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Increases in ocean surface water dissolved carbon dioxide (CO 2 ) concentrations retard biocalcification by reducing calcite supersaturation ( Ω c ). 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 Ω c =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.

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.

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. Published in 2007 by John Wiley & Sons, Ltd.

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

It is the nature of the scientific method to use a variety of models, procedures, techniques and data to quantify and analyse natural phenomena. Recently, in Reddy et al. (2006), we published a study in which υ18O values for precipitation, surfaceand ground-water samples from the Shingobee River Headwaters Area (SRHA) were analysed using an amplitude-attenuation (convolution integral) approach for estimating mean residence times (MRTs). This approach has been used in many small watershed studies (e.g. Stewart and McDonnell, 1991; DeWalle et al., 1997; Burns and McDonnell, 1998; McGuire et al., 2002; Rodgers et al., 2005; McGuire and McDonnell, 2006). In a comment, Criss and Winston (2006) disagree with our method and present an alternative approach for interpreting υ18O values in the SRHA. We feel that this comparison with our methodology is unfair. Criss and Winston (2006) focus their attention on the weaknesses in our method and the strengths of theirs, while overlooking our detailed evaluation of model predictions with other independent watershed hydrologic properties. The comment by Criss and Winston (2006) makes several points, some of which we agree are valid criticisms of our paper. In this response, we will address their concerns regarding (1) our interpretation of the current state of the literature, (2) the data we used in the analysis, and (3) the relative merits of the two modelling approaches. In so doing, we will update the dataset with precipitation υ18O data from 1990 to 2004, and compare the two approaches to provide a fair basis for understanding the strengths and weaknesses of both methods. Additionally, we will discuss some technical issues that arise for scientists in choosing between simple and complex models.

18O 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. 18O variations (δ18O), 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 δ18O seasonal variations similar to those of groundwaters, and seasonal δ18O variations plotted versus time fit seasonal sine functions. These seasonal δ18O 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 km2 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 δ18O amplitude approach appear to be consistent within the limits of each method. The results from this study suggest that use of the δ18O seasonal variation method to determine MRTs can help assess groundwater recharge areas in small headwaters catchments. Copyright © 2005 John Wiley & Sons, Ltd.

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.

Williams Lake, Minnesota is a closed-basin lake that is a flow-through system with respect to ground water. Ground-water input represents half of the annual water input and most of the chemical input to the lake. Chemical budgets indicate that the lake is a sink for calcium, yet surficial sediments contain little calcium carbonate. Sediment pore-water samplers (peepers) were used to characterize solute fluxes at the lake-water–ground-water interface in the littoral zone and resolve the apparent disparity between the chemical budget and sediment data. Pore-water depth profiles of the stable isotopes δ18O and δ2H were non-linear where ground water seeped into the lake, with a sharp transition from lake-water values to ground-water values in the top 10 cm of sediment. These data indicate that advective inflow to the lake is the primary mechanism for solute flux from ground water. Linear interstitial velocities determined from δ2H profiles (316 to 528 cm/yr) were consistent with velocities determined independently from water budget data and sediment porosity (366 cm/yr). Stable isotope profiles were generally linear where water flowed out of the lake into ground water. However, calcium profiles were not linear in the same area and varied in response to input of calcium carbonate from the littoral zone and subsequent dissolution. The comparison of pore-water calcium profiles to pore-water stable isotope profiles indicate calcium is not conservative. Based on the previous understanding that 40–50 % of the calcium in Williams Lake is retained, the pore-water profiles indicate aquatic plants in the littoral zone are recycling the retained portion of calcium. The difference between the pore-water depth profiles of calcium and δ18O and δ2H demonstrate the importance of using stable isotopes to evaluate flow direction and source through the lake-water–ground-water interface and evaluate mechanisms controlling the chemical balance of lakes. Published in 2003 by John Wiley & Sons, Ltd.

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.

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 calculatedspecies distributions are used to estimate a mercury-fulvicacid 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 inEverglades' surface water, mercury-sulfide complexes shoulddominate dissolved inorganic mercury solution speciation. Inthe absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominateEverglades' dissolved inorganic mercury speciation.

Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth. All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial Ω = 20, where Ω = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial Ω = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (Ω >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances. The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism was established and maintained during the constant-composition experiments. CSDs having shapes intermediate between lognormal and Ostwald also were generated by varying the initial levels of supersaturation (initial Ω = 28.2 to 69.2) in rapidly mixed solutions. Lognormal CSDs were observed for natural calcite crystals that are found in septarian concretions occurring in southeastern Colorado. Based on the model described above, these CSDs indicate initial growth by surface control, followed by supply-controlled growth. Thus, CSDs may be used to deduce crystal growth mechanisms from which geologic conditions early in the growth history of a mineral can be inferred. Conversely, CSD shape can be predicted during industrial crystallization by applying the appropriate conditions for a particular growth mechanism.

