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Assessing first-order emulator inference for physical parameters in nonlinear mechanistic models

We present an approach for estimating physical parameters in nonlinear models that relies on an approximation to the mechanistic model itself for computational efficiency. The proposed methodology is validated and applied in two different modeling scenarios: (a) Simulation and (b) lower trophic level ocean ecosystem model. The approach we develop relies on the ability to predict right singular vectors (resulting from a decomposition of computer model experimental output) based on the computer model input and an experimental set of parameters. Critically, we model the right singular vectors in terms of the model parameters via a nonlinear statistical model. Specifically, we focus our attention on first-order models of these right singular vectors rather than the second-order (covariance) structure.

Journal of Agricultural, Biological, and Environme↗

Interstitial brines in playa sediments

Study of several closed drainages in the Great Basin has shown that the interstitial solutions of shallow, fine-grained playa deposits store a large quantity of dissolved solids and are often more concentrated than associated lakes and ponds, except in peripheral zones of stream or ground-water inflow. These interstitial fluids, when compared with local runoff, impoundments, or spring waters, commonly have a distinctive ionic composition which sometimes cannot be explained by either simple mixing of surface and subsurface inflow or by evaporative concentration. At Abert Lake, Oregon, the interstitial solute concentrations increased with depth to values as much as five times greater than the lake, except where springs indicate significant ground-water input. Where Na + , Cl, and CO 2 species constitute more than 90% of the solutes, Na + Cl − "> Na+Cl− ratios in the lake water are lower than in interstitial solutions of bottom cores and higher than in playa fluids. At the same time, Na + K + "> Na+K+ ratios are highest in the fluids of lake bottom muds and lowest in playa interstitials. In deeper playa profiles, interstitial Na + Cl − "> Na+Cl− tended to decrease with depth (5 ft. maximum). In the Abert Lake area, as in other parts of the western Great Basin, Na + Cl − "> Na+Cl− ratios are indicative of total CO 2 in solution and the effects of organic decay in surficial sediments. These ratios, coupled with data on silica and bulk density, show that higher P CO2 accompanying decay promotes silicate dissolution and hydrogen ion exchange, stripping alkalis from sediment which had preferentially adsorbed K + when entering the lake. On subsequent loss of pore fluid in the playa regime, silica initially released to solution in the lake environment is readsorbed on dissolution products.

Oregon↗

The age curves of sulfur and oxygen isotopes in marine sulfate and their mutual interpretation

Three hundred new samples of marine evaporite sulfate, of world-wide distribution, were analyzed for δ 34 S, and 60 of these also for δ 18 O in the sulfate ion. Detailed δ 34 S age curves for Tertiary—Cretaceous, Permian—Pennsylvanian, Devonian, Cambrian and Proterozoic times document large variations in δ 34 S. A summary curve forδ 18 O also shows definite variations, some at different times than δ 34 S, and always smaller. The measured δ 34 S and δ 18 O correspond to variations in these isotopes in sulfate of the world ocean surface. The variations of δ 18 O are controlled by input and output fluxes of sulfur in the ocean, three of which are the same that control δ 34 S: deposition and erosion of sulfate, and deposition of sulfide. Erosion of sulfide differs in its effect on the S and O systems. δ 18 O in the sulfate does not seem to be measurably affected by equilibration with either seawater or with subsurface waters after crystallization. In principle, the simultaneous application of both δ 34 S and δ 18 O age curves should help reduce the number of assumptions in calculations of the cycles of sulfur and oxygen through geological time, and a new model involving symmetrical fluxes is introduced here to take advantage of the oxygen data. However, all previously published models as well as this one lead to anomalies, such as unreasonable calcium or oxygen depletions in the ocean—atmosphere system. In addition, most models are incapable of reproducing the sharp rises of the δ 34 S curve in the late Proterozoic, the Devonian and the Triassic which would be the result of unreasonably fast net sulfide deposition. This fast depletion could result from an ocean that has not always been mixed (as previously assumed in all model calculations).

