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Aquatic Geochemistry (v.6, #1)
The Equation of State of Lakes by Frank J Millero (pp. 1-17).
In recent years, a number of workers have studied the stability of deep lakes such as Lake Tanganyika, Lake Baikal and Lake Malawi. In this paper, the methods that can be used to determine the effect that the components of lakes have on the equation of state are examined. The PVT properties of Lakes have been determined by using apparent molal volume data for the major ionic components of the lake. The estimated PVT properties (densities, expansibility and compressibilities) of the lakes are found to be in good agreement with the PVT properties (P) of seawater diluted to the same salinity. This is similar to earlier work that showed that the PVT properties of rivers and estuarine waters could also be estimated from the properties of seawater.The measured densities of Lake Tanganyika were found to be in good agreement (± 2 × 10-6 g cm-3) with the values estimated from partial molal properties and the values of seawater at the same total salinity (ST = 0.568‰). The increase in the densities of Lake Tanganyika waters increased due to changes in the composition of the waters. The measured increase in the measured density (45 × 10-6 g cm-3) is in good agreement (46 × 10-6 g cm-3) with the values calculated for the increase in Na+, HCO3 -, Mg2+, Ca2+ and Si(OH)4.Methods are described that can be used to determine the conductivity salinity of lakes using the equations developed for seawater. By combining these relationships with apparent molal volume data, one can relate the PVT properties of the lake to those of seawater.
Keywords: lakes; density; compressibility; expansibility; conductivity; stability; pvt properties
Oxyanion Concentrations in Eastern Sierra Nevada Rivers – 3. Boron, Molybdenum, Vanadium, and Tungsten by Kevin H. Johannesson; W. Berry Lyons; Elizabeth Y. Graham; Kathleen A. Welch (pp. 19-46).
Water samples were collected from 10 locations along the Truckee River system, 14 locations along the Walker River system, and 12 locations along the Carson River, and analyzed for B, Mo, V, W, Na, Cl, and pH. Boron concentrations ranged from approximately 2 μmol/kg in the upper reaches of the Truckee River to almost 1,200 μmol/kg in Pyramid Lake. Molybdenum, V, and W had concentrations in the nanomolal range; Mo varied from a low of about 12 nmol/kg to a high of 3,200 nmol/kg (Walker Lake); V ranged from 9 nmol/kg to approximately 470 nmol/kg; and W varied from a low value around 0.8 nmol/kg (West Walker River) to 1,030 nmol/kg. The high concentrations of these oxyanion-forming trace elements in the rivers reflects (1) the relative stability of these oxyanions (e.g., MoO4 2-, HVO4 2-, WO4 2-, B(OH)3, and/or B(OH)4 -) in the alkaline, well oxygenated river and lake waters, (2) contributions of hydrothermal waters (especially for B), and (3) weathering of rocks/regolith with high concentrations of these elements. In the case of Mo, V, and W, each exhibited relatively conservative behavior in the upper, oxygenated reaches of all three rivers. During the study period the region experienced a prolonged drought such that the lower reaches of each river were typified by no flow or stagnant waters and probably low oxygen and/or anoxic conditions (although not measured). Reductive processes occurring in the low flow to stagnant reaches of each river could have led to removal of Mo, V, and W from solution as coprecipitates with Fe monosulfides, or via sorption to Fe oxides/oxyhydroxides and/or organic matter. Boron, however, exhibited essentially no or minor removal from these rivers, and instead was added to each river via B-rich hydrothermal waters (e.g., Steamboat Creek from Steamboat Hot Springs), or by B-rich groundwaters via base-flow during the extensive drought.
Keywords: Boron; eastern Sierra Nevada rivers; Lake Tahoe; molybdenum; oxyanions; Pyramid Lake; tungsten; vanadium; Walker Lake
Orthogonal Variance Structures in Lake Water Quality Data and Their Use for Geo-chemical Classification of Dimictic, Glacial/Boreal Lakes by Tomas K. E. Thierfelder (pp. 47-64).
