Calcite growth rate inhibition by low molecular weight polycarboxylate ions: Chapter 2
No abstract available.
Book chapter↗
Geology topics
Michael M. Reddy
Publications and source records attributed to Michael M. Reddy.
Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation
Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.
Journal of Crystal Growth↗
Summary of chemical data from onsite and laboratory analyses of groundwater samples from the surficial aquifer, Las Vegas, Nevada, April and August 1993 and September 1994
This report presents a summary of data collected during April and August 1993 and September 1994. These results are to be used as a wet-site analog to southern Nevada soils located at the Amargosa Desert Research Site near Beatty, Nevada. The samples were collected and analyzed in conjunction with the Nevada Basin and Range study unit of the U.S. Geological Survey, National Water-Quality Assessment Program (NAWQA). Samples were collected from groundwater wells in and about the city of Las Vegas, Nevada, and were analyzed for selected major, minor and trace constituents. Analyses of blank and reference samples are summarized as mean and standard deviation values for all positive results.
Nevada↗
Summary of data from onsite and laboratory analyses of surface water and marsh porewater from South Florida Water Management District Water Conservation Areas, the Everglades, South Florida, March 1995
This report presents results of chemical analysis for samples collected during March, 1995, as part of a study to quantify the interaction of aquatic organic material (referred to here as dissolved organic carbon with dissolved metal ions). The work was done in conjunction with the South Florida Water Management District, the U.S. Environmental Protection Agency, the U.S. Geological Survey South Florida Ecosystems Initiative, and the South Florida National Water Quality Assessment Study Unit. Samples were collected from surface canals and from marsh sites. Results are based on onsite and laboratory measurements for 27 samples collected at 10 locations. The data file contains sample description, dissolved organic carbon concentration and specific ultraviolet absorbance, and additional analytical data for samples collected at several sites in the Water Conservation Areas, the Everglades, south Florida.
Florida↗
Calcium carbonate nucleation in an alkaline lake surface water, Pyramid Lake, Nevada, USA
Calcium concentration and calcite supersaturation (Ω) needed for calcium carbonate nucleation and crystal growth in Pyramid Lake (PL) surface water were determined during August of 1997, 2000, and 2001. PL surface water has Ω values of 10-16. Notwithstanding high Ω, calcium carbonate growth did not occur on aragonite single crystals suspended PL surface water for several months. However, calcium solution addition to PL surface-water samples caused reproducible calcium carbonate mineral nucleation and crystal growth. Mean PL surface-water calcium concentration at nucleation was 2.33 mM ( n = 10), a value about nine times higher than the ambient PL surface-water calcium concentration (0.26 mM); mean Ω at nucleation (109 with a standard deviation of 8) is about eight times the PL surface-water Ω. Calcium concentration and Ω regulated the calcium carbonate formation in PL nucleation experiments and surface water. Unfiltered samples nucleated at lower Ω than filtered samples. Calcium concentration and Ω at nucleation for experiments in the presence of added particles were within one standard deviation of the mean for all samples. Calcium carbonate formation rates followed a simple rate expression of the form, rate (mM/min) = A (Ω) + B . The best fit rate equation "Rate (Δ mM/Δ min) = -0.0026 Ω + 0.0175 ( r = 0.904, n = 10)" was statistically significant at greater than the 0.01 confidence level and gives, after rearrangement, Ω at zero rate of 6.7. Nucleation in PL surface water and morphology of calcium carbonate particles formed in PL nucleation experiments and in PL surface-water samples suggest crystal growth inhibition by multiple substances present in PL surface water mediates PL calcium carbonate formation, but there is insufficient information to determine the chemical nature of all inhibitors.
Nevada↗
Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, the Suwannee River, Georgia, USA and by polycarboxylic acids
Calcite crystallization rates are characterized using a constant solution composition at 25°C, pH=8.5, and calcite supersaturation (Ω) of 4.5 in the absence and presence of fulvic acids isolated from Big Soda Lake, Nevada (BSLFA), and a fulvic acid from the Suwannee River, Georgia (SRFA). Rates are also measured in the presence and absence of low-molar mass, aliphatic-alicyclic polycarboxylic acids (PCA). BSLFA inhibits calcite crystal-growth rates with increasing BSLFA concentration, suggesting that BSLFA adsorbs at growth sites on the calcite crystal surface. Calcite growth morphology in the presence of BSLFA differed from growth in its absence, supporting an adsorption mechanism of calcite-growth inhibition by BSLFA. Calcite growth-rate inhibition by BSLFA is consistent with a model indicating that polycarboxylic acid molecules present in BSLFA adsorb at growth sites on the calcite crystal surface. In contrast to published results for an unfractionated SRFA, there is dramatic calcite growth inhibition (at a concentration of 1 mg/L) by a SRFA fraction eluted by pH 5 solution from XAD-8 resin, indicating that calcite growth-rate inhibition is related to specific SRFA component fractions. A cyclic PCA, 1, 2, 3, 4, 5, 6-cyclohexane hexacarboxylic acid (CHXHCA) is a strong calcite growth-rate inhibitor at concentrations less than 0.1 mg/L. Two other cyclic PCAs, 1, 1 cyclopentanedicarboxylic acid (CPDCA) and 1, 1 cyclobutanedicarboxylic acid (CBDCA) with the carboxylic acid groups attached to the same ring carbon atom, have no effect on calcite growth rates up to concentrations of 10 mg/L. Organic matter ad-sorbed from the air onto the seed crystals has no effect on the measured calcite crystal-growth rates.