Chemical Geology↗

Geochemistry of a Tertiary sedimentary phosphate deposit: Baja California Sur, Mexico

The San Gregorio Formation in Baja California Sur, a phosphate-enriched sedimentary unit of late Oligocene to early Miocene age, has been analyzed in two areas (La Purisima and San Hilario) for its chemical composition (major oxides, Cu, Cd, Cr, Co, V, and rare-earth elements - REE) and isotopic composition (??18O and ??13C). A detrital and a marine component were determined from major oxides. The detrital component consists of an unaltered volcanic-ash fraction and a terrigenous clay-silt fraction. The marine component, which accumulated initially as biogenic and hydrogenous material, is now present as opal-A, opal-CT, CaCO3, organic matter, and an authigenic phosphate fraction, mostly pelletal and composed of the carbonate-fluorapatite mineral francolite. The minor elements have been partitioned into these components by assuming a constant composition for the two detrital fractions. The composition of the marine component of minor elements can then be interpreted by assuming that the stoichiometry of the original accumulating organic matter was equal to that of modern plankton. The Cu and Cd contents in the marine component of all rocks require that the seawater-derived fractions of these two metals were supplied to the seafloor solely by organic matter. Enrichments of Cr and V at both sites required an additional marine input. On the basis of their geochemistry in the modern ocean, Cr and V could have precipitated, or been adsorbed, onto settling particles from an O2 minimum zone in which the O2 content was low enough to promote denitrification rather than oxygen respiration. An enrichment of the REE, now within the apatite fraction, resulted from their adsorption onto particulates also in the O2 minimum zone and to the dissolution and alteration of biogenic phases (predominantly silica) within the sediment. Co and Fe2O3 show no enrichment above a detrital contribution. The ??18O-values of apatites from the La Purisima site are heavier than those of apatites from the San Hilario site, whereas the ??13C-values show the opposite trend. One possible interpretation of these variations is that ??18O reflects seawater values and ??13C sediment pore water values. This interpretation suggests that upwelling rates and primary productivity within the water column were greater at La Purisima, an interpretation that is corroborated by a greater abundance of apatite measured in outcrop at La Purisima. The Ce anomalies of the phosphate-enriched samples also differ between the two sites, indicating that they also recorded water masses, similar to the ??18O-values. ?? 1991.

Chemical Geology↗

The radiocarbon budget for Mono Lake: An unsolved mystery

Since 1957 the 14 C/C ratio of the dissolved inorganic carbon in Mono Lake has risen by about 60‰. The magnitude of this increase is about four times larger than that expected from the invasion of bomb-produced 14 C from the atmosphere. We have eliminated the following explanations: (1) measurement error, (2) an unusually high physical exchange rate for non-reactive gases, (3) inorganic enhancement of the CO 2 exchange rate, and (4) biological enhancement of the CO 2 exchange rate. Clandestine disposal of waste radiocarbon remains a dark-horse explanation. In the course of our investigations we have uncovered evidence for at least one episodic input of radiocarbon-free carbon to the lake over the last 1000 years. We speculate that this injection was related to a hydrothermal event resulting from sublacustrine volcanic activity.

Earth and Planetary Science Letters↗

The longevity of the South Pacific isotopic and thermal anomaly

The South Pacific is anomalous in terms of the Sr, Nd, and Pb isotope ratios of its hot spot basalts, a thermally enhanced lithosphere, and possibly a hotter mantle. We have studied the Sr, Nd, and Pb isotope characteristics of 12 Cretaceous seamounts in the Magellans, Marshall and Wake seamount groups (western Pacific Ocean) that originated in this South Pacific Isotopic and Thermal Anomaly (SOPITA). The range and values of isotope ratios of the Cretaceous seamount data are similar to those of the island chains of Samoa, Tahiti, Marquesas and Cook/Austral in the SOPITA. These define two major mantle components suggesting that isotopically extreme lavas have been produced at SOPITA for at least 120 Ma. Shallow bathymetry, and weakened lithosphere beneath some of the seamounts studied suggests that at least some of the thermal effects prevailed during the Cretaceous as well. These data, in the context of published data, suggest: (1)|SOPITA is a long-lived feature, and enhanced heat transfer into the lithosphere and isotopically anomalous mantle appear to be an intrinsic characteristic of the anomaly. (2)|The less pronounced depth anomaly during northwesterly plate motion suggests that some of the expressions of SOPITA may be controlled by the direction of plate motion. Motion parallel to the alignment of SOPITA hot spots focusses the heat (and chemical input into the lithosphere) on a smaller cross section than oblique motion. (3)|The lithosphere in the eastern and central SOPITA appears to have lost its original depleted mantle characteristics, probably due to enhanced plume/lithosphere interaction, and it is dominated by isotopic compositions derived from plume materials. (4)|We speculate (following D.L. Anderson) that the origin of the SOPITA, and possibly the DUPAL anomaly is largely due to focussed subduction through long periods of the geological history of the earth, creating a heterogeneous distribution of recycled components in the lower mantle

