The partial molal volume of silicic acid in 0.725 M NaCl at 1°C determined by the neutralization of Na2SiO3

The partial molal volume of silicic acid ($\text{V}\text{?}\text{(Si(OH)}{}_4\text{)}$) in 0.725 M NaCl at 1°C was calculated from the measured volume change (Δ$\text{V}\text{?}{}_{\mathrm{n}}$) due to the neutralization of anhydrous sodium metasilicate with HCl and the $\text{V}\text{?}\text{(HCl)}$ and $\text{V}\text{?}\text{(NaCl)}$ obtained from the literature. $\text{V}\text{?}\text{(Si(OH)}{}_4\text{) = 59.0 cm}{}^3\text{mol}\text{? 1}$, determined under experimental conditions of pH = 2.2, compares favorably with $\text{V}\text{?}\text{(Si(OH)}{}_4\text{) = 58.9 cm}{}^3\text{mol}{}^{\mathrm{?1}}$ calculated from the measured volume change due to the hydrolysis of the meta-silicate salt at pH = 11 and from the partial molal volume due to electrostriction ($\text{V}\text{?}{}_{\mathrm{elect}}$) of water by charged Si species present in the solution at the high pH. This agreement lends support to a semiempirical model for calculating $\text{V}\text{?}{}_{\mathrm{elect}}$ in developed by Millero (1969). $\text{V}\text{?}\text{(NaOH) = ? 5.45 cm}{}^3\text{mol}{}^{\mathrm{?1}}$ in 0.725 M NaCl needed for this calculation was also determined in this work. The rate of polymerization of Si(OH)₄ at 1°C was monitored to insure that the monomer Si(OH)₄ was the main Si species present during the determination of $\text{V}\text{?}\text{(Si(OH)}{}_4\text{)}$ by neutralization of the alkali silicate. $\text{V}\text{?}\text{(Si(OH)}{}_4\text{)}$ determined in this study compares favorably with the value calculated from high pressure solubility measurements.     

Partial molal volume calculations for the dissolution of aged amorphous silica in salt water and seawater at 0–2°C

Measurement of solubility as a function of pressure allows calculation of $\text{3}\text{V}\text{?}{}_1$. Using this experimental approach, the best estimate of $\text{3}\text{V}\text{?}{}_1$ for the dissolution of aged amorphous silica in salt water or seawater at 0–2°C is ?9.9 cm³ mol^?1 (standard error = 0.4 cm³ mol^?1). This gives , which compares well with other published values of .     

The partial molal volume of silicic acid in 0.725 m NaCl

The partial molal volume ($\text{V}\text{?}$) of silicic acid in 0.725 m NaCl at 20°C has been calculated from (1) direct volume changes due to the dissolution of anhydrous sodium silicate and (2) some literature values for the partial molal volumes of NaOH and water. , unconnected for electrostriction effects, was found to be 53 ± 2 ml mole^?1. , corrected for volume changes due to solvent electrostriction by charged Si species, was estimated to be in the range 58–62 ml mole^?1; this range is 7–11 ml mole^?1 greater than the calculated from Willey's (Mar. Chem. 2, 239–250, 1974) solubility data obtained from the dissolution, in seawater, of amorphous silica subjected to hydrostatic pressure. Our does, however, agree within experimental error with the calculated from Jones and Pytkowicz's (Bull. Soc. Roy. Sci. Liege 42, 118–120, 1973) data for the solubility of amorphous silica in seawater at high pressure and is nearly in agreement with Willey's (Ph.D. thesis, Dalhousie University, 1975) solubility data for amorphous silica in 0.6 m NaCl.     

