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Radionuclides in ground water of the Carson River Basin, western Nevada and eastern California, U.S.A.

Ground water is the main source of domestic and public supply in the Carson River Basin. Ground water originates as precipitation primarily in the Sierra Nevada in the western part of Carson and Eagle Valleys, and flows down gradient in the direction of the Carson River through Dayton and Churchill Valleys to a terminal sink in the Carson Desert. Because radionuclides dissolved in ground water can pose a threat to human health, the distribution and sources of several naturally occurring radionuclides that contribute to gross-alpha and gross-beta activities in the study area were investigated. Generally, alpha and beta activities and U concentration increase from the up-gradient to down-gradient hydrographic areas of the Carson River Basin, whereas 222 Rn concentration decreases. Both 226 Ra and 228 Ra concentrations are similar throughout the study area. Alpha and beta activities and U concentration commonly exceed 100 pCi/l in the Carson Desert at the distal end of the flow system. Radon-222 commonly exceeds 2,000 pCi/l in the western part of Carson and Eagle Valleys adjacent to the Sierra Nevada. Radium-226 and 228 Ra concentrations are <5pCi/l. Four ground water samples were analyzed for 210 Po and one sample contained a high concentration of 21 pCi/l. Seven samples were analyzed for 210 Pb; six contained <3pCi/l and one contained 12 pCi/l. Thorium-230 was detected at concentrations of 0.15 and 0.20 pCi/l in two of four samples. Alpha-emitting radionuclides in the ground water originated from the dissolution of U-rich granitic rocks in the Sierra Nevada by CO 2 , oxygenated water. Dissolution of primary minerals, mainly titanite (sphene) in the granitic rocks, releases U to the water. Dissolved U is probably removed from the water by adsorption on Fe- and Mn-oxide coatings on fracture surfaces and fine-grained sediment, by adsorption on organic matter, and by coprecipitation with Fe and Mn oxides. These coated sediments are transported throughout the basin by fluvial processes. Thus, U is transported as dissolved and adsorbed species. A rise in the water table in the Carson Desert because of irrigation has resulted in the oxidation of U-rich organic matter and dissolution of U-bearing coatings on sediments, producing unusually high U concentration in the ground water. Alpha activity in the ground water is almost entirely from the decay of U dissolved in the water. Beta activity in ground water samples is primarily from the decay of 40 K dissolved in the water and ingrowth of 238 U progeny in the sample before analysis. Approximately one-half of the measured beta activity may not be present in ground water in the aquifer, but instead is produced in the sample after collection and before analysis. Potassium-40 is primarily from the dissolution of K-containing minerals, probably K-feldspar and biotite. Radon-222 is primarily from the decay of 226 Ra in the aquifer materials. Radium in the ground water is thought to be mainly from alpha recoil associated with the decay of Th in the aquifer material. Some Ra may be from dissolution (or desorption) or Ra-rich coatings on sediments.

California, Nevada↗

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

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

Colorado↗

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

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

Applied Geochemistry↗

Environmental conditions affecting concentrations of He, CO2, O2 and N2 in soil gases

The measurement of concentrations of volatile species in soil gases has potential for use in geochemical exploration for concealed ore deposits and for monitoring of subsurface contaminants. However, the interpretation of anomalies in surficial gases can be difficult because soil-gas concentrations are dependent on both meteorological and environmental conditions. For this study, concentrations of He, CO 2 , O 2 and N 2 and meteorological conditions were monitored for 10–14 months at eight nonmineralized sites in both humid and dry environments. Gases were collected at 0.6–0.7-m depth at seven sites. At one site, gases were collected from 0.3-, 0.6-, 1.2-, and 2.0-m depths; diurnal monitoring studies were conducted at this site also. Rain and snowfall, soil and air temperatures, barometric pressure, and relative humidity were monitored at all the sites. The sand, silt and clay content, and the organic carbon content of surficial soil were measured at each site. Meteorological conditions generally affected He and CO 2 concentrations in the same way at all the sites; however, these effects were modified by local environmental conditions. Both seasonal and diurnal concentration changes occurred. The most important seasonal concentration changes were related to rain and snowfall and soil and air temperatures. Seasonal changes tended to be larger then the diurnal changes, but both could be related to the same processes. Local conditions of soil type and organic content affected the amount of pore space and moisture present in the soil and therefore the soil-gas concentrations.

