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Model Parameter Estimation Experiment (MOPEX): An overview of science strategy and major results from the second and third workshops

The Model Parameter Estimation Experiment (MOPEX) is an international project aimed at developing enhanced techniques for the a priori estimation of parameters in hydrologic models and in land surface parameterization schemes of atmospheric models. The MOPEX science strategy involves three major steps: data preparation, a priori parameter estimation methodology development, and demonstration of parameter transferability. A comprehensive MOPEX database has been developed that contains historical hydrometeorological data and land surface characteristics data for many hydrologic basins in the United States (US) and in other countries. This database is being continuously expanded to include more basins in all parts of the world. A number of international MOPEX workshops have been convened to bring together interested hydrologists and land surface modelers from all over world to exchange knowledge and experience in developing a priori parameter estimation techniques. This paper describes the results from the second and third MOPEX workshops. The specific objective of these workshops is to examine the state of a priori parameter estimation techniques and how they can be potentially improved with observations from well-monitored hydrologic basins. Participants of the second and third MOPEX workshops were provided with data from 12 basins in the southeastern US and were asked to carry out a series of numerical experiments using a priori parameters as well as calibrated parameters developed for their respective hydrologic models. Different modeling groups carried out all the required experiments independently using eight different models, and the results from these models have been assembled for analysis in this paper. This paper presents an overview of the MOPEX experiment and its design. The main experimental results are analyzed. A key finding is that existing a priori parameter estimation procedures are problematic and need improvement. Significant improvement of these procedures may be achieved through model calibration of well-monitored hydrologic basins. This paper concludes with a discussion of the lessons learned, and points out further work and future strategy. ?? 2005 Elsevier Ltd. All rights reserved.

Conference Paper

Single receiver target localization in mobile marine acoustic telemetry

Many marine ecological studies track animal movement and migration using acoustic telemetry, in which animals are implanted with acoustic transmitters broadcasting a unique ID code. Receivers detect and decode these transmissions and provide an estimate of the animal’s location. As transmissions can be detected at distances of hundreds of meters to even several kilometers, localization performed using binary detection information is very coarse. Fine-scale localization can be performed using time difference of arrival systems, but such systems are costlier and require a greater number of receivers. We present a Bayesian method for target localization using only binary detection information collected by a single receiver mounted on a mobile platform. The approach reduces error in the location estimate by considering the distance-dependent probability of detection (detection efficiency curve), which must first be characterized. Stationary receivers are used to infer failed detections. This localization method is then used to inform waypoint selection for the mobile platform, using the second nondominated sorting genetic algorithm considering the tradeoff between the travel distance of the platform and localization error. Simulation results examine the effects of detection efficiency curve characteristics, number of transmissions, and travel distance on the localization error. The proposed method is further supported by experimental results from field trials conducted with an autonomous surface vehicle in Lake Huron.

IEEE Journal of Oceanic Engineering

Characteristics of hydrolysis of the complex Na2SnF6 in hydrothermal solutions-An experimental study

Characteristics of hydrolysis of the complex Na2SnF6, which is used as the starting material, in hydrothermal solutions have been studied at 200-602??C and 1 kbar. Experimental results show that intense hydrolysis of Na2SnF6 occurs at high temperatures and that with the rise of temperature the hydrolysis will become more intense. Under the present experimental conditions the most possible existing form of Sn in the hydrothermal solutions is SnF3(OH) or Na2SnF3(OH). In addition, the hydrolysis constants for Na2SnF6 have also been calculated at 200-602??C, and the relationship between Na2SnF6 hydrolysis and temperature is discussed. ?? 1987 Science Press.