Nevada, Georgia↗
Meteorological Data near Rabbit Ears Pass, Colorado, U.S.A., 1984-2008
In 1983, a snowmelt energy budget study was initiated by the U.S. Geological Survey on a small watershed near Rabbit Ears Pass, Colorado, to better understand snowmelt processes. The study included data collection from hydrological and meteorological instrumentation. Interest in long term, high-altitude meteorological sites has increased recently due to the increased awareness of global climate change. The meteorological data collected near Rabbit Ears Pass may aid researchers involved in global climate change studies. Meteorological data from 1984 to 2008 are presented.
Data Series↗
Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada
Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14 C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.
Nevada↗
Characterization of surface and ground water δ18O seasonal variation and its use for estimating groundwater residence times
18 O is an ideal tracer for characterizing hydrological processes because it can be reliably measured in several watershed hydrological compartments. Here, we present multiyear isotopic data, i.e. 18 O variations (δ 18 O), for precipitation inputs, surface water and groundwater in the Shingobee River Headwaters Area (SRHA), a well-instrumented research catchment in north-central Minnesota. SRHA surface waters exhibit δ 18 O seasonal variations similar to those of groundwaters, and seasonal δ 18 O variations plotted versus time fit seasonal sine functions. These seasonal δ 18 O variations were interpreted to estimate surface water and groundwater mean residence times (MRTs) at sampling locations near topographically closed-basin lakes. MRT variations of about 1 to 16 years have been estimated over an area covering about 9 km 2 from the basin boundary to the most downgradient well. Estimated MRT error (±0·3 to ±0·7 years) is small for short MRTs and is much larger (±10 years) for a well with an MRT (16 years) near the limit of the method. Groundwater transit time estimates based on Darcy's law, tritium content, and the seasonal δ 18 O amplitude approach appear to be consistent within the limits of each method. The results from this study suggest that use of the δ 18 O seasonal variation method to determine MRTs can help assess groundwater recharge areas in small headwaters catchments.
Minnesota↗
Scientific advances provide opportunities to improve pediatric environmental health
The health consequences of contaminants in the environment, with respect to the health of children and infants, recently have been dramatically brought to public attention by the motion pictures Erin Brockovich and A Civil Action . These productions focused public attention on the potential link between water contaminants and pediatric health, a continuing subject of public concern. As a consequence of the increasing production of new commercial chemicals, many chemicals have appeared in the scientific and public awareness as potential threats to health. These new or novel compounds eventually distribute in the environment and often are termed emerging contaminants . Gitterman and Bearer stated, "Children may serve as unwitting sentinels for society; they are often the youngest exposed to many environmental toxicants and may become the youngest in age to manifest adverse responses." The discipline of pediatric environmental health is still in its adolescence, but it will be increasingly important as new chemicals are generated and as more is learned about the health effects of chemicals already in commerce. Here, we provide an overview of recent advances in biomonitoring and environmental monitoring of environmental contaminants including emerging contaminants. Our purpose in writing this commentary is to make pediatricians aware of the current resources available for learning about pediatric environmental health and of ongoing research initiatives that provide opportunities to improve pediatric environmental health.
Journal of Pediatrics↗
Fulvic acid-sulfide ion competition for mercury ion binding in the Florida everglades
Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculated species distributions are used to estimate a mercury-fulvic acid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC, modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10-7 M or greater) is present in Everglades' surface water, mercury-sulfide complexes should dominate dissolved inorganic mercury solution speciation. In the absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominate Everglades' dissolved inorganic mercury speciation.