Applied Geochemistry↗

In search of earthquake-related hydrologic and chemical changes along Hayward Fault

Flow and chemical measurements have been made about once a month, and more frequently when required, since 1976 at two springs in Alum Rock Park in eastern San Jose, California, and since 1980 at two shallow wells in eastern Oakland in search of earthquake-related changes. All sites are on or near the Hayward Fault and are about 55 km apart. Temperature, electric conductivity, and water level or flow rate were measured in situ with portable instruments. Water samples were collected for later chemical and isotopic analyses in the laboratory. The measured flow rate at one of the springs showed a long-term decrease of about 40% since 1987, when a multi-year drought began in California. It also showed several increases that lasted a few days to a few months with amplitudes of 2.4 to 8.6 times the standard deviations above the background rate. Five of these increases were recorded shortly after nearby earthquakes of magnitude 5.0 or larger, and may have resulted from unclogging of the flow path and increase of permeability caused by strong seismic shaking. Two other flow increases were possibly induced by exceptionally heavy rainfalls. The water in both wells showed seasonal temperature and chemical variations, largely in response to rainfall. In 1980 the water also showed some clear chemical changes unrelated to rainfall that lasted a few months; these changes were followed by a magnitude 4 earthquake 37 km away. The chemical composition at one of the wells and at the springs also showed some longer-term variations that were not correlated with rainfall but possibly correlated with the five earthquakes mentioned above. These correlations suggest a common tectonic origin for the earthquakes and the anomalies. The last variation at the affected well occurred abruptly in 1989, shortly before a magnitude 5.0 earthquake 54 km away. ?? 1993.

California↗

Geochemical interactions between constituents in acidic groundwater and alluvium in an aquifer near Globe, Arizona

Acidic water from a copper-mining area has contaminated an alluvial aquifer and stream near Globe, Arizona. The most contaminated groundwater has a pH of 3.3, and contains about 100 mmol/1 SO 4 , 50 mmol/1 Fe, 11 mmol/1 Al and 3 mmol/1 Cu. Reactions between alluvium and acidic groundwater were first evaluated in laboratory column experiments. A geochemical model was developed and used in the equilibrium speciation program, MINTEQA2, to simulate breakthrough curves for different constituents from the column. The geochemical model was then used to simulate the measured changes in concentration of aqueous constituents along a flow path in the aquifer. The pH was predominantly controlled by reaction with carbonate minerals. Where carbonates had been dissolved, adsorption of H + by iron oxides was used to simulate pH. Acidic groundwater contained little or no dissolved oxygen, and most aqueous Fe was present as Fe(II). In the anoxic core of the plume, Fe(II) was oxidized by MnO 2 to Fe(III), which then precipitated as Fe(OH) 3 . Attenuation of aqueous Cu, Co, Mn, Ni and Zn was a function of pH and could be quantitatively modeled with the diffuse-layer, surface complexation model in MINTEQA2. Aluminum precipitated as amorphous Al(OH) 3 at pH < 4.7 and as AlOHSO 4 at pH < 4.7. Aqueous Ca and SO 4 were close to equilibrium with gypsum. After the alluvium in the column had reached equilibrium with acidic groundwater, uncontaminated groundwater was eluted through the column to evaluate the effect of reactants on groundwater remediation. The concentration of Fe, Mn, Cu, Co, Ni and Zn rapidly decreased to the detection limits within a few pore volumes. All of the gypsum that had precipitated initially redissolved, resulting in elevated Ca and SO 4 concentrations for about 5 pore volumes. Aluminum and pH exhibited the most potential for continued adverse effects on groundwater quality. As H + desorbed from Fe(OH) 3 , pH remained below 4.5 for more than 20 pore volumes, resulting in dissolution of AlOHSO 4 and elevated aqueous Al.