The accumulating volumes of data collected within environmental monitoring programs facilitate the use of exploratory statistical methods of data analysis as a supplement to traditional methods of characterizing lake water quality. When principal component analysis and multidimensional scaling are applied to a matrix containing approximately 24000 samples of lake water quality variables pH, alkalinity, conductivity, hardness, color, Secchi depth and total phosphorus concentration, it is found that the total matrix variance can be approximately reproduced in an orthogonal two-dimensional base with transformations of hardness and color as best principal component representatives. This base is suggested as an empirical lake classification standard where the variance structure of subset lake populations (such as single lakes) can be referenced to the water quality standard of the generic population. Since the principal axes of the base exclusively contain inorganic and organic related variables respectively, the combined inorganic/organic characteristics of the lake can be expressed with the hardness and color variables alone. With the data matrix being large enough to produce high significance levels, and with variable ranges wide enough to represent a majority of dimictic, glacial/boreal lakes, the analysis results should be valid in many lakes throughout the world.
Keywords: Classification; Empirical; Geochemical; Lake Water Quality; Statistical
Remineralization Ratios in the Subtropical North Pacific Gyre by Yuan-Hui Li; David M. Karl; Christopher D. Winn; Fred T. Mackenzie; Kathleen Gans (pp. 65-85).
Based on a new mixing model of two end-members, the water column remineralization ratios of P/N/Corg - O2 = 1/13 ± 1/135 ± 18/170 ± 9 are obtained for the Hawaii Ocean Time-series (HOT) data set at station ALOHA. The traditional Redfield ratios of P/N/Corg/–O2 = 1/16/106/138 have standard deviations of more than 50%, when they are based on the average composition of phytoplankton. Apparently, the remineralization processes in the water column have smoothed out the observed large variability of plankton compositions. A new molar formula for the remineralized plankton may be written as 135H280O105N13P or C25(CH2O)101(CH4)9(NH3)13(H3PO4). Oxidation of this formula results inC25(CH2O)101(CH4)9(NH3)13(H3PO4) + 170O2 → 135CO2 + 132H2O + 13NO3 - + H2PO4 - + 14H+.For comparison, remineralization using Redfield's formula gives:(CH2O)106(NH3)16(H3PO4) + 138O2 → 106CO2 + 122H2O + 16NO3 -+ H2PO4 - + 17H+
Keywords: Mixing model; preformed nutrients; Redfield ratios; Remineralization ratios
Dissolution Kinetics of Calcite in 0.1 M NaCl Solution at Room Temperature: An Atomic Force Microscopic (AFM) Study by Ryoji Shiraki; Peter A. Rock; William H. Casey (pp. 87-108).
Atomic force microscopy (AFM) was used to study the rates of migration of the (10¯1 4) plane of a single-crystal of calcite dissolving in 0.1 M NaCl aqueous solutions at room temperature. The solution pH and PCO 2 controlled in the ranges 4.4 < pH < 12.2 and 0 < PCO 2 < 10-3.5 atm (ambient), respectively. Measured step velocities were compared with the mineral dissolution rates determined from the calcium fluxes. The step velocity is defined as the average of the velocities of the obtuse and acute steps. Rates of step motion increased gradually from 1.4(±0.2) at pH 5.3 to 2.4(±0.3) nm s-1 at pH 8.2, whereas the rates inverted and decreased to the minimum value of 0.69(±0.18) nm s-1 at pH 10.8. For pH > 10.8, only the velocity of the obtuse steps increased as pH increased, whereas that of acute steps gradually decreased.The dissolution rate of the mineral can be calculated from the measured step velocities and average slope, which is proportional to the concentration of exposed monomolecular steps on the surface. The average slope of the dissolving mineral, measured at pH 5.6 and 9.7, was 0.026 (±0.015). Using this slope, we calculate bulk dissolution rates for 5.3 < pH < 12.2 of 4.9(±3.0) × 10-11 to 1.8(±1.0) × 10-10 mol cm-2 s-1. The obtained dissolution rate can be expressed by the following empirical equation:Rdss = 10-4.66(±0.13)[H+] + 10-3.87(±0.06)[HCO3 -] + 10-7.99(plusmn; 0.08)[OH-]We propose that calcite dissolution in these solutions is controlled by elementary reactions that are similar to those that control the dissolution of other amphoteric solids, such as oxides. The mechanisms include the proton-enhanced hydration and detachment of calcium-carbonate ion pairs. The detachments are enhanced by the presence of adsorbed nucleophiles, such as hydroxyl and bicarbonate ions, and by protons adsorbed to key oxygens. A molecular model is proposed that illustrates these processes.
Keywords: AFM; calcite; dissolution kinetics; microtopography; step velocity