Earth and Planetary Science Letters↗

The nature, distribution, and origin of gas hydrate in the Chile Triple Junction region

A bottom simulating reflector (BSR) is regionally distributed throughout much of the Chile Triple Junction (CTJ) region. Downhole temperature and logging data collected during Ocean Drilling Program (ODP) Leg 141 suggest that the seismic BSR is generated by low seismic velocities associated with the presence of a few percent free gas in a ??? 10 m thick zone just beneath the hydrate-bearing zone. The data also indicate that the temperature and pressure at the BSR best corresponds to the seawater/methane hydrate stability field. The origin of the large amounts of methane required to generate the hydrates is, however, problematic. Low total organic carbon contents and low alkalinities argue against significant in situ biogenic methanogenesis, but additional input from thermogenic sources also appears to be precluded. Increasing thermal gradients, associated with the approach of the spreading ridge system, may have caused the base of the hydrate stability field to migrate 300 m upwards in the sediments. We propose that the upward migration of the base of the stability field has concentrated originally widely dispersed hydrate patches into the more continuous hydrate body we see today. The methane can be concentrated if the gas hydrates can form from dissolved methane, transported into the hydrate zone via diffusion or fluid advection. A strong gradient may exist in dissolved methane concentration across the BSR leading to the steady reabsorbtion of the free gas zone during the upward migration of the BSR even in the absence of fluid advection.

Earth and Planetary Science Letters↗

Simultaneous flow of water and solutes through geological membranes-I. Experimental investigation

The relative retardation by geological membranes of cations and anions generally present in subsurface waters was investigated using a high pressure and high temperature ‘filtration cell’. The solutions were forced through different clays and a disaggregated shale subjected to compaction pressures up to 9500 psi and to temperatures from 20 to 70°C. The overall efficiences measured increased with increase of exchange capacity of the material used and with decrease in concentration of the input solution. The efficiency of a given membrane increased with increasing compaction pressure but decreased slightly at higher temperatures for solutions of the same ionic concentration. The results further show that geological membranes are specific for different dissolved species. The retardation sequences varied depending on the material used and on experimental conditions. The sequences for monovalent and divalent cations at laboratory temperatures were generally as follows: Li < Na < NH 3 < K < Rb < Cs Mg < Ca < Sr < Ba. The sequences for anions at room temperature were variable, but at 70°C, the sequence was: HCO 3 < I < B < SO 4 < Cl < Br. Monovalent cations contrary to some field data were generally retarded with respect to divalent cations. The differences in the filtration ratios among the divalent cations were smaller than those between the monovalent cations. The passage rate of B, HCO 3 , I and NH 3 was greatly increased at 70°C.

Geochimica et Cosmochimica Acta↗

Mass transfer and carbon isotope evolution in natural water systems

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

Geochimica et Cosmochimica Acta↗

Geochemistry of Great Salt Lake, Utah I: Hydrochemistry since 1850

The hydrochemistry of Great Salt Lake, Utah, has been defined for the historic period, 1850 through 1982, from published data combined with new observations. The water balance depends largely on river inflow, atmospheric precipitation onto the lake surface and evaporation. Input of the major solutes can best be accounted for by mixing dilute calcium-bicarbonate type river waters with NaCl-dominated hydrothermal springs. Prior to 1930, lake concentrations fluctuated inversely with lake volume in response to small climatic variations. Since then, salt precipitation and dissolution have significantly modified lake brine compositions and have led to density stratification and the formation of brine pockets of differing composition. Brine mixing has become an important component of brine evolution. We have used calculated evaporation curves with mineral precipitation and dissolution to clarify these processes. Pore fluids represent important storage for solutes. Solute profiles can be modeled by simple one-dimensional diffusion calculations. Short-term historic variations in lake composition affect shallow pore fluids in the upper 2 metres of sediment. ?? 1985.