Applied Geochemistry↗

Use of long-term tritium records from the Colorado River to determine timescales for hydrologic processes associated with irrigation in the Imperial Valley, California

Tritium records were used to study hydrologic processes associated with irrigation and drainage in the Imperial Valley, a 2000-km 2 agricultural area in the southeastern California desert. Tritium was analyzed in surface water, ground water, soil-pore water and drain water, and the results were compared to the historical record of tritium in the Colorado River. The Colorado River record was reconstructed using a simple reservoir model and precipitation data in the Colorado River Basin for the period prior to 1965, and from continuous measurements in the river for 1965–1988. This historical record is especially useful in the arid Imperial Valley because recent agricultural development has been entirely dependent on irrigation water diverted from the Colorado River and local recharge is negligible. Results indicate that it takes about 5 a for irrigation drainage to move through the soil to a depth of 2–3 m. Drainwaters have a wide range in tritium concentrations because of varying degrees of influence from ground-water intrusion, and from rapid percolation of irrigation through preferred pathways. The net result is that drainwater from about 40 fields had a range in tritium concentration similar to that of the Colorado River over the last 9 a (1980–1988), a period during which tritium concentration was declining about 15% annually in the river.

California↗

Geochemical soil sampling for deeply-buried mineralized breccia pipes, northwestern Arizona

Thousands of solution-collapse breccia pipes crop out in the canyons and on the plateaus of northwestern Arizona; some host high-grade uranium deposits. The mineralized pipes are enriched in Ag, As, Ba, Co, Cu, Mo, Ni, Pb, Sb, Se, V and Zn. These breccia pipes formed as sedimentary strata collapsed into solution caverns within the underlying Mississippian Redwall Limestone. A typical pipe is approximately 100 m (300 ft) in diameter and extends upward from the Redwall Limestone as much as 1000 m (3000 ft). Unmineralized gypsum and limestone collapses rooted in the Lower Permian Kaibab Limestone or Toroweap Formation also occur throughout this area. Hence, development of geochemical tools that can distinguish these unmineralized collapse structures, as well as unmineralized breccia pipes, from mineralized breccia pipes could significantly reduce drilling costs for these orebodies commonly buried 300–360 m (1000–1200 ft) below the plateau surface. Design and interpretation of soil sampling surveys over breccia pipes are plagued with several complications. (1) The plateau-capping Kaibab Limestone and Moenkopi Formation are made up of diverse lithologies. Thus, because different breccia pipes are capped by different lithologies, each pipe needs to be treated as a separate geochemical survey with its own background samples. (2) Ascertaining true background is difficult because of uncertainties in locations of poorly-exposed collapse cones and ring fracture zones that surround the pipes. Soil geochemical surveys were completed on 50 collapse structures, three of which are known mineralized breccia pipes. Each collapse structure was treated as an independent geochemical survey. Geochemical data from each collapse feature were plotted on single-element geochemical maps and processed by multivariate factor analysis. To contrast the results between geochemical surveys (collapse structures), a means of quantifying the anomalousness of elements at each site was developed. This degree of anomalousness, named the “correlation value”, was used to rank collapse features by their potential to overlie a deeply-buried mineralized breccia pipe. Soil geochemical results from the three mineralized breccia pipes (the only three of the 50 that had previously been drilled) show that: (1) Soils above the SBF pipe contain significant enrichment of Ag, Al, As, Ba, Ga, K, La, Mo, Nd, Ni, Pb, Sc, Th, U and Zn, and depletion in Ca, Mg and Sr, in contrast to soils outside the topographic and structural rim; (2) Soils over the inner treeless zone of the Canyon pipe show Mo and Pb enrichment anf As and Ga depletion, in contrast to soils from the surrounding forest; and (3) The soil survey of the Mohawk Canyon pipe was a failure because of the rocky terrane and lack of a B soil horizon, or because the pipe plunges. At least 11 of the 47 other collapse structures studied contain anomalous soil enrichments similar to the SBF uranium ore-bearing pipe, and thus have good potential as exploration targets for uranium. One of these 11, #1102, does contain surface mineralized rock. These surveys suggest that soil geochemical sampling is a useful tool for the recognition of many collapse structures with underlying ore-bearing breccia pipes.