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.

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 th...

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.

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 Ca2+. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (

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.

Dissolution experiments using augite (Mg0.87Ca0.85Fe0.19Na0.09Al0.03Si2O6) and diopside (Mg0.91Ca0.93Fe0.07Na0.03Al0.03Si2O6) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO2 through a solution of 0.01 M KHCO3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O2 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 O2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O2 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.

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.

A chemical budget analysis for Williams Lake, Minnesota, tracks the seasonal progression of carbon inputs and outputs. CO, exchanges with the atmosphere reverse seasonally, with uptake by the lake in summer preceded and followed by larger losses to the atmosphere. Calcium bicarbonate-rich groundwaters seep steadily into the lake, augmented by remobilization of lacustrine marls. Most of the carbon used in summer photosynthesis nevertheless derives from depletion of lake carbon stores, facilitated significantly by plant calcification. Calcification in summer reduces alkalinity and calcium inventories by 15 and 25%, respectively, while generating equal molar quantities of CO,. Marl precipitates mainly on submersed macrophytes, several of which calcify in 1 : 1 ratio to photosynthesis when incubated in Ca-supplemented lake water. Despite calcite supersaturation within the epilimnion, there is little authigenic calcification.

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 cm3/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.

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

An investigation of the strong-acid characteristics (PK a 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 ( 13 C-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% ofthe strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

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.

The apparent acid dissociation constant of humic substances increases by 2-4 pK units as ionization of the humic carboxylate groups proceeds. This change in apparent acid strength is due in part to the increase in electrical charge on the humic molecules as protons are shed. In addition, proton dissociation reactions are complicated because humic substances are heterogeneous with respect to proton dissociating groups and molecular size. In this paper, the authors use the Debye-Hueckel theory to describe the effects of electrostatic interactions on proton dissociation of humic substances. Simulations show that, for a size-heterogeneous system of molecules, the weight-average molecular weight is preferable to the number-average value for averaging the effects of electrostatic interactions. Analysis of published data on the proton dissociation of fulvic acid from the Suwannee River shows that the electrostatic interactions can be satisfactorily described by a hypothetical homogeneous compound having a molecular weight of 1,000 (similar to the experimentally determined weight-average value).

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 Mouintains showed that rainfall acidity varied over the course of summer storms, with low initial pH values increasing as storm intensity increased.

Reactive mixing fronts can occur at large scales, e.g. when chemical amendments are injected in wells, or at small scales (pore-scales) when reactive intermediates are being generated in situ at grain boundaries, cell surfaces and adjacent to biofilms. The product of the reactions such as mineral precipitates, biofilms or filtered colloids modifies permeability leading to the complex coupling between flow and reactions and precipitation. The objectives are to determine how precipitates are distributed within large and small scale mixing fronts, how permeability and flow is modified by precipitation, how the mobility of a representative contaminant, strontium, is affected by the precipitation of carbonates, and how subsequent dissolution of the carbonates result in mobilization of Sr and increased flow. The desired outcomes of the project are to help develop methods leading to sequestration of metal contaminants, and to determine how macroscopic field-scale modeling can be applied to predict the outcome of remediation activities.

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.

The influence of the presence of humic, fulvic, and polyacrylic acid on the nucleation and crystal growth of calcium carbonate in aqueous supersaturated solutions was investigated in batch reactors at 25°C and pH = 8.50. The nucleation of calcium carbonate was investigated by free drift methods, and the crystal growth was investigated with seeded crystal growth experiments at constant supersaturation. In all cases calcite was found to form exclusively, and the presence of all tested compounds at concentrations between 0.1 – 1.0 ppm prolonged the induction time preceding the spontaneous formation of calcite. Humic acid at concentration up to 0.5 ppm inhibited the growth of calcite seeds up to 95% and polyacrylic acid at concentrations up to 0.1 ppm gave the same degree of inhibition. Polyacrylic acid was found to be stronger inhibitor. A concentration of 0.25 ppm of polyacrylic acid completely stopped crystal growth of calcite. Humic acid at concentration 1.0 ppm completely stopped crystal growth of calcite seed crystals. The retardation was explained by the adsorption of the polyelectrolytes onto the active growth sites of the crystals. Application of a Langmuir-type adsorption model on the kinetics data obtained in the presence of the inhibitors tested yielded a higher affinity constant of polyacrylic acid for the calcite seed crystals.