Utah↗

Isotopic constraints on the origin of the Atlantis II, Suakin and Valdivia brines, Red Sea

The origin of three Red Sea submarine brine pools was investigated by analysis of the S and O isotope ratios of dissolved sulfate and Sr isotope ratios of dissolved Sr in the brines. Sulfur and O isotope ratios of sulfate and Sr isotope ratios of evaporitic source rocks for the brines were measured for comparison. The S, O and Sr isotope ratios of evaporites recovered from DSDP site 227 are consistent with an upper Miocene evaporites age. The Valdivia Deep brine formed by karstic dissolution of Miocene evaporites by overlying seawater and shows no signs of hydrothermal input. The Suakin Deep brines are derived from, or have isotopically exchanged with Miocene or older evaporites. There has been only minor dilution of the brine by overlying seawater. Strontium isotope ratios of Suakin brine may indicate addition of a minor (15%) amount of volcanic Sr to the brine, but there is no evidence of high temperature brine-rock interaction. The sulfate in the Atlantis II brine was apparently derived from seawater. The O isotope ratio of sulfate in the present Atlantis II brine could reflect isotopic exchange between seawater sulfate and the brine at approximately 255°C. Approximately 30% of the Sr in the Atlantis II brine is derived from the underlying basalt, probably by hydrothermal leaching. Atlantis II brine is the only known example from the Red Sea which has a significant high-temperature hydrothermal history.

Geochimica et Cosmochimica Acta↗

The effects of early diagenesis on the chemical and stable carbon isotopic composition of wood

Studies of modern and ancient buried wood show that there is a linear correlation between carbohydrate content and the stable carbon isotope composition as carbohydrates are preferentially degraded during early diagenesis. As the carbohydrate content decreases, the &#x3B4; 13 C "> δ 13 C value of the degraded wood decreases 1 to 2 per mil, approaching the value of the residual lignin. These results indicate that carbohydrate degradation products are lost and not incorporated into the aromatic structure as lignin is selectively preserved during early diagenesis of wood. These results also indicate that attempts to quantify terrestrial inputs to modern sedimentary organic matter based on &#x3B4; 13 C "> δ 13 C values should consider the possibility of a 1 to 2 per mil decrease in the &#x3B4; 13 C "> δ 13 C value of degraded wood.

Geochimica et Cosmochimica Acta↗

Organic geochemistry and brine composition in Great Salt, Mono, and Walker Lakes

Samples of Recent sediments, representing up to 1000 years of accumulation, were collected from three closed basin lakes (Mono Lake, CA, Walker Lake, NV, and Great Salt Lake, UT) to assess the effects of brine composition on the accumulation of total organic carbon, the concentration of dissolved organic carbon, humic acid structure and diagenesis, and trace metal complexation. The Great Salt Lake water column is a stratified Na-Mg-Cl-SO 4 brine with low alkalinity. Algal debris is entrained in the high density (1.132–1.190 g/cc) bottom brines, and in this region maximum organic matter decomposition occurs by anaerobic processes, with sulfate ion as the terminal electron acceptor. Organic matter, below 5 cm of the sediment-water interface, degrades at a very slow rate in spite of very high pore-fluid sulfate levels. The organic carbon concentration stabilizes at 1.1 wt%. Mono Lake is an alkaline (Na-CO 3 -Cl-SO 4 ) system. The water column is stratified, but the bottom brines are of lower density relative to the Great Salt Lake, and sedimentation of algal debris is rapid. Depletion of pore-fluid sulfate, near l m of core, results in a much higher accumulation of organic carbon, approximately 6 wt%. Walker Lake is also an alkaline system. The water column is not stratified, and decomposition of organic matter occurs by aerobic processes at the sediment-water interface and by anaerobic processes below. Total organic carbon and dissolved organic carbon concentrations in Walker Lake sediments vary with location and depth due to changes in input and pore-fluid sulfate concentrations. Nuclear magnetic resonance studies ( 13 C) of humic substances and dissolved organic carbon provide information on the source of the Recent sedimentary organic carbon (aquatic vs. terrestrial), its relative state of decomposition, and its chemical structure. The spectra suggest an algal origin with little terrestrial signature at all three lakes. This is indicated by the ratio of aliphatic to aromatic carbon and the absence of chemical structures indicative of the lignin of vascular plants. The dissolved organic carbon of the Mono Lake pore fluids is structurally related to humic acid and is also related to carbohydrate metabolism. The alkaline pore fluids, due to high pH, solubilize high molecular weight organic matter from the sediments. This hydrophilic material is a metal complexing agent. Despite very high algal productivities, organic carbon accumulation can be low in stratified lakes if the anoxic bottom waters are hypersaline with high concentrations of sulfate ion. Labile organic matter is recycled to the water column and the sedimentary organic matter is relatively nonsusceptible to bacterial metabolism. As a result, pore-fluid dissolved organic carbon and metal-organic complexation are low.