Arizona↗

Lead and barium sources in Cambrian siliciclastics and sediment provenance of a sector of the Taconic Orogen, Quebec: a mixing scenario based on Pb-isotopic evidence

To test the hypothesis that siliciclastic rocks constituted the major source of Pb and Ba in barite-galena deposits of the Taconic Orogen, we determined Pb-isotope ratios in galena, barren rocks and contained minerals, as well as concentrations of Pb, U, Th and Ba in the latter (detrital feldspars, sandstones, mudstones, rock clasts and carbonate cements and clasts). Ranges in 206 Pb/ 204 Pb, 207 Pb/ 204 Pb and 208 Pb/ 204 Pb of 28 galena samples are 17.96–18.05, 15.56–15.59 and 37.75–37.93, respectively; ranges for 41 barren rocks and minerals are 16.17–23.31, 15.26–15.86 and 35.98–42.51, respectively. The lowest ratios are in feldspar, and the highest in carbonate and mudstone. Values of the mudstones samples overlap those of galena when corrected for in situ decay of U and Th since galena precipitation (∼450Ma). We thus propose that mudstones constituted a source of lead. Corrected ratios for anomalously Pb-rich mudstones are virtually identical to galena-Pb ratios and may be due to contamination by lead-bearing brines. Assuming that burial diagenesis did not disturb the Pb-isotope values of sandstones, these rocks contributed only a minor fraction of lead to the galena, estimated at∼20% for one deposit. The source of barite-Ba was probably perthite. Low Ba and Pb concentrations of sandstone adjacent to this deposit, compared to high concentrations remote from it, support leaching of barium (and minor lead) from feldspar penecontemporaneous with feldspar dissolution. Geological data indicate that the provenance of the siliciclastic rocks was mainly from Grenville terrane. A comparison of our Pb-isotopic data for Taconic perthite with those of Grenville K-feldspar, as well as ratios of trace elements, support this provenance for both sandstones and mudstones. The presence of carbonate platforms peripheral to the orogen, and the Middle Ordovician-Middle Devonian depositional range of the studied and Mississippi Valley type deposits north (Newfoundland) and south (U.S.A. Appalachians) of our study area suggest targets for exploration in these platforms.

Applied Geochemistry↗

Uraniferous waters of the Arkansas River valley, Colorado, U.S.A.: A function of geology and land use

The effect of local geology and land-use practices on dissolved U was investigated by analysis of surface water and some springs in the Arkansas River valley of southeastern Colorado. Water samples were collected during a 2 week period in April, 1991. The rate of increase of U concentration with distance downriver increased markedly as the river flowed from predominantly undeveloped lands underlain by igneous and metamorphic rocks to agriculturally developed lands underlain by marine shale and limestone. An additional abrupt increase in dissolved U was observed along the section of river where discharge is often greatly reduced because of extensive diversions for irrigation and where remaining flow is largely composed of irrigation return water. Dissolved U in this last section of river and in most of its tributaries exceeded the proposed U.S. drinking water standard of 20 μ/L In water samples collected from agricultural areas dissolved U showed strong positive correlation with major dissolved constituents Na, Ca, Mg, and SO 4 that increase as a result of sulfate mineral dissolution and clay mineral ion-exchange reactions in weathered shale bedrock and shaley soils. Highly soluble minor and trace elements Cl, Li, B, Sr, and Se that are not subject to strong sorptive uptake or precipitation in this setting also correlated positively with U. These combined observations indicate that natural leaching of U-bearing shale bedrock and derivative soils, additional leaching of rock and soil by irrigation water, and evaporative concentration in a semi-arid climate can produce concentrations of dissolved U in surface water and shallow ground water that may threaten nearby drinking water supplies. Other agriculturally developed areas of the semi-arid Western U.S. with similar geology are likely to contain high concentrations of U in irrigation drain water.

Colorado↗

Effects of colloids on metal transport in a river receiving acid mine drainage, upper Arkansas River, Colorado, U.S.A.