Density calculations for silicate liquids. I. Revised method for aluminosilicate compositions

Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature T_r, is given by $\text{V}{}_{\mathrm{r}}\text{= ∑X}{}_{\mathrm{i}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{i}}\text{+ X}{}_{\mathrm{A}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$, where the summation is taken over all oxide components except A1₂O₃, X stands for mole fraction, terms are constants derived independently from an analysis of volume-composition relations in alumina-free silicate liquids, and $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is the composition-dependent apparent partial molar volume of Al₂O₃. The thermal expansion coefficient of aluminosilicate liquids is given by $\text{α = ∑X}{}_{\mathrm{i}}\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}\text{+ X}{}_{\mathrm{A}}\text{}\text{?}\text{ga}{}_{\mathrm{A}}{}^{\mathrm{o}}$, where $\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}$ terms are constants independent of temperature and composition, and $\text{}\text{?}\text{ga}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is a composition-dependent term representing the effect of Al₂O₃ on the thermal expansion. Parameters necessary to calculate the volume of silicate liquids at any temperature T according to V(T) = V_rexp[α(T-T_r)], where T_r = 1400°C have been evaluated by least-square analysis of selected density measurements in aluminosilicate melts. Mean molar volumes of aluminosilicate liquids calculated according to the model equation conform to experimentally measured volumes with a root mean square difference of 0.28 $\text{cc}\text{mole}$ and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is discussed in terms of several possible interpretations of the structural role of Al³⁺ in aluminosilicate melts.     

A recycle flow flotation machine model

Residence time measurements were made on a Denver laboratory flotation machine with and without the DR ring assembly. Soluble and insoluble tracers were used (a dye and fine quartz, respectively), and the variables studied were tank liquid volume, $\text{V}$, water and air volumetric flow rates, Q and Q_A respectively, and some geometric and design variables.By analogy with nominal residence time, $\text{t}{}_{\mathrm{<mtext>N</mtext>}}\text{(=}\text{V}\text{Q}\text{)}$, a term “effective residence time” $\text{t}{}_{\mathrm{<mtext>E</mtext>}}$ is defined by:

$\text{f}\text{(t)=}\text{exp}\text{[?}\text{t}\text{t}{}_{\mathrm{E}}$

where f(t) is the fraction of tracer remaining in the tank at time t. Perfect mixing is indicated if and only if: (i) data satisfies the exponential relationship; and (ii) $\text{t}{}_{\mathrm{<mtext>E</mtext>}}\text{t}{}_{\mathrm{<mtext>N</mtext>}}\text{= 1}$.Using the soluble tracer the machine behaved substantially as a perfect mixer under all operating conditions, except with the DR ring at values of Q_A nearly double the natural aeration capacity of the machine; condition (i) above was satisfied, but $\text{t}{}_{\mathrm{<mtext>E</mtext>}}\text{t}{}_{\mathrm{<mtext>N</mtext>}}\text{～ 1.1}$.With the insoluble tracer the machine behaved as a perfect mixer only without air. As Q_A increased, $\text{t}{}_{\mathrm{<mtext>E</mtext>}}\text{t}{}_{\mathrm{<mtext>N</mtext>}}$ increased from unity to about 1.2, and the effect was emphasized by the DR ring. In all cases condition (i) above was satisfied.A model in which the flow pattern in the tank includes a large component of pulp recirculation through the impeller region is developed. This model can account for the experimental findings but the details remain to be elucidated.     

Carbonate equilibria in hydrothermal systems: First ionization of carbonic acid in NaCl media to 300°C

The ionization quotients of aqueous carbon dioxide (carbonic acid) have been precisely determined in NaCl media to 5 m and from 50° to 300°C using potentiometric apparatus previously developed at Oak Ridge National Laboratory. The pressure coefficient was also determined to 250°C in the same media. These results have been combined with selected information in the literature and modeled in two ways to arrive at the best fits and to derive the thermodynamic parameters for the ionization reaction, including the equilibrium constant, activity coefficient quotients, and pressure coefficients. The variation with temperature of the two fundamental quantities $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ and $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ were examined along the saturation vapor pressure curve and at constant density. The results demonstrated again that for reactions with minimal electrostriction changes the magnitudes and variations of $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ with temperature are small and, in addition, $\text{Δ}\text{C}\text{?}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}$ are approximately independent of salt concentration.The results have also been applied to an examination of the solubility of calcite as a function of pH (in a given NaCl medium) for the neutral to acidic region both for systems with fixed CO₂ pressure and systems where the calcium ion concentration equals the concentration of carbon. The pH of saturated solutions of calcite with P_CO2 of 12 bars increases from 5.1 to 5.5 between 100° and 300°C.     