Chinese Journal of Geochemistry

Shallow storage of the explosive Earthquake Flat Pyroclastics magma body, Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand: Evidence from phase-equilibria experiments

Rhyolitic tuffs range widely in their crystal contents from nearly aphyric to crystal-rich, and their crystal cargoes inform concepts of upper crustal magma reservoirs. The Earthquake Flat pyroclastics (Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand) are 10 km 3 of rhyolitic tuffs with abundant (~ 40 vol.%) plagioclase and quartz, minor biotite, hornblende, and orthopyroxene, and accessory Fe-Ti oxides, apatite, and zircon, set in high-silica rhyolitic glass. Major minerals form large, euhedral phenocrysts and abundant glomerocrysts with few disequilibrium textures excepting some faintly resorbed quartz. Plagioclase phenocrysts have thick rims of nearly constant composition near An 30 , and hornblende is weakly zoned or unzoned. The abundant and texturally complex mineral assemblage contrasts with the nearby (~ 25 km), nearly synchronous, but more voluminous and crystal-moderate rhyolite tuffs from Rotoiti caldera. New H 2 O-saturated phase-equilibria results on the erupted Earthquake Flat melt (glass) determine its co-saturation with the partial phenocryst assemblage of plagioclase, quartz, biotite, and Fe-Ti oxides at: 140 MPa, 755 ºC. These closely approximate the conditions of the pre-eruptive magma body assuming it was saturated with nearly pure H 2 O and at an f O 2 of ~ Ni–NiO. Absence of hornblende and orthopyroxene from the synthesized assemblages may result from those minerals being in a peritectic reaction relation with melt to produce biotite, so they would not grow from the liquid used as starting material. Experimental results on Rotoiti rhyolite (Nicholls et al. 1992) show that the two bodies resided at similar pressures, temperatures, and f O 2 s. Lower crystal abundance of the Rotoiti tuffs may result from slight compositional differences. We interpret that the Earthquake Flat pyroclastics were sourced from the crystal-rich periphery of a mushy reservoir system with the Rotoiti occupying a more melt-rich central location. Uncertain is whether this was a single intrusion zoned continuously in crystallinity, or discrete adjacent intrusions, but our results illustrate and quantify complexities of magma storage across relatively short distances.

North Island, Taupo Volcanic Zone

Adsorption of bacteriophages on clay minerals

The ability to predict the fate of microorganisms in soil is dependent on an understanding of the process of their sorption on soil and subsurface materials. Presently, we have focused on studying the thermodynamics of sorption of bacteriophages (T-2, MS-2, and φX-174) on clays (hectorite, saponite, kaolinite, and clay fraction of samples collected from a landfill site). The thermodynamic study not only determines the feasibility of the process but also provides information on the relative magnitudes of the different forces under a particular set of conditions. The total free energy of interaction during sorption of bacteriophages on clays (Δ G ) has been assumed to be the summation of Δ G H (Δ G due to hydrophobic interactions) and Δ G EL (Δ G due to electrostatic interactions). The magnitude of Δ G H was determined from the different interfacial tensions (γ) present in the system, while Δ G EL was calculated from ζ-potentials of the colloidal particles. Calculated results show that surface hydrophobicities of the selected sorbents and sorbates dictate sorption. Among the selected bacteriophages, maximum sorption was observed with T-2, while hectorite has the maximum sorption capacity. Experimental results obtained from the batch adsorption studies also corroborated those obtained from the theoretical study.

Environmental Science & Technology

Warming experiments underpredict plant phenological responses to climate change

Warming experiments are increasingly relied on to estimate plant responses to global climate change. For experiments to provide meaningful predictions of future responses, they should reflect the empirical record of responses to temperature variability and recent warming, including advances in the timing of flowering and leafing. We compared phenology (the timing of recurring life history events) in observational studies and warming experiments spanning four continents and 1,634 plant species using a common measure of temperature sensitivity (change in days per degree Celsius). We show that warming experiments underpredict advances in the timing of flowering and leafing by 8.5-fold and 4.0-fold, respectively, compared with long-term observations. For species that were common to both study types, the experimental results did not match the observational data in sign or magnitude. The observational data also showed that species that flower earliest in the spring have the highest temperature sensitivities, but this trend was not reflected in the experimental data. These significant mismatches seem to be unrelated to the study length or to the degree of manipulated warming in experiments. The discrepancy between experiments and observations, however, could arise from complex interactions among multiple drivers in the observational data, or it could arise from remediable artefacts in the experiments that result in lower irradiance and drier soils, thus dampening the phenological responses to manipulated warming. Our results introduce uncertainty into ecosystem models that are informed solely by experiments and suggest that responses to climate change that are predicted using such models should be re-evaluated.