Geochimica et Cosmochimica Acta↗

Mechanisms controlling Cu, Fe, Mn, and Co profiles in peat of the Filson Creek Fen, northeastern Minnesota

Filson Creek Fen, located in northeastern Minnesota, overlies a Cu-Ni sulfide deposit. A site in the fen was studied to evaluate the hydrogeochemical mechanisms governing the development of Fe, Mn, Co, and Cu profiles in the peat. At the study site, surface peat approximately 1 m thick is separated from the underlying mineralized bedrock by a 6–12 m thickness of lake and glaciofluvial sediments and till. Concentrations of Fe, Mn, Co, and Cu in peat and major elements in pore water delineate a shallow, relatively oxidized, Cu-rich zone overlying a deeper, reduced, Fe-, Mn-, and Co-rich zone within the peat. Sequential metal extractions from peat samples reveal that 40–55% of the Cu in the shallow zone is associated with organic material, whereas the remaining Cu is distributed between iron-oxide, sulfide, and residual fractions. Sixty to seventy percent of the Fe, Mn, and Co concentrated in the deeper zone occur in the residual phase. The metal profiles and associations probably result from non-steady-state input of metals and detritus into the fen during formation of the peat column. The enrichment of organic-associated Cu in the upper, oxidized zone represents a combination of Cu transported into the fen with detrital plant fragments and soluble Cu, derived from weathering of outcrop and subcrop of the mineral deposit, transported into the fen, and fixed onto organic matter in the peat. The variable stratigraphy of the peat indicates that weathering processes and surface vegetation have changed through time in the fen. The Fe, Mn, and Co maxima at the base of the peat are associated with a maximum in detrital matter content of the peat resulting from a transition between the underlying inorganic sedimentary environment to an organic sedimentary environment. The chemistry of sediments and ground water collected beneath the peat indicate that mobilization of metals from sulfide minerals in the buried mineral deposit or glacial deposits is minimal. Therefore, the primary source of Cu to the peat at the study site is outcrops and shallow subcrops of the mineral deposit adjacent to the fen.

Geochimica et Cosmochimica Acta↗

Age determinations and growth rates of Pacific ferromanganese deposits using strontium isotopes

87 Sr 86 Sr ratios, trace element and REE compositions, and textural characteristics were determined for three hydrogenetic Fe-Mn crusts, one hydrothermal deposit, and two mixed hydrothermalhydrogenetic crusts from the Pacific. The Sr isotope data are compared to the Sr seawater curve for the Cenozoic to determine the ages and growth rates of the crusts. The 87 Sr 86 Sr in the crusts does not increase monotonically with depth as expected if the Sr were solely derived from seawater and perfectly preserved since deposition. This indicates post-depositional exchange of Sr or heterogeneous sources for the Sr originally contained in the crusts. Textures of hydrogenetic crusts generally correlate with Sr isotopic variations. The highest porosity intervals commonly exhibit the highest 87 Sr 86 Sr ratios, indicating exchange with younger seawater. Intervals with the lowest porosity commonly have lower 87 Sr 86 Sr and may preserve the original Sr isotopic ratios. Minimum ages of crust growth inception were calculated from dense, low porosity intervals. Growth of the hydrogenetic crusts began at or after 23 Ma, although their substrates are Cretaceous. Estimated average growth rates of the three hydrogenetic crusts vary between 0.9 and 2.7 mm/Ma, consistent with published rates determined by other techniques. Within the Marshall Islands crust, growth rates for individual layers varied greatly between 1.0 and 5.4 mm/Ma. For one crust, very low 87 Sr 86 Sr ratios occurred in detrital-rich intervals. Hydrothermal Fe-Mn oxide from the active Lau Basin back-arc spreading axis (Valu Fa Ridge) has an 87 Sr 86 Sr ratio with a predominantly seawater signature ( 87 Sr 86 Sr 87 Sr 86 Sr 0.709196 "> 0.709196 ), indicating a maximum age of 0.9 Ma. One crust from an off-axis seamount west of Gorda Ridge may have begun precipitating hydrogenetically at 0.5 Ma (0.709211), and had increasing hydrothermal or volcanic input in the top half of the crust, indicated by a significantly lower 87 Sr 86 Sr ratio (0.709052).