The effect of pressure on the solubility of minerals in water and seawater

The effect of presure on the solubility of minerals in water and seawater can be estimated from In

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.     

Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity,and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

We have calculated the total individual ion activity coefficients of carbonate and calcium, and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of and are $\text{0.038 ± 0.002}$ and $\text{0.173 ± 0.010}$, respectively. These values of and are independent of liquid junction errors and internally consistent with the value . By defining and on a common scale (), the product is independent of the assigned value of and may be determined directly from thermodynamic measurements in seawater. Using the value and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978, Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.     

Luna 20: mineral chemistry of spinel,pleonaste, chromite,ulvöspinel,ilmenite and rutile

Electron microprobe analyses of the spinel mineral group, ilmenite and rutile have been carried out on part of the Luna 20 soil sample. The spinel group shows an almost continuous trend from MgAl₈O₄ to FeCr₂O₄ and a discontinuous trend from FeCr₂O₄ to Fe₂TiO₄. Well defined non-linear relationships exist within the spinel group for Fe-Mg substitution, for divalent ($\text{FeO}\text{FeO + MgO}$) versus trivalent ($\text{Cr}{}_2\text{O}{}_3\text{Cr}{}_2\text{O}{}_3\text{+ A1}{}_2\text{O}{}_3$), and for divalent versus $\text{TiO}{}_2\text{TiO}{}_2\text{+ A1}{}_2\text{O}{}_3\text{+ Cr}{}_2\text{O}{}_3$. For Cr-Al substitution the relationship is linear and is negative for Mg-rich spinel and positive for Fe-Ti rich spinel. In general a combination of aluminous-rich chromite and ulvöspinel in the Luna 16 samples, combined with the chromian-pleonaste in Apollo 14 define comparable major compositional trends to those observed in Luna 20. Ilmenite is present in trace amounts. It is exsolved from pleonaste and pyroxene, is present in subsolidusreduced ulvöspinel and has undergone reequilibration to produce oriented intergrowths of chromite + rutile. Primary ilmenite is among the most magnesian-rieh (6 wt.% MgO) yet found in the lunar samples. The high MgO, inferred high Cr₂O₃ concentrations and the iron content of rutile (2.5 wt.% FeO) suggest crystallization at high temperatures and pressures for some components of the Luna 20 soil.     

The use of the specific interaction model to estimate the partial molal volumes of electrolytes in seawater

The specific interaction model has been used to determine the partial molal volume of electrolytes in 0.725 m NaCl and 35‰ salinity seawater solutions at 25°C. The partial molal volumes of electrolytes (MX) were estimated at a given ionic strength (I) from

$\text{V}\text{(}\text{MX}\text{) =}\text{V}{}^0\text{(}\text{MX}\text{) +}\text{S}{}_{\mathrm{v}}\text{I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(1 + I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}\text{+ v}{}_{\mathrm{M}}\text{∑}\text{X}\text{B}{}_{\mathrm{<mtext>MX</mtext>}}\text{[X] + v}{}_{\mathrm{X}}\text{∑}\text{M}\text{B}{}_{\mathrm{<mtext>MX</mtext>}}\text{[X]}$

, where S_V is the Debye-Hückel limiting law slope, v_i is the number of ions i formed when MX dissociated, [i] is the total molality of ion i and B_MX is a specific interaction parameter that varies slowly with ionic strength. The values of $\text{V}\text{(}\text{MX}\text{)}$ estimated by using this equation were found to agree very well with experimental values in NaCl and seawater providing there are not strong interactions between M and X. For electrolytes that form ion pairs (i.e. MX°) corrections must be made. Methods are discussed for making these corrections.     

Geochemistry and petrogenesis of lamproites,late cretaceous age,Woodson County,Kansas, U.S.A.