Nature

Geochemical effects of deep-well injection of the Paradox Valley brine into Paleozoic carbonate rocks, Colorado, U.S.A.

Brine seepage into the Dolores River from ground water in Paradox Valley, Colorado constitutes a major source of salt to the Colorado River. Plants are enderway to remove this source of salt by drawing down the Paradox Valley brine (PVB) and forcibly injecting it into a deep disposal well (4.8 km). Experiments were conducted to determine the effects of deep-well injection of PVB. The results show that PVB is near saturation with anhydrite at 25°C, and that heating results in anhydrite precipitation. The amount and the rate at which anhydrite forms is temperature, pressure, and substrate dependent. Paradox Valley brine heated in the presence of Precambrian rocks from the drill core produces the same amount of anhydrite as PVB heated alone, but at a greatly accelerated rate. A 30% dilution of PVB with Dolores River water completely eliminates anhydrite precipitation when the fluid is heated with the Precambrian rocks. Interaction of PVB and Leadville Limestone is characterized by dolomitization of calcite by brine Mg which releases Ca to solution. This added Ca reacts with SO 4 to form increased amounts of anhydrite. A 20% dilution of PVB by Dolores River water has no effect on dolomitization and reduces the amount of anhydrite only slightly. A 65% dilution of PVB by Dolores River water still does not prevent dolomitization but does suppress anhydrite formation. Computer modeling of PVB by programs utilizing the Pitzer ion-interaction parameters is in general agreement with the experimental results. Ion-activity products calculated by both SOLMINEQ and PHRQPITZ are close to equilibrium with both anhydrite and dolomite whenever these phases are present experimentally, although the calculations over-estimate by a factor of 2 the degree of saturation. Some discrepancies in the calculated results between the two programs are due largely to differences in mineral solubility data.

Colorado

Three-dimensional measurements of flow in uncased wells completed in basalt, Mountain Home Air Force Base, Idaho, March 2000

Several ground-water monitoring wells on the Mountain Home Air Force Base in southwestern Idaho were constructed in February 2000 to replace existing monitoring wells that became ineffective as a result of declining water levels. Upon completion of the replacement wells, borehole geophysical logs were collected, including natural gamma radiation, electromagnetic induction, caliper, fluid temperature, and resistivity. A prototype borehole acoustic doppler velocimeter (B-ADV) was used to make experimental three-dimensional measurements of lateral and vertical flow in two of the replacement wells, MW11–2 and MW3–2, each 450 feet deep, to better understand ground-water flow in the basalt underlying this area. Measurements indicated two independent flow zones in each well: unit B, from about 380 to about 415 feet below land surface, and unit C, from about 415 to about 430 feet below land surface. In each well, direction of flow in unit B was north-northwest toward Canyon Creek and, in unit C, south-southwest toward the Snake River. Measurements also indicated downward intraborehole flow in both wells. Unit B appeared to represent a local-scale flow regime; unit C appeared to represent a regional flow regime. This information suggests the existence of a complex three-dimensional hydrogeologic setting that cannot be discriminated easily on conventional waterlevel maps. Although data from only two wells are insufficient to construct a conceptual model of the ground-water flow regime, these experimental results demonstrate the capability of the B-ADV to obtain detailed flow measurements that, combined with data from other types of geophysical logs, discrete measurements of hydraulic head, and water chemistry, would aid in future studies and management of the ground-water resources, including contaminant transport and remediation.

