Hans C. Claassen

Kinetic model for the short-term dissolution of a rhyolitic glass

Abstract Aqueous dissolution experiments with the vitric phase of a rhyolitic tuff were performed at 25°C and constant pH in the range 4.5–7.5. Results suggest interchange of aqueous hydrogen ions for cations situated both on the surface and within the glass. At time intervals from 24 to 900 hr., dissolution kinetics are controlled by ion transport to and from sites within the glass. Experimental data indicate that parabolic diffusion rate of a chemical species from the solid is a nonlinear function of its aqueous concentration. A numerical solution to Ficks second law is presented for diffusion of sodium, which relates its aqueous concentration to its concentration on glass surface, by a Freundlich adsorption isotherm. The pH influence on sodium diffusion in the model can be accounted for by use of a pH-dependent diffusion coefficient and a pH-independent adsorption isotherm.

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.

Estimates of Evapotranspiration or Effective Moisture in Rocky Mountain Watersheds from Chloride Ion Concentrations in Stream Baseflow

The principle that atmospherically derived chloride is a conservative tracer in many watersheds can be used to calculate average annual evapotranspiration or effective moisture if estimates are available for (1) the average annual chloride input to the watershed, (2) the average annual precipitation, and (3) the baseflow chloride concentration are known. The method assumes that no long-term storage of chloride occurs and there is no lithologic source of chloride, or that such source releases only insignificant amounts to groundwater compared to the atmospheric source. National Atmospheric Deposition Program estimates of chloride wet deposition, watershed precipitation records or hyetal map estimates of precipitation input to watersheds, and a single sample of chloride concentration in base flow were used to calculate evapotranspiration for diverse Rocky Mountain watersheds. This estimate was compared to evapotranspiration determined by subtracting mean discharge from precipitation. Of the 19 watersheds used to test the method, 13 agreed within 10%, 2 appear to have not met the lithology criterion, 1 appears to have not met the flow criterion, and 1 neither criterion. The methods greatest strength is the minimal data requirements and its greatest weakness is that for some watersheds it may be difficult to obtain reliable estimates of precipitation and chloride deposition. If reliable discharge data are available, the method may be used to estimate watershed-average precipitation; this is especially useful in high-altitude mountain watersheds where little or no precipitation data are available.

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.

A possible deficiency in estimates of wet deposition obtained from data generated by the NADP/NTN network

Abstract A conventional precipitation scavenging model is used to evaluate the effect of the performance of a wet-deposition collector on the reported deposition amounts. Three National Atmospheric Deposition Program/National Trends Network sites in semi arid western Colorado were chosen to evaluate chloride and sulfate wet deposition. Observations of the performance of a wet-deposition collector have demonstrated a delay in opening and cycling during a precipitation event. A significant fraction of wet deposition may be excluded when small amounts of initial precipitation are not sampled and a potentially large fraction of annual wet deposition may be excluded if a majority of precipitation events are small. The actual amount missed depends on the precipitation intensity, variability of intensity with time, raindrop or snowflake size and the individual performance characteristics of the collector. Detailed performance data are needed for individual welt-deposition collectors before accurate estimates of wet deposition can be expected.

Late-Wisconsin paleohydrology of the West-Central Amargosa Desert, Nevada, U.S.A.

Studies of isotopes in groundwater using 14C, 2H (deuterium) and 18O have provided significant insight into the paleoclimate of middle and late Wisconsin age in a typical arid environment of southern Nevada, the west-central Amargosa Desert. Evidence indicates that recharge probably was through infiltration of runoff in paleostream channels and that this runoff was important only from ∼ 17,000 to ∼ 10,000 yr. B.P. Mean annual temperature at 17,000 yr. B.P. was ∼ 8°C less than present mean annual temperature; some summer moisture was effective in recharge. Winter (October–May) temperature at ∼ 10,000 yr. B.P. was ∼ 1°C less than present; summer moisture did not contribute to recharge.

Conceptual models governing leaching behavior and their long-term predictive capability

Abstract Six models that may be used to describe the interaction of radioactive waste solids with aqueous solutions are as follows: 1. 1. Simple linear mass transfer; 2. 2. Simple parabolic mass transfer; 3. 3. Parabolic mass transfer with the formation of a diffusion-limiting surface layer at an arbitrary time; 4. 4. Initial parabolic mass transfer followed by linear mass transfer at an arbitrary time; 5. 5. Parabolic (or linear) mass transfer and concomitant surface sorption; and 6. 6. Parabolic (or linear) mass transfer and concomitant chemical precipitation. Some of these models lead to either illogical or unrealistic predictions when published data are extrapolated to long times. These predictions result because most data result from short-term experimentation. Probably for longer times, processes will occur that have not been observed in the shorter experiments. This hypothesis has been verified by mass-transfer data from laboratory experiments using natural volcanic glass to predict the composition of groundwater. That such rate-limiting mechanisms do occur is reassuring, although now it is not possible to deduce a single mass-transfer limiting mechanism that could control the solution concentration of all components of all waste forms being investigated. Probably the most reasonable mechanisms are surface sorption and chemical precipitation of the species of interest. Another is limiting of mass transfer by chemical precipitation on the waste form surface of a substance not containing the species of interest, that is, presence of a diffusion-limiting layer. The presence of sorption and chemical precipitation as factors limiting mass transfer has been verified in natural groundwater systems, whereas the diffusion-limiting mechanism has not been verified yet.

Performance characteristics of an automated wet deposition collector and possible effect on computed annual deposition

Abstract Performance characteristics of what is believed to be a typical automated wet deposition collector were examined. For properly functioning collectors, the primary characteristic affecting wet deposition collection efficiency was found to be precipitation rate. Low precipitation rates resulted in the early precipitation not being collected; often at very low, but typical, rates no precipitation was collected. This results in underreporting of both precipitation amounts (if raingage data are not used) and wet deposition, even if corrections to deposition are made using raingage data. This is true because the early precipitation contains the largest solute concentrations. A precipitation scavenging model was used to estimate the amount of wet deposition uncollected for a wide range of precipitation rates and amounts. Correction factors that could be applied to published data for semi-arid sites similar to those in Colorado were developed. The most probable, but conservative, estimate of corrected wet deposition was found to be: true wet deposition = 1.10 to 1.25 (measured wet deposition).

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 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 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 ± 0.2m2/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.