Lamproite sills and their associated sedimentary and contact metamorphic rocks from Woodson County, Kansas have been analyzed for major elements, selected trace elements, and strontium isotopic composition. These lamproites, like lamproites elsewhere, are alkalic (molecular $\text{K}{}_2\text{O + Na}{}_2\text{O}\text{Al}{}_2\text{O}{}_3\text{= 1.6–2.6}$), are ultrapotassic $\text{(}\text{K}{}_2\text{O}\text{Na}{}_2\text{O}\text{= 9.6–150)}$, are enriched in incompatible elements (LREE or light rare-earth elements, Ba, Th, Hf, Ta, Sr, Rb), and have moderate to high initial strontium isotopic compositions (0.7042 and 0.7102). The silica-saturated magma (olivine-hypersthene normative) of the Silver City lamproite could have formed by about 2 percent melting of a phlogopite-garnet lherzolite under high $\text{H}{}_2\text{O}\text{CO}{}_2$ ratios in which the Iherzolite was enriched before melting in the incompatible elements by metasomatism. The Rose Dome lamproite probably formed in a similar fashion although the extreme alteration due to addition of carbonate presumably from the underlying limestone makes its origin less certain. Significant fractional crystallization of phases that occur as phenocrysts (diopside, olivine, K-richterite, and phlogopite) in the Silver City magma and that concentrate Co, Cr, and Sc are precluded as the magma moved from the source toward the surface due to the high abundances of Co, Cr, and Sc in the magma similar to that predicted by direct melting of the metasomatized Iherzolite.Ba and, to a lesser extent, K and Rb and have been transported from the intrusions at shallow depth into the surrounding contact metamorphic zone. The Silver City lamproite has vertical fractionation of some elements due either to volatile transport or to variations in the abundance of phenocrysts relative to groundmass most probably due to flow differentiation although multiple injection or fractional crystallization cannot be conclusively rejected.     

Thermodynamic stability studies of the basic copper carbonate mineral,malachite

Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined:

(infinite dilution)

$\text{K}{}^1{}_{\mathrm{sp}}\text{=}\text{[Cu}{}^{\mathrm{2+}}\text{]}{}^2\text{[CO}{}^{\mathrm{2?}}{}_3\text{]K}{}^2{}_{\mathrm{w}}\text{a}{}^2{}_{\mathrm{H+}}\text{= 10. ± 0.2 × 10}{}^{\mathrm{?32}}$

(0.72 ionic strength)

(36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, K_sp⁺, of the form:

has been measured at I = 0.72, yielding the relationship:

$\text{log K}{}^2{}_{\mathrm{sp}}\text{= (? 9.8 ± 0.03) × 10}{}^4\text{(}\text{1}\text{T°K}\text{) + (1.52 ± 0.09)}$

within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution $\text{K'}{}_{\mathrm{sp}}\text{(1000 bar)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 240}$ and in seawater $\text{K′}{}_{\mathrm{sp}}\text{(1000)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 44}$.Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H₂O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater (S = 36.9%., TA = 2.3 meq/kg H₂O, pH = 8.1), $\text{[Cu}{}^{\mathrm{2+}}\text{]}\text{T(Cu)}$ is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater.     

Correction of ground-water chemistry and carbon isotopic composition for effects of CO2 outgassing

Direct measurements on water samples from several CO₂-charged warm springs are significantly higher than values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO₂ outgassing during pH measurement. Because samples for direct measurement can be taken with minimal disturbance to the water chemistry, we have used the measured to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of $\text{δ}{}^{13}\text{C}$, pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH.     

Selective flotation of inherently hydrophobic minerals by controlling the air/solution interfacial tension

Selective wettability and floatability of several inherently hydrophobic minerals have been investigated using aqueous methanol solutions of various surface tensions. The relationship between the critical surface tension of wetting, $\text{γ}{}_{\mathrm{<mtext>c</mtext>}}$, and of floatability, $\text{γ}{}_{\mathrm{<mtext>cf</mtext>}}$, of the samples is examined. Experimental evidence is provided to show that a flotation feed cannot be represented by an uniquely defined $\text{γ}{}_{\mathrm{<mtext>cf</mtext>}}$ value. It is appropriate to specify for an inherently hydrophobic solid a critical surface tension range of floatability with upper and lower limits, $\text{γ}{}_{\mathrm{<mtext>cmf</mtext>}}$ and $\text{γ}{}_{\mathrm{<mtext>clf</mtext>}}$ respectively. The particles which are predominated by cleavage or crystal faces determine the lower limit, while those with some threshold degree of ionic character determine the upper limit. Examples of separation tests presented demonstrate that in the case of equality between $\text{γ}{}_{\mathrm{<mtext>c</mtext>}}$ values of two inherently floatable solids (or their $\text{γ}{}_{\mathrm{<mtext>clf</mtext>}}$ values), a difference in $\text{γ}{}_{\mathrm{<mtext>cmf</mtext>}}$ values determines the efficiency of their separation. It is also shown that the interfacial tension of maximum separation efficiency may be predicted from the individual surface tension of floatability curves which may be represented by second-order functions.     