Idaho

Effects of suspended sediment on the reproductive success of the tricolor shiner, a crevice-spawning minnow

Excessive sedimentation of rivers and creeks has been linked to increasing levels of imperilment in the diverse fish fauna of the southeastern United States. In particular, benthic-spawning fishes have decreased in both numbers and range. The tricolor shiner Cyprinella trichroistia is a crevice-spawning minnow that is widespread in the eastern Mobile River drainage above the Fall Line. While they are less sensitive to perturbation than the federally threatened blue shiner C. caerulea, tricolor shiners have decreased in numbers and range during the past few decades. This experiment examined the effects of 0 (control), 100, 300, and 600 mg/L initial concentrations of suspended sediment on the reproductive success of the tricolor shiner. Increasing levels of suspended sediment caused decreasing levels of reproductive success (fewer spawns and fewer eggs laid when spawning occurred). Increasing levels of suspended sediment also delayed the onset of spawning, resulting in distinct frequency distributions of clear eggs, eyed eggs, and larvae across treatments. Mortality of eggs and larvae was not a factor in the experiment. We examined daily sediment concentration data recorded at three sites in the upper Coosa River over the April-August spawning season of 1963. By weighting our experimental results by the number of days above each sediment concentration, we estimated that 20% fewer eggs were laid than would have been laid if conditions had been like those of the controls. Albeit our model is simplistic, it provides insight into how excessive sedimentation contributes to population extirpation. Mitigation of suspended sediments is an important management action for the conservation of southern Appalachian fishes that spawn in benthic habitats.

Transactions of the American Fisheries Society

Salinity tolerance of non-native suckermouth armoured catfish (Loricariidae: Pterygoplichthys sp.) from Kerala, India

Loricariid catfishes of the genus Pterygoplichthys are native to South America and have been introduced in many localities around the world. They are freshwater fishes, but may also use low-salinity habitats such as estuaries for feeding or dispersal. Here we report results of a field survey and salinity-tolerance experiments for a population of Pterygoplichthys sp. collected in Kerala, India. In both chronic and acute salinity-tolerance trials, fish were able to withstand salinities up to 12 ppt with no mortality; however, fish transferred to salinities > 12 ppt did not survive. The experimental results provide evidence that nonnative Pterygoplichthys sp. are able to tolerate mesohaline conditions for extended periods, and can easily invade the brackish water ecosystems of the state. Further, Pterygoplichthys sp. from Kerala have greater salinity tolerance than other congeners. These data are vital to predicting the invasion of non-native fishes such as Pterygoplichthys spp. into coastal systems in Kerala and worldwide. This is particularly important as estuarine ecosystems are under threat of global climate change and sea-level rise. In light of the results of the present study and considering the reports of negative impacts of the species in invaded water bodies, management authorities may consider controlling populations and/or instituting awareness programmes to prevent the spread of this nuisance aquatic invasive species in Kerala.

Kerala

Exploratory laboratory study of lateral turbulent diffusion at the surface of an alluvial channel

In natural streams turbulent diffusion is one of the principal mechanisms by which liquid and suspended-particulate contaminants are dispersed in the flow. A knowledge of turbulence characteristics is therefore essential in predicting the dispersal rates of contaminants in streams. In this study the theory of diffusion by continuous movements for homogeneous turbulence is applied to lateral diffusion at the surface of an open channel in which there is uniform flow. An exploratory-laboratory investigation was conducted in which the lateral dispersion at the water surface of a sand-Led flume was studied by measuring the lateral spread from a point source of small floating polyethylene articles. The experiment was restricted to a single set of low and channel geometry conditions. The results of the study indicate that with certain restrictions lateral dispersion in alluvial channels may be successfully described by the theory of diffusion by continuous movements. The experiment demonstrates a means for evaluating the lateral diffusion coefficient and also methods for quantitatively estimating fundamental turbulence properties, such as the intensity and the Lagrangian integral scale of turbulence in an alluvial channel. The experimental results show that with increasing distance from the source the coefficient of lateral turbulent diffusion increases initially but tends toward a constant limiting value. This result is in accordance with turbulent diffusion theory. Indications are that the distance downstream from the source required for the diffusion coefficient to reach its limiting value is actually very small when compared to the length scale of most diffusion phenomena in natural streams which are of practical interest.