Inflows of metal-rich, acidic water that drain from mine dumps and tailings piles in the Leadville, Colorado, area enter the non-acidic water in the upper Arkansas River. Hydrous iron oxides precipitate as colloids and move downstream in suspension, particularly downstream from California Gulch, which has been the major source of metal loads. The colloids influence the concentrations of metals dissolved in the water and the concentrations in bed sediments. To determine the role of colloids, samples of water, colloids, and fine-grained bed sediment were obtained at stream-gaging sites on the upper Arkansas River and at the mouths of major tributaries over a 250-km reach. Dissolved and colloidal metal concentrations in the water column were operationally defined using tangential-flow filtration through 0.001-pm membranes to separate the water and the colloids. Surface-extractable and total bed sediment metal concentrations were obtained on the <60-μm fraction of the bed sediment. The highest concentrations of metals in water, colloids, and bed sediments occurred just downstream from California Gulch. Iron dominated the colloid composition, but substantial concentrations of As, Cd, Cu, Mn, Pb, and Zn also occurred in the colloidal solids. The colloidal load decreased by one half in the first 50 km downstream from the mining inflows due to sedimentation of aggregated colloids to the streambed. Nevertheless, a substantial load of colloids was transported through the entire study reach to Pueblo Reservoir. Dissolved metals were dominated by Mn and Zn, and their concentrations remained relatively high throughout the 250-km reach. The composition of extractable and total metals in bed sediment for several kilometers downstream from California Gulch is similar to the composition of the colloids that settle to the bed. Substantial concentrations of Mn and Zn were extractable, which is consistent with sediment-water chemical reaction. Concentrations of Cd, Pb, and Zn in bed sediment clearly result from the influence of mining near Leadville. Concentrations of Fe and Cu in bed sediments are nearly equal to concentrations in colloids for about 10 km downstream from California Gulch. Farther downstream, concentrations of Fe and Cu in tributary sediments mask the signal of mining inflows. These results indicate that colloids indeed influence the occurrence and transport of metals in rivers affected by mining.

Colorado↗

Gross-beta activity in ground water: natural sources and artifacts of sampling and laboratory analysis

Gross-beta activity has been used as an indicator of beta-emitting isotopes in water since at least the early 1950s. Originally designed for detection of radioactive releases from nuclear facilities and weapons tests, analysis of gross-beta activity is widely used in studies of naturally occurring radioactivity in ground water. Analyses of about 800 samples from 5 ground-water regions of the United States provide a basis for evaluating the utility of this measurement. The data suggest that measured gross-beta activities are due to (1) long-lived radionuclides in ground water, and (2) ingrowth of beta-emitting radionuclides during holding times between collection of samples and laboratory measurements. Although 40 K and 228 Ra appear to be the primary sources of beta activity in ground water, the sum of 40 K plus 228 Ra appears to be less than the measured gross-beta activity in most ground-water samples. The difference between the contribution from these radionuclides and gross-beta activity is most pronounced in ground water with gross-beta activities > 10 pCi/L, where these 2 radionuclides account for less than one-half the measured ross-beta activity. One exception is groundwater from the Coastal Plain of New Jersey, where 40 K plus 228 Ra generally contribute most of the gross-beta activity. In contrast, 40 K and 228 Ra generally contribute most of beta activity in ground water with gross-beta activities < 1 pCi/L. The gross-beta technique does not measure all beta activity in ground water. Although 3 H contributes beta activity to some ground water, it is driven from the sample before counting and therefore is not detected by gross-beta measurements. Beta-emitting radionuclides with half-lives shorter than a few days can decay to low values between sampling and counting. Although little is known about concentrations of most short-lived beta-emitting radionuclides in environmental ground water (water unaffected by direct releases from nuclear facilities and weapons tests), their activities are expected to be low. Ingrowth of beta-emitting radionuclides during sample holding times can contribute to gross-beta activity, particularly in ground water with gross-beta activities > 10 pCi/L. Ingrowth of beta-emitting progeny of 238 U, specifically 234 Pa and 234 Th, contributes much of the measured gross-beta activity in ground water from 4 of the 5 areas studied. Consequently, gross-beta activity measurements commonly overestimate the abundance of beta-emitting radionuclides actually present in ground water. Differing sample holding times before analysis lead to differing amounts of ingrowth of the two progeny. Therefore, holding times can affect observed gross-beta measurements, particularly in ground water with 238 U activities that are moderate to high compared with the activity of 40 K plus 228 Ra. Uncertainties associated with counting efficiencies for beta particles with different energies further complicate the interpretation of gross-beta measurements.