Geochimica et Cosmochimica Acta↗

Radium isotope geochemistry of thermal waters, Yellowstone National Park, Wyoming, USA

Radium isotope activities ( 226 Ra, 228 Ra, and 224 Ra), chemical compositions, and sulfur isotope ratios in sulfate were determined for water samples from thermal areas in Yellowstone National Park, Wyoming. Activities of 226 Ra in these waters range from <0.2 to 37.9 dpm/kg. Activity ratios of 228 Ra 226 Ra "> 228Ra226Ra range from 0.26 to 14.2, and those of 224 Ra 228 Ra "> 224Ra228Ra range from 0.73 to 3.1. Radium concentrations are inversely correlated with aquifer equilibration temperatures (estimated from dissolved silica concentrations), while[ Ra Ba "> RaBa ] aq and 228 Ra 226 Ra "> 228Ra226Ra activity ratios depend upon U Ba "> UBa and Th U "> ThU ratios in aquifer rocks. Major controls on Ra concentration in Yellowstone thermal waters are inferred to be 1. (1) barite saturation (at Morris Geyser Basin, Mammoth Hot Springs, and other northern areas) and 2. (2) zeolitewater ion exchange (at Upper Geyser Basin). The data are consistent with a model in which 3. (1) radium and barium are supplied to water by bulk dissolution of aquifer rock, and 4. (2) chemical equilibration of water with rock is rapid relative to the 1602 year half-life of 226 Ra. The 228 Ra 226 Ra "> 228Ra226Ra activity ratios of the waters may in some cases reflect surface enrichments of 232 Th and/or may indicate that α-recoil input of 228 Ra is rapid relative to water-rock chemical equilibration. Activity ratios of 224 Ra 228 Ra "> 224Ra228Ra indicate a nearly ubiquitous 224 Ra excess that generally increases with decreasing pH. Near-surface (≤100 m) thermal water flow velocities at Mammoth Hot Springs are estimated from 224 Ra 228 Ra "> 224Ra228Ra variation to be ≥ 1 m h −1 .

Wyoming↗

Reconnaissance estimates of natural recharge to desert basins in Nevada, U.S.A., by using chloride-balance calculations

A chloride-balance method for estimating average natural recharge to groundwater basins in the Basin and Range Province of the western United States may be a useful alternative or complement to current techniques. The chloride-balance method, as presented in this paper, equates chloride in recharge water and runoff to chloride deposited in mountainous recharge-source areas by precipitation and dry fallout. Given estimates of annual precipitation on these source areas and chloride concentrations of bulk precipitation and recharge water, the rate of recharge can be estimated providing that: (1) no other major sources of chloride exist; (2) direct runoff to discharge areas in the basin is small or can otherwise be taken in account in the balance; and (3) the recharge sources for the basin are correctly delineated. The estimates are sensitive to the estimated rate of input of chloride from the atmosphere; this is the greatest data need for future applications of the method. Preliminary applications of the method to sixteen basins in Nevada, including Las Vegas Valley, indicate that the method can be a useful tool for hydrologists and resource managers. Correlation coefficients between recharge efficiencies for the basins - estimated on the basis of recharge estimates that use the chloride-balance method and two other currently used techniques - range from 0.54 to 0.95, depending on assumptions about where the method may be applied.

Nevada↗

Fluxes of water and solute in a coastal wetland sediment. 2. Effect of macropores on solute exchange with surface water

Chloride was highly concentrated relative to seawater in matrix porewater but was comparatively dilute in macropores. Concentration differences in pore-size classes declined with depth until indistinguishable below 10 cm. The segregated chloride distribution can be explained if recharge to the sediment occurred by downward infiltration in macropores and discharge occurred by an upward flux in matrix pores to satisfy evapotranspiration. Without disturbance by the downward infiltration flux in macropores, upward advection of chloride in matrix pores and evapoconcentration increased chloride concentrations in matrix pores to a level well above the concentration in seawater. The resulting high concentrations of chloride in matrix pores induced a large diffusive efflux of chloride into surface water that was sufficient to balance new input of chloride by infiltration of seawater in macropores (0.085 mmol Cl cm -2 day-1). Transport models that were constrained by water balance measurements at the field site explained both the exponential form of the vertical distribution of chloride in matrix pores and the rate of change in storage of chloride in sediment porewater over a one month period.

Journal of Hydrology↗