Florida↗
Statistical compilation of NAPAP chemical erosion observations
In the mid 1980s, the National Acid Precipitation Assessment Program (NAPAP), in cooperation with the National Park Service (NPS) and the U.S. Geological Survey (USGS), initiated a Materials Research Program (MRP) that included a series of field and laboratory studies with the broad objective of providing scientific information on acid rain effects on calcareous building stone. Among the several effects investigated, the chemical dissolution of limestone and marble by rainfall was given particular attention because of the pervasive appearance of erosion effects on cultural materials situated outdoors. In order to track the chemical erosion of stone objects in the field and in the laboratory, the Ca 2+ ion concentration was monitored in the runoff solution from a variety of test objects located both outdoors and under more controlled conditions in the laboratory. This report provides a graphical and statistical overview of the Ca 2+ chemistry in the runoff solutions from (1) five urban and rural sites (DC, NY, NJ, NC, and OH) established by the MRP for materials studies over the period 1984 to 1989, (2) subevent study at the New York MRP site, (3) in situ study of limestone and marble monuments at Gettysburg, (4) laboratory experiments on calcite dissolution conducted by Baedecker, (5) laboratory simulations by Schmiermund, and (6) laboratory investigation of the surface reactivity of calcareous stone conducted by Fries and Mossotti. The graphical representations provided a means for identifying erroneous data that can randomly appear in a database when field operations are semi-automated; a purged database suitable for the evaluation of quantitative models of stone erosion is appended to this report. An analysis of the sources of statistical variability in the data revealed that the rate of stone erosion is weakly dependent on the type of calcareous stone, the ambient temperature, and the H + concentration delivered in the incident rain. The analysis also showed that the rate of stone erosion is strongly dependent on the rain-delivery conditions and on the surface morphology and orientation.
Open-File Report↗
Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades
Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca 2+ . Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13 C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pH pzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.
Florida↗
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.
Minnesota↗
Interactions of mercury with dissolved organic carbon in the Florida Everglades
There has been increased awareness by both public and scientific communities over mercury contamination of game fish in South Florida. Effective management strategies for dealing with this problem will require a more thorough understanding of the factors and processes that result in the generation and transport of mercury, and control its reactivity in the Everglades. The role of mercury complexation by dissolved organic carbon (DOC) has been proposed by several investigators as a primary mechanism for the transport of mercury in aquatic systems. However, this relationship has been simply proposed based on a strong correlation between dissolved mercury and DOC concentrations in ground, lake and stream waters. Interactions with DOC may be an important process for controlling the transport and bioavailability of mercury. The issue of carbon reactivity in South Florida is especially relevant due to the high natural production of organic carbon in the peat soils and wetlands, the relatively high carbon content of shallow ground water systems in the region, the interactions of organic matter with mercury, other trace metals, and anthropogenic compounds, accumulation of organic carbon in corals and carbonate precipitates, and the potential changes in the quality and reactivity of dissolved organic carbon (DOC) resulting from land use practices. This study will attempt to meet the need to more clearly understand the dynamics of organic matter mercury interactions in the Florida Everglades by focusing research on the effect of dissolved organic carbon (DOC) on the transport and reactivity of Hg in the Everglades.
Florida↗
Effects of acid deposition on dissolution of carbonate stone during summer storms in the Adirondack Mountains, New York, 1987-89
This study is part of a long-term research program designed to identify and quantify acid rain damage to carbonate stone. Acidic deposition accelerates the dissolution of carbonate-stone monuments and building materials. Sequential sampling of runoff from carbonate-stone (marble) and glass (reference) microcatchments in the Adirondack Mountains in New York State provided a detailed record of the episodic fluctuations in rain rate and runoff chemistry during individual summer storms. Rain rate and chemical concentrations from carbonate-stone and glass runoff fluctuated three to tenfold during storms. Net calcium-ion concentrations from the carbonatestone runoff, a measure of stone dissolution, typically fluctuated twofold during these storms. High net sulfate and net calcium concentrations in the first effective runoff at the start of a storm indicated that atmospheric pollutants deposited on the stone surface during dry periods formed calcium sulfate minerals, an important process in carbonate stone dissolution. Dissolution of the carbonate stone generally increased up to twofold during coincident episodes of low rain rate (less than 5 millimeters per hour) and decreased rainfall (glass runoff) pH (less than 4.0); episodes of high rain rate (cloudbursts) were coincident with a rapid increase in rainfall pH and also a rapid decrease in the dissolution of carbonate-stone. During a storm, it seems the most important factors causing increased dissolution of carbonate stone are coincident periods of low rain rate and decreased rainfall pH. Dissolution of the carbonate stone decreased slightly as the rain rate exceeded about 5 millimeters per hour, probably in response to rapidly increasing rainfall pH during episodes of high rain rate and shorter contact time between the runoff and the stone surface. High runoff rates resulting from cloudbursts remove calcium sulfate minerals formed during dry periods prior to storms and also remove dissolution products formed in large measure by chemical weathering as a result of episodes of low rain rate and decreased rainfall pH during a storm.
Water-Resources Investigations Report↗
Effects of acid rain and sulfur dioxide on marble dissolution
Acid precipitation and the dry deposition of sulfur dioxide (SO2) accelerate damage to carbonate-stone monuments and building materials. This study identified and quantified environmental damage to a sample of Vermont marble during storms and their preceding dry periods. Results from field experiments indicated the deposition of SO2 gas to the stone surface during dry periods and a twofold increase in marble dissolution during coincident episodes of low rain rate and decreased rainfall pH. The study is widely applicable to the analysis of carbonate-stone damage at locations affected by acid rain and air pollution.
Materials Performance↗