Applied Geochemistry↗

Methane production and consumption monitored by stable H and C isotope ratios at a crude oil spill site, Bemidji, Minnesota

Stable isotopic ratios of C and H in dissolved CH 4 and C in dissolved inorganic C in the ground water of a crude-oil spill near Bemidji, Minnesota, support the concept of CH 4 production by acetate fermentation with a contemporaneous increase in HCO 3 − concentration. Methane concentrations in the saturated zone decrease from 20.6 mg L −1 to less than 0.001 mg L −1 along the investigated flow path. Dissolved N 2 and Ar concentrations in the ground water below the oil plume are 25 times lower than background; this suggests that gas exsolution is removing dissolved CH 4 (along with other dissolved gases) from the ground water. Oxidation of dissolved CH 4 along the flow path seems to be minimal because no measurable change in isotopic composition of CH 4 occurs with distance from the oil body. However, CH 4 is partly oxidized to CO 2 as it diffuses upward from the ground water through a 5- to 7-m thick unsaturated zone; the δ 13 C of the remaining CH 4 increases, the δ 13 C of the CO 2 decreases, and the partial pressure of CO 2 increases. Calculations of C fluxes in the saturated and unsaturated zones originating from the degradation of the oil plume lead to a minimum estimated life expectancy of 110 years. This is a minimum estimate because the degradation of the oil body should slow down with time as its more volatile and reactive components are leached out and preferentially oxidized. The calculated life expectancy is an order of magnitude estimate because of the uncertainty in the average linear ground-water velocities and because of the factor of 2 uncertainty in the calculation of the effective CO 2 diffusion coefficient.

Minnesota↗

Simulation of phosphate transport in sewage-contaminated groundwater, Cape Cod, Massachusetts

Sewage-contaminated groundwater currently discharges to Ashumet Pond, located on Cape Cod, Massachusetts. Phosphate concentrations as high as 60 μmol l −1 have been measured in groundwater entering Ashumet Pond, and there is concern that the rate of eutrophication could increase. Phosphate in the sewage plume is sorbed by aquifer sediment; the amount is a function of phosphate concentration and pH. A nonelectrostatic surface-complexation model coupled with a one-dimensional solute-transport code was used to simulate sorption and desorption of phosphate in laboratory column experiments. The model simulated sorption of phosphate reasonably well, although the slow rate of approach to complete breakthrough indicated a nonequilibrium process that was not accounted for in the solute-transport model. The rate of phosphate desorption in the column experiments was relatively slow. Phosphate could still be measured in effluent after 160 pore volumes of uncontaminated groundwater had been flushed through the columns. Desorption was partly a function of the slowly decreasing pH in the columns and could be modeled quantitatively. Disposal of sewage at this site is scheduled to stop in 1995; however, a large reservoir of sorbed phosphate exists on aquifer sediment upgradient from Ashumet Pond. Computer simulations predict that desorption of phosphate could result in contamination of Ashumet Pond for decades.

Applied Geochemistry↗

Spatial radon anomalies on active faults in California

Radon emanation has been observed to be anomalously high along active faults in many parts of the world. We tested this relationship by conducting and repeating soil air radon surveys with a portable radon meter across several faults in California. The results confirm the existence of fault-associated radon anomalies, which show characteristic features that may be related to fault structures but vary in time due to other environmental changes, such as rainfall. Across two creeping faults in San Juan Bautista and Hollister, the radon anomalies showed prominent double peaks straddling the fault gouge zone during dry summers, but the peak-to-background ratios diminished after significant rain fall during winter. Across a locked segment of the San Andreas fault near Olema, the anomaly has a single peak located several meters southwest of the slip zone associated with the 1906 San Francisco earthquake. Across two fault segments that ruptured during the magnitude 7.5 Landers earthquake in 1992, anomalously high radon concentration was found in the fractures three weeks after the earthquake. We attribute the fault-related anomalies to a slow vertical gas flow in or near the fault zones. Radon generated locally in subsurface soil has a concentration profile that increases three orders of magnitude from the surface to a depth or several meters; thus an upward flow that brings up deeper and radon-richer soil air to the detection level can cause a significantly higher concentration reading. This explanation is consistent with concentrations of carbon dioxide and oxygen, measured in soil-air samples collected during one of the surveys.

