A Linear Programming Approach to Determine the Normative Composition of Sedimentary Rocks

The analysis of modal and normative composition of sedimentary rocks is widely used for studying their sources and tectonic settings. The normative calculation of the mineral composition of rocks in this study is formulated as a linear programming problem and is solved by means of the simplex method. This enables both simultaneous and successive subtraction of a set of basic minerals from a rock sample represented by its chemical composition {SiO₂...LOI}. Such an approach provides a more exact calculation of the contribution of basic minerals in the rock. This mathematical approach is used to study two representative sets of sandstones and fine-grained rocks from a Meso- to Neoproterozoic marginal basin of southeastern Siberia (Uchur–Maya region, Yakutia) and a Pennsylvanian-Lower Permian uplifted continental block in Colorado, USA. The calculated normative mineral compositions of the Siberian sandstones are consistent with the observed modal compositions. These sandstones vary from K- Feldspar rich arkoses at the base of the sequence (the Uchur Group, lower Riphean) to quartz arenites or lithic sandstones and wacke in transgressive successions of the middle-upper Riphean. Arkoses and quartz arenites are dominant in Meso- to Neoproterozoic Siberia. These samples represent craton interior uplifted basement and quartzose, recycled orogen provenance of a stable craton in Rodinia. There are higher but consistent discrepancies between the calculated and observed compositions for the Pennsylvanian to Lower-Permian arkoses and quartz arenites (Sangre de Cristo, Belden, and Maroon Formations). The differences between the predicted and observed mineralogy may be due to uncertainties in the modes in the matrix and cement of the sandstones. This normative program should supplement modal calculations and provide better genetic constructions, especially in case of matrix-rich sandstones.     

Geochemical signature of provenance in sand-size material in soils and stream sediments near the Tobacco Root batholith, Montana, U.S.A.

Trace-element geochemistry of sandstones are being used to determine provenance. We have conducted preliminary and limited experiments to determine to what extent daughter sands retain the geochemical signature of parent rocks. Six sets of first-order stream sediments, soils from adjacent slopes, and a variety of parent rocks were collected from southwestern Montana, U.S.A. Sampling in a low-relief area ensured that climate and residence time of soils on slopes could be eliminated as variables. Sand-size fractions of stream sediments and soils, and the corresponding parent rocks (granodiorite, quartz monzonite, granite gneiss, biotite-tonalite gneiss and amphibolite) were analyzed for most major elements and selected trace elements. Petrologic modal analysis of the parent rocks and the 0.25–0.50-mm fraction of each sand was done to monitor major mineralogic control, if any, on chemical compositions of the samples.

Our data show that the abundances of the Si and Al in sediments do not discriminate provenance. Abundances of Ca, Mg, Fe and Ti may broadly distinguish between sands derived from metamorphic and igneous source rocks, at least in the area studied. Differences in abundances of the Ba and Th, and the ratio of La/Lu between granitic, tonalitic and amphibolitic parent rocks are preserved in the daughter sediments that we studied. However, the size of the Eu anomaly in the REE patterns of different daughter sediments is not diagnostic of parent rocks. Abundances of Co and Sc distinguish between sediments derived from felsic and mafic rocks. A better provenance discrimination is obtained if the ratios La/Sc, Th/Sc, La/Co, Ba/Sc and Ba/Co are used.

Petrologic modal data show that mineral contents and chemical compositions of parent rocks are compatible with each other. The chemical composition of the sands may be roughly correlated to the petrological modal data but the abundances of some minor and trace elements of sediments cannot be inferred from modal mineralogy. This is expected because these elements may concentrate in accessory minerals and/or may weather out into aqueous or clay mineral fractions; it is also compatible with conclusions of previous studies that some of these elements do not reside in sand-size fractions of siliciclastic sediments.     

Elemental mobility during the weathering of exposed lower crust: the kinzigitic paragneisses from the Serre, Calabria, southern Italy

Weathering and transportation studies of the chemical composition of sediments have determined how surface fractionation processes modify the elemental signature due to provenance and tectonic setting of siliciclastic rocks. Although the bulk of the exposed upper continental crust comprises granitoids, metamorphic rocks from the intermediate to lower crust may be, in some geological contexts, the provenance of siliciclastic sediments. A preferential enrichment of the LREE relative to the HREE is observed in weathered, garnet-rich, kinzigitic paragneisses from the Calabrian Arc, southern Italy. This fractionation is due mostly to the mineralogical control exerted by monazite, which is concentrated in the silt-size fraction of the soil. However, a significant part of HREE, released during garnet alteration, is trapped by secondary minerals in the clay-sized fraction of the soil, in a manner similar to Pb²⁺ and Cs⁺, cations of some concern in environmental geochemistry. In the weathered material monazite is also important in controlling the Eu-anomaly, the negative size of which increases with increasing Th addition. The Eu-anomaly in the clay-sized fraction of the soil is very similar to that of the fresh rock, suggesting that the Eu/Eu* index in pelitic sediments deriving from the intermediate to lower crust may be regarded as a reliable indicator of parental affinity. Other provenance indicators include La/Th, which share the same mineralogical control; indicators of contrasting mafic and felsic provenance, e.g. Sc/Th, should be used with care.     

Rare-earths in size fractions and sedimentary rocks of Pennsylvanian-Permian age from the mid-continent of the U.S.A.