Genesis of cordierite-gedrite-cummingtonite rocks of the northern portion of the khetri Copper Belt,Rajasthan, India

The cordierite-gedrite-cummingtonite rocks occur in the zone of sulphide mineralization. Field and petrographic evidences suggest formation of these rocks from the $\text{chlorite}\text{±}\text{garnet}$ schists which are associated with them. Time relations between crystallization and deformation, as evident by textural relations, suggest that this transformation constitutes a progressive sequence in time during prograde metamorphism in the area. Bulk chemical compositions of the cordierite-gedrite-cummingtonite rocks plot in the compositional range of the chlorite schists in the AKF, ACF and AFM diagrams. The AFM diagram shows a discontinuity in the topology as revealed by the intersection of the coexisting garnet-chlorite join with the three-phase field of cordierite-gedrite-garnet, suggesting the reaction: $\text{Al-chlorite}\text{+}\text{quartz}\text{(±}\text{garnet}\text{) ?}\text{gedrite}\text{+}\text{cordierite}\text{+}\text{H}{}_2\text{O}$. The reaction took place under conditions of , brought about by dilution of pore fluid by B, Cl, F, S, etc., which reduce the activity of water.     

Settling velocities of particulate systems, 3. Power series expansion for the drag coefficient of a sphere and prediction of the settling velocity

The following equation has been previously developed for the drag coefficient of a sphere.

$\text{C}{}_{\mathrm{D}}\text{= C}{}_0\text{[1 + (σ}{}_0\text{/Re}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)]}{}^2$

In this work the authors propose a power series expansion for C₀ in terms of the Reynolds number:

$\text{C}{}_0\text{= 0 284153}\text{Σ}\text{α=0}\text{n}\text{B}{}_{\mathrm{\alpha }}\text{Re}{}^{\mathrm{\alpha }}$

A fifth-order polynomial permits obtaining the drag coefficient and the settling velocity of a sphere, up to a Reynolds number of 3 × 10⁵, with an average relative error of about 2%.     

Secular variations in kerogen structure and carbon,nitrogen and phosphorus concentrations in pre-Phanerozoic and Phanerozoic sedimentary rocks