Circular

The stability of sulfate and hydrated sulfate minerals near ambient conditions and their significance in environmental and planetary sciences

Sulfate and hydrated sulfate minerals are abundant and ubiquitous on the surface of the Earth and also on other planets and their satellites. The humidity-buffer technique has been applied to study the stability of some of these minerals at 0.1 MPa in terms of temperature-relative humidity space on the basis of hydration-dehydration reversal experiments. Updated phase relations in the binary system MgSO 4 -H 2 O are presented, as an example, to show how reliable thermodynamic data for these minerals could be obtained based on these experimental results and thermodynamic principles. This approach has been applied to sulfate and hydrated sulfate minerals of other metals, including Fe (both ferrous and ferric), Zn, Ni, Co, Cd, and Cu. Metal-sulfate salts play important roles in the cycling of metals and sulfate in terrestrial systems, and the number of phases extends well beyond the simple sulfate salts that have thus far been investigated experimentally. The oxidation of sulfide minerals, particularly pyrite, is a common process that initiates the formation of efflorescent metal-sulfate minerals. Also, the overall abundance of iron-bearing sulfate salts in nature reflects the fact that the weathering of pyrite or pyrrhotite is the ultimate source for many of these phases. Many aspects of their environmental significance are reviewed, particularly in acute effects to aquatic ecosystems related to the dissolution of sulfate salts during rain storms or snow-melt events. Hydrous Mg, Ca, and Fe sulfates were identified on Mars, with wide distribution and very large quantities at many locations, on the basis of spectroscopic observations from orbital remote sensing and surface explorations by rovers. However, many of these findings do not reveal the detailed information on the degree of hydration that is essential for rigorous interpretation of the hydrologic history of Mars. Laboratory experiments on stability fields, reactions pathways, and reaction rates of hydrous sulfates likely to be found on Mars enhance our understanding of the degrees of hydration of various sulfates that should currently exist on Mars at various seasons and locations and during various atmospheric pressure and obliquity periods. Two sets of systematic experiments were described; one on hydrous Mg sulfates and the other on hydrous Fe 3+ sulfates. Also, their implications to Mars sulfates mineralogy were discussed.

Journal of Asian Earth Sciences

Behaviour of calcium carbonate in sea water

Anomalies in the behaviour of calcium carbonate in natural solutions diminish when considered in context. Best values found by traditional oceanographie methods for the apparent solubility product constant K ' CaCO 3 in sea water at atmospheric pressure are consistent mineralogically—at 36 parts per thousand salinity and T-25°C, K ' aragonlte is estimated as 1.12 × 10 −6 and K ' calcite as 0.61 × 10 −6 . At 30°C the corresponding values are 0.98 × 10 −6 for aragonite and 0.53 × 10 −6 for calcite. Because the K ' computations do not compensate for ionic activity, however, they cannot give thermodynamically satisfactory results. It is of interest, therefore, that approximate methods and information now available permit the estimation from the same basic data of an activity product constant K CaCO 3 close to that found in solutions to which Debye-Hückel theory applies. Such methods indicate approximate K aragonite 7.8 × 10 −9 for surface sea water at 29°C; K calcite would be proportionately lower. Field data and experimental results indicate that the mineralogy of precipitated CaCO 3 depends primarily on degree of supersaturation, thus also on kinetic or biologic factors that facilitate or inhibit a high degree of supersaturation. The shallow, generally hypersaline bank waters west of Andros Island yield aragonitic sediments with O 18 O 16 "> O18O16 ratios that imply precipitation mainly during the warmer months, when the combination of a high rate of evaporation, increasing salinity (and ionic strength), maximal temperatures and photosynthetic removal of CO 2 result in high apparent supersaturation. The usual precipitate from solutions of low ionic strength is calcite, except where the aragonite level of supersaturation is reached as a result of diffusion phenomena ( e.g. dripstones), gradual and marked evaporation, or biologic intervention. Published data also suggest the possibility of distinct chemical milieus for crystallographic variations in skeletal calcium carbonate. It appears that in nature aragonite precipitates from solutions that are supersaturated with respect to both calcite and aragonite and calcite between saturation levels for the two species. Such a relation is consistent with Ostwald's rule of successive reactions. Aragonitc of marine origin persists in contact with supersaturated interstitial solutions at ordinary temperature and pressure. Conversion to calcite follows transfer to solutions undersaturated with respect to aragonite or upon exposure to the moist atmosphere.