Applied Geochemistry↗

The effect of using different 0.45 μm filter membranes on 'dissolved' element concentrations in natural waters

The effect of 4 different 0.45 μm pore size filter membrane systems on the ‘dissolved’ concentration of 28 elements in 5 natural water samples of varying matrix is reported. In 3 of the 5 waters, consistently higher concentrations of most elements (minor and trace) are obtained using Nucleopore 47 mm filter and the cellulose acetate/nitrate 47 mm filter than those measured using the 142 mm cellulose nitrate MFS filter or the Gelman capsule 47 mm filter. These distinct and coherent patterns in elemental behaviour disappear for the other 2 samples, an organic-rich peat water of high suspended load and a mineralised sample high in Si and Ca. Thus the nature and degree of filtration artifacts is matrix-dependent. These trends are evident in both data sets produced by 2 independent laboratories using different instrumentation, techniques and calibrating procedures. The average relative standard deviation in elemental concentration across the 4 filter types is in the range 9–21%. The presence of such filtration artifacts must be considered in projects where, for example, seasonal variability of water composition is under examination, data from various sources are being merged or hydrogeochemical surveys are being conducted.

Applied Geochemistry↗

Preservation of water samples for arsenic(III/V) determinations: An evaluation of the literature and new analytical results

Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.

Applied Geochemistry↗

Occurrence of hexavalent chromium in ground water in the western Mojave Desert, California

About 200 samples from selected public supply, domestic, and observation wells completed in alluvial aquifers underlying the western Mojave Desert were analyzed for total dissolved Cr and Cr(VI). Because Cr(VI) is difficult to preserve, samples were analyzed by 3 methods. Chromium(VI) was determined in the field using both a direct colorimetric method and EPA method 218.6, and samples were speciated in the field for later analysis in the laboratory using a cation-exchange method developed for the study described in this paper. Comparison of the direct colorimetric method and EPA method 218.6 with the new cation-exchange method yielded r2 values of 0.9991 and 0.9992, respectively. Total dissolved Cr concentrations ranged from less than the 0.1 ??g/l detection limit to 60 ??g/l, and almost all the Cr present was Cr(VI). Near recharge areas along the mountain front pH values were near neutral, dissolved O2 concentrations were near saturation, and Cr(VI) concentrations were less than the 0.1 ??g/l detection limit. Chromium(VI) concentrations and pH values increased downgradient as long as dissolved O 2 was present. However, low Cr(VI) concentrations were associated with low dissolved O2 concentrations near ground-water discharge areas along dry lakes. Chromium(VI) concentrations as high as 60 ??g/l occurred in ground water from the Sheep Creek fan alluvial deposits weathered from mafic rock derived from the San Gabriel Mountains, and Cr(VI) concentrations as high as about 36 ??g/l were present in ground water from alluvial deposits weathered from less mafic granitic, metamorphic, and volcanic rocks. Chromium(III) was the predominant form of Cr only in areas where dissolved O2 concentrations were less than 1 mg/l and was detected at a median concentration of 0.1 ??g/l, owing to its low solubility in water of near-neutral pH. Depending on local hydrogeologic conditions and the distribution of dissolved O2, Cr(VI) concentrations may vary considerably with depth. Samples collected under pumping conditions from different depths within wells show that Cr(VI) concentrations can range from less than the 0.1 ??g/l detection limit to 36 ??g/l in a single well and that dissolved O2 concentrations likely control the concentration and redox speciation of Cr in ground water.

California↗