulk precipitation from two high-altitude sites, established in 1971 near the Continental Divide in southwestern Colorado, has been monitored by season during the past decade. Calcium ions are the predominant cationic species; sulfate is the major anionic consitituent. Bulk precipitation major ion concentrations exhibit log-normal distributions. Representative mean and standard deviation values for the major inorganic ionic species present in bulk precipitation have been calculated for three years of consecutive seasons. Standard deviations for all species, except nitrate, are similar. For two years of data grouped into quarters, deviations from mean values fall well within the plus or minus two standard deviation limit. There does not seem to be a systematic deviation from the mean concentration values, with respect to either ionic component or season.

Influence of Humic Compounds on the Crystal Growth of Hydroxyapatite

The influence of several natural and synthetic additives containing hydroxy and/or carboxyl groups on the kinetics of crystal growth of hydroxyapatite (HAP) at sustained supersaturation has been investigated using the constant composition method. Addition of low levels (0.25 to 5 parts per million) of fulvic acid, tannic acid, benzene hexacarboxylic acid, and poly(acrylic acid) to supersaturated calcium phosphate solutions has an inhibitory influence upon the rate of crystal growth of HAP. Salicyclic acid, under similar experimental conditions, is an ineffective HAP growth inhibitor. Kinetic analysis suggests Langmuir-type adsorption of added ions on the HAP surfaces with a relatively high affinity for the substrate in the concentration range investigated.

Carbonate Precipitation in Pyramid Lake, Nevada

Magnesium ion inhibition of calcium carbonate (calcite) formation explains present-day controls on carbonate formation in Pyramid Lake. Concentrations of magnesium ion are sufficient to reduce calcium carbonate nucleation rates and calcite formation rates in present-day supersaturated lake water. Calcium carbonate nucleation and crystal growth measurements in the presence of magnesium ion are consistant with whole-lake whitings and carbonate mound formation in and around Pyramid Lake.

Kinetic Inhibition of Calcium Carbonate Crystal Growth in the Presence of Natural and Synthetic Organic Inhibitors

Addition of carboxylate-containing polymeric materials to a metastable supersaturated calcium carbonate solution greatly reduced calcite crystal growth rates at constant supersaturation and pH = 8.5. Calcite crystallization rates were decreased to half their value in pure solutions by a tannic acid concentration of about 0.3 ppm (parts per million); a fulvic acid concentration of about 0.2 ppm; and a poly(acrylic acid) concentration of about 0.0175 ppm. An equation relating the calcite crystallization rate and the additive concentration follows an expression based on a Langmuir adsorption model. However, the Langmuir isotherm plot has two linear segments suggesting that these polyelectrolyte inhibitors may selectively adsorb initially at the fastest growing crystal faces. This relation between polyelectrolyte concentration and calcite growth rates implies inhibition by carboxylate-containing polymeric materials involves blockage of crystal growth sites on the calcite surface.