Geochimica et Cosmochimica Acta

Experimental chemical weathering of various bedrock types at different pH-values. 1. Sandstone and granite

Experimental chemical weathering of the so-called Old Rag Granite and Massanutten Sandstone, Virginia, U.S.A., has produced a comparison with the natural environment, and prediction of the effect of acid precipitation. The experimental results of the release of elements, dissolution of minerals, total rock weathered and the degree of weathering as function of volume of leachate were plotted. These data were compared with the natural environment. The use of the plots to predict the effect of high levels of rain acidity on weathering of these rocks is demonstrated. A nonexpandable 14-Å clay was developed from the alteration of biotite during the experimental chemical weathering of the granite at pH 4. This interstratified Al(OH)—mica clay resembles those of the soil developed on the granite and sandstone. Hydroxy-Al may be precipitating between the mica interlayers and producing a 14-Å spacing. Development of this clay by chemical alteration of biotite may change the current hypotheses about its origin in the soils of northeastern U.S.A. While Al-hydroxide seems to regulate Al concentrations in stream waters at the present level of rain acidity, it was found that at lower pH and in the presence of high sulfate concentrations, Al solubility may be controlled by Al-sulfate phase(s).

Virginia

A new organic reference material, L-glutamic acid, USGS41a, for δ 13 C and δ 15 N measurements − a replacement for USGS41

Rationale The widely used l -glutamic acid isotopic reference material USGS41, enriched in both 13 C and 15 N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41. Methods USGS41a was prepared by dissolving analytical grade l -glutamic acid enriched in 13 C and 15 N together with l -glutamic acid of normal isotopic composition. The δ 13 C and δ 15 N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate ( δ 13 C VPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate ( δ 13 C VPDB = −46.6 mUr), and IAEA-N-1 ammonium sulfate ( δ 15 N Air = +0.43 mUr) and USGS32 potassium nitrate ( δ 15 N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry. Results USGS41a is isotopically homogeneous; the reproducibility of δ 13 C and δ 15 N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ 13 C value of +36.55 mUr relative to VPDB and a δ 15 N value of +47.55 mUr relative to N 2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41. Conclusions The new isotopic reference material USGS41a can be used with USGS40 (having a δ 13 C VPDB value of −26.39 mUr and a δ 15 N Air value of −4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

Rapid Communications in Mass Spectrometry

The potential applications of using compost chars for removing the hydrophobic herbicide atrazine from solution

One commercial compost sample was pyrolyzed to produce chars as a sorbent for removing the herbicide atrazine from solution. The sorption behavior of compost-based char was compared with that of an activated carbon derived from corn stillage. When compost was pyrolyzed, the char yield was greater than 45% when heated under air, and 52% when heated under N2. In contrast, when the corn stillage was pyrolyzed under N2, the yield was only 22%. The N2-BET surface area of corn stillage activated carbon was 439 m2/g, which was much greater than the maximum compost char surface area of 72 m2/g. However, the sorption affinity of the compost char for dissolved atrazine was comparable to that of the corn stillage activated carbon. This similarity could have resulted from the initial organic waste being subjected to a relatively long period of thermal processes during composting, and thus, the compost was more thermally stable when compared with the raw materials. In addition, microorganisms transformed the organic wastes into amorphous humic substances, and thus, it was likely that the microporisity was enhanced. Although this micropore structure could not be detected by the N2-BET method, it was apparent in the atrazine sorption experiment. Overall, the experimental results suggested that the compost sample in current study was a relatively stable material thermally for producing char, and that it has the potential as a feed stock for making high-quality activated carbon. ?? 2007 Elsevier Ltd. All rights reserved.