Variations in the chemical composition of sedimentary rocks and the nature of kerogen through geologic time were investigated in order to obtain information on biological and environmental evolution during the pre-Phanerozoic eon. Rock samples differing in lithology, depositional environment, and age were pulverized, pre-extracted with organic solvents, and analyzed for total nitrogen (N), phosphorus (P) and organic carbon (org. C or C_T). Variations in the molecular structure of kerogen were measured by determining the ratio of org. C content after pyrolysis (C_R) to org. C content before pyrolysis (C_T), the $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio being considered an index of the degree of condensed-aromatic (as opposed to aliphatic) character. The rocks included mudstones (Early Archean (> 3 · 10⁹ years old) to Miocene), carbonate rocks (mid-Proterozoic (1.3 · 10⁹ years old) to Eocene), cherts (Early Archean (> 3 · 10⁹ years old) to Late Proterozoic (0.8 · 10⁹ years old)), and coal (Archean (> 2.7 · 10⁹ years old) to Early Proterozoic (～1.8 · 10⁹ years old)).The mudstones and carbonates showed progressive increase in org. C content with decreasing age, as reported by other investigators, but the cherts unexpectedly showed a decrease in org. C content with decreasing age. In all samples, a simple inverse correlation between $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and org. C was observed, each rock type forming its own trend separate from but parallel to those of the other rock types. Thus, the older cherts tend to be richer in org. C and have lower $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios, but the older carbonates and mudstones are poorer in org. C and have higher $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios. For a given org. C concentration, chert has the highest $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and carbonate rock the lowest, mudstone being intermediate; this may mean that chert is relatively ineffective as a catalyst for the thermal cracking of kerogen or that it inhibits cracking. N appears to be correlated with org. C. The relationship between $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and org. C or N suggests that the concentrations of org. C and N in sedimentary rocks are largely determined by selective elimination of labile aliphatic and nitrogenous groups of kerogen during post-depositional maturation, although the nature, abundance and depositional environment of the organic source material must be taken into consideration as well. The observed secular variations of org. C, N and $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio may be ascribed to several possible causes, including age-dependent post-depositional alteration of kerogen, secular decrease in the $\text{CO}{}_2\text{O}{}_2$ ratio of the atmosphere and hydrosphere during pre-Phanerozoic time, secular increase in rates of accumulation of organic matter in sediments and evolutionary changes in the composition of the biological source material. The secular variations of the carbonates and mudstones could be accounted for by age-dependent cumulative effects of post-depositional alteration alone, whereas the secular variations of the cherts probably reflect changes in the nature of the biological source material and the composition of the atmosphere and hydrosphere. The available evidence suggests that primary characteristics of kerogen are better preserved in chert than in the other types of sediment.The $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios of the carbonates and cherts correlate negatively with the $\text{A}{}_{\mathrm{<mtext>465</mtext><mtext>m</mtext><mtext>\mu </mtext>}}\text{A}{}_{\mathrm{<mtext>665</mtext><mtext>m</mtext><mtext>\mu </mtext>}}$ absorbance ratios of “humic matter” extracted from the same rock samples with benzene—methanol. Thus, the greater the degree of condensed-aromatic character of the kerogen, the greater the degree of condensed-aromatic character of the solvent-extractable bituminous “humic matter” with which it is associated. In addition, the ratio of aliphatic to carbonyl-type groups ($\text{CH}{}_2\text{C=O}$) in the extractable “humic matter” of carbonates and cherts correlates with the non-extractable org. C content of the rocks, suggesting that the org. C data are related to the degree of aliphatic character of the kerogen. The chemical similarity between extractable “humic matter” and its associated kerogen is evidence that the “humic matter” is as old as its rock matrix and can be accepted as a valid chemical fossil. It also suggests that information obtainable from kerogen may be gotten more easily, rapidly and cheaply from solvent-extractable organic matter. The mudstones showed little or no relationship between $\text{A}{}_{\mathrm{<mtext>465</mtext><mtext>m</mtext><mtext>\mu </mtext>}}\text{A}{}_{\mathrm{<mtext>665</mtext><mtext>m</mtext><mtext>\mu </mtext>}}$ ratio and $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio, or between $\text{CH}{}_2\text{C=O}$ ratio and org. C content. The data are consistent with the hypothesis that the kerogen in the carbonates and cherts is autochthonous, whereas the kerogen in the mudstones is partly allochthonous, implying the existence of soil humus and soil organisms in pre-Phanerozoic times. Moreover, the existence of coal in Archean sediments is consistent with the existence of very shallow-water and possibly terrestrial microfloras possessing adaptations for protection against ultraviolet solar radiation.The P content of the sediments showed a complicated zig-zag pattern of variation through geologic time. All the different suites of samples gave similar results, indicating that the variations represent phenomena whose effects were worldwide and independent of local environment. P levels are low in the early pre-Phanerozoic but rise with decreasing age until ～ 1 · 10⁹ years B.P., then fall to a minimum at (～0.7–0.8) · 10⁹ years B.P., and rise again to a lower Paleozoic (Ediacarian?) maximum, decline to a later Paleozoic minimum, and then rise again. The low P content of early pre-Phanerozoic sediments could be due to several factors, including high CO₂ content of seawater, anaerobic conditions in the sea, absence of stable-shelf environments, and low rates of primary production. The minimum in the Late Proterozoic is tentatively attributed to the Late Proterozoic glaciations. The data are consistent with the theory that the glacial episode was of worldwide extent.