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.

Calcite crystal growth rates measured in the presence of several polycarboxyclic acids show that tetrahydrofurantetracarboxylic acid (THFTCA) and cyclopentanetetracarboxylic acid (CPTCA) are effective growth rate inhibitors at low solution concentrations (0.01 to 1 mg/L). In contrast, linear polycarbocylic acids (citric acid and tricarballylic acid) had no inhibiting effect on calcite growth rates at concentrations up to 10 mg/L. Calcite crystal growth rate inhibition by cyclic polycarboxyclic acids appears to involve blockage of crystal growth sites on the mineral surface by several carboxylate groups. Growth morphology varied for growth in the absence and in the presence of both THFTCA and CPTCA. More effective growth rate reduction by CPTCA relative to THFTCA suggests that inhibitor carboxylate stereochemical orientation controls calcite surface interaction with carboxylate inhibitors. Copyright 2001 Academic Press.

Preservation of building and monument stone exposed to acidic environments relies on the understanding of acidic precipitation deposition processes and damage mechanisms. Presented here is a model which predicts sulfur accumulation in porous limestone subjected to dry deposition of SO2. The model assumes deposition and reaction of SO2 to form a thin gypsum crust on the moist surface of the stone, and subsequent sulfur (as aqueous sulfate) transport and accumulation in the stone interior driven by diurnal wetting and drying of the stone surface. Characterization of the limestone pore structure contributes significantly to the evaluation and interpretation of modeled sulfate transport and accumulation in porous building materials. Predicted sulfur accumulation in the stone interior is dependent on the surface boundary conditions, the stone pore geometry and structure, and the rates and mechanisms of aqueous/solid sulfur partitioning (i.e. adsorption, precipitation and dissolution). Model results are compared to moisture content and sulfur accumulation measured in limestone briquettes exposed to a natural dry deposition environment. The model successfully predicts moisture transport in field-exposed limestone, but overestimates the rate of sulfur accumulation. The model may be improved by quantification of the time dependence of the surface sulfate concentration and better understanding of the sulfate partitioning mechanisms.

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.

The development and refinement of a two-phase model for describing the potentionmetric properties of crosslinked weak acid polyelectrolyte gels and their linear analogues are discussed. Application of this approach has been facilitated by identifying functional group heterogeneity and separate phase effects as the major complications in the description of ion binding by humic substances. By their separation and quantification, equilibrium properties of these systems have been anticipated. This approach may be described as a "discrete ligand" model with solution chemistry effects taken into consideration. Examples of its applications are enumerated and an attempt is made to compare the approach with others.

In the past, ice-core records from mid-latitude glaciers in alpine areas of the continental United States were considered to be poor candidates for paleoclimate records because of the influence of meltwater on isotopic stratigraphy. To evaluate the existence of reliable paleoclimatic records, a 160-m ice core, containing about 250 yr of record was obtained from Upper Fremont Glacier, at an altitude of 4000 m in the Wind River Range of south-central North America. The {gamma}{sup 18}O (SMOW) profile from the core shows a -0.95{per_thousand} shift to lighter values in the interval from 101.8 to 150 m below the surface, corresponding to the latter part of the Little Ice Age (LIA). Numerous high-amplitude oscillations in the section of the core from 101.8 to 150 m cannot be explained by site-specific lateral variability and probably reflect increased seasonality or better preservation of annual signals as a result of prolonged cooler temperatures that existed in this alpine setting. An abrupt decrease in these large amplitude oscillations at the 101.8-m depth suggests a sudden termination of this period of lower temperatures which generally coincides with the termination of the LIA. Three common features in the {gamma}{sup 18}O profiles between Upper Fremont Glacier and themore » better dated Quelccaya Ice Cap cores indicate a global paleoclimate linkage, further supporting the first documented occurrence of the LIA in an ice-core record from a temperate glacier in south-central North America.« less

This paper describes a laboratory experiment on the effects of acidic deposition on carbonate stone erosion. It can serve as the basis for an undergraduate (or pre college) experiment in environmental chemistry. Recent field investigations are described that provide measurements of carbonate stone dissolution and mechanical erosion under weathering conditions that are prevalent in the eastern US. The purpose of the laboratory work is to answer questions concerning the effects of hydrogen ion deposition on stone erosion processes that were difficult to resolve on the basis of field experiments alone.

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.