Bioresource Technology

Effects of dispersal on total biomass in a patchy, heterogeneous system: Analysis and experiment

An intriguing recent result from mathematics is that a population diffusing at an intermediate rate in an environment in which resources vary spatially will reach a higher total equilibrium biomass than the population in an environment in which the same total resources are distributed homogeneously. We extended the current mathematical theory to apply to logistic growth and also showed that the result applies to patchy systems with dispersal among patches, both for continuous and discrete time. This allowed us to make specific predictions, through simulations, concerning the biomass dynamics, which were verified by a laboratory experiment. The experiment was a study of biomass growth of duckweed ( Lemna minor Linn.), where the resources (nutrients added to water) were distributed homogeneously among a discrete series of water-filled containers in one treatment, and distributed heterogeneously in another treatment. The experimental results showed that total biomass peaked at an intermediate, relatively low, diffusion rate, higher than the total carrying capacity of the system and agreeing with the simulation model. The implications of the experiment to dynamics of source, sink, and pseudo-sink dynamics are discussed.

Mathematical Biosciences

Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

Dissolution of synthetic strontianite-aragonite solid solutions was followed analytically to stoichiometric saturation using large solid to solution ratios in CO 2 -H 2 O solution at 25 and 76°C. The compositional dependence of the equilibrium constant was calculated from the composition of saturated (stoichiometric) solutions and used to calculate the activities and activity coefficients of CaCO 3 and SrCO 3 in the solid Ca (1− x ) Sr x CO 3 at 25 and 76°C. The results show that the solid-solution is not regular but unsymmetrical. The excess free energy of mixing is closely modeled for all compositions by the relation where A 0 is 8.49 ± 0.30 and 7.71 ± 0.20 KJ/mole and A 1 is −4.51 ± 0.20 and −3.36 ± 0.40 KJ/mole at 25 and 76°C, respectively. The equilibrium constant is denned as a function of the SrCO 3 mole fraction, x , by the relation where R is the gas constant, T is in Kelvins and K A and K S are the aragonite and strontianite equilibrium constants. The experimental results indicate the Henry's law coefficients of SrCO 3 in aragonites containing 0 to 6 mole percent SrCO 3 are approximately 91± 8 and 23 ± 1 at 25 and 76°C, respectively and for strontianites the Henry's law coefficients and applicable compositional ranges are approximately 7.3 ± 0.3 (0.84 ≤ x ≤ 1.00) and 3.3 ± 0.5 (0.50 ≤ x ≤ 1.00) at 25 and 76°C, respectively. Substitution of small amounts of Sr in aragonite and Ca in strontianite initially increases the stability of the solid. The most stable aragonites and strontianites contain 0.58 ± 0.03 and 12.5 ± 1.1 mole percent SrCO 3 and CaCO 3 at 25°C and 3.1 ± 0.3 and 17.2 ± 1.1 mole percent SrCO 3 and CaCO 3 at 76°C, respectively. The spinode occurs over the regions 0.065 ± 0.001 ≤ x ≤ 0.620 ± 0.014 at 25°C and 0.103 ± 0.007 ≤ x ≤ 0.585 ± 0.019 at 76°C where all compositions are unstable. A miscibility gap occurs over the compositional ranges 0.0058 ± 0.0003 ≤ x ≤ 0.875 ± 0.011 at 25°C and 0.031 ± 0.003 ≤ x ≤ 0.828 ± 0.011 at 76°C and is in reasonable agreement with reported compositions of natural aragonites and strontianites. Marine aragonites are neither at equilibrium nor stoichiometric saturation with surface seawater. The experimentally observed distribution coefficient of Sr in aragonite is 12 times larger than the calculated equilibrium value (0.095) at 25°C. Naturally occurring strontianites contain large amounts of calcium primarily because Ca/Sr ratios in natural waters are typically large. Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

Geochimica et Cosmochimica Acta