The REE (rare-earth) contents of sixty-three <2 μ fractions of Pennsylvanian and Permian platform sediment from the mid-continent of the U.S.A. vary considerably (ΣREE = 46–439 ppm;La/ Lu = 5.2–15.7; correlation coefficient of REE with La/Lu = 0.89), but the Eu/Sm ratios are nearly constant even in reducing environments that concentrate U (0.16–0.22). There is no correlation of REE content to clay mineralogy.Lower Permian <2 μ fractions from continental to nearshore marine sediment in Oklahoma have higher REE content (244–261 ppm) than marine facies in Kansas (46–140ppm), but <2μ Upper Permian fractions in an evaporite basin have constant but high REE content (288–281 ppm; one = 153—ppm). All Pennsylvanian <2 μ fractions from Oklahoma have high REE content (209–439 ppm), and fractions from Kansas cyclothems have variable REE content (86–438 ppm). REE content in the <2 μ fractions is inherited from the provenance, but is modified by ion exchange during weathering, transportation, or deposition. Exchangable REE tend to be concentrated in clay minerals in basic environments, but removed in acid environments.Sand and gravel-size fractions consist mostly of quartz or chert so their REE content is low (7.9–40.6 ppm) although heavy minerals may contribute a large fraction of the REE content. Unexpectedly, silt-size fractions have REE contents (74–355 ppm) that are usually lower but similar to their <2 μ fractions, and the REE contents do not correlate to clay mineral/quartz ratios. The interpretation of REE content in sedimentary rocks needs to be done cautiously due to the above factors.     

Mineralogy and petrology of cretaceous subsurface lamproite sills, southeastern Kansas, USA

Cores and cuttings of lamproite sills and host sedimentary country rocks in southeastern Kansas from up to 312 m depth were analyzed for major elements in whole rocks and minerals, certain trace elements in whole rocks (including the REE) and Sr isotopic composition of the whole rocks. The lamproites are ultrapotassic (K₂O/Na₂O = 2.0–19.9), alkalic [molecular (K₂O/Na₂O)/Al₂O₃ = 1.3-2.8], enriched in mantle-incompatible elements (light REE, Ba, Rb, Sr, Th, Hf, Ta) and have nearly homogeneous initial Sr isotopic compositions (0.707764-0.708114).

These lamproites could have formed by variable degrees of partial melting of harzburgite country rock and cross-cutting veins composed of phlogopite, K-Ti richterite, titanite, diopside, K-Ti silicates, or K-Ba-phosphate under high H₂O/CO₂ ratios and reducing conditions. Variability in melting of veins and wall rock and variable composition of the metasomatized veins could explain the significantly different composition of the Kansas lamproites.

Least squares fractionation models preclude the derivation of the Kansas lamproites by fractional crystallization from magmas similar in composition to higher silica phlogopite-sanidine lamproites some believe to be primary lamproite melts found elsewhere. In all but one case, least squares fractionation models also preclude the derivation of magmas similar in composition to any of the Kansas lamproites from one another. A magma similar in composition to the average composition of the higher SiO₂ Ecco Ranch lamproite (237.5–247.5 m depth) could, however, have marginally crystallized about 12% richterite, 12% sanidine, 7% diopside and 6% phlogopite to produce the average composition of the Guess lamproite (305–312 m depth).

Lamproite from the Ecco Ranch core is internally fractionated in K₂O, Al₂O₃, Ba, MgO, Fe₂O₃, Co and Cr most likely by crystal accumulation-removal of ferromagnesian minerals and sanidine. In contrast, the Guess core (305–312 m depth) has little fractionation throughout most of the sill except in several narrow zones. Lamproite in the Guess core has large enrichments in TiO₂, Ba, REE, Th, Ta and Sc and depletions in MgO, Cr, Co and Rb possibly concentrated in these narrow zones during the last dregs of crystallization of this magma.

The Ecco Ranch sill did not show any evidence of loss of volatiles or soluble elements into the country rock. This contrasts to the previously studied, shallow Silver City lamproite which did apparently lose H₂O-rich fluid to the country rock. Perhaps a greater confining pressure and lesser amount of H₂O-rich fluid prevented it from escaping.     

Sedimentary evolution of the Mesozoic continental redbeds using geochemical and mineralogical tools: the case of Upper Triassic to Lowermost Jurassic Monte di Gioiosa mudrocks (Sicily,southern Italy)

The continental redbeds from the Internal Domains of the central-western Mediterranean Chains have an important role in the palaeogeographic and palaeotectonic reconstructions of the Alpine circum-Mediterranean orogen evolution since these redbeds mark the Triassic-Jurassic rift-valley stage of Tethyan rifting. The composition and the sedimentary evolution of the Middle Triassic to Lowermost Jurassic continental redbeds of the San Marco d’Alunzio Unit (Peloritani Mountains, Southern Italy), based on mineralogical and chemical analyses, suggests that the studied mudrock sediments share common features with continental redbeds that constitute the Internal Domains of the Alpine Mediterranean Chains. Phyllosilicates are the main components in the mudrocks. The 10 Å-minerals (illite and micas), the I–S mixed layers, and kaolinite are the most abundant phyllosilicates. The amount of illitic layers in I–S mixed layers coupled with the illite crystallinity values (IC) are typical of high degree of diagenesis, corresponding to a lithostatic/tectonic loading of about 4–5 km. The mineralogical assemblage coupled with the A-CN-K plot suggest post-depositional K-enrichments. Palaeoweathering proxies (PIA and CIW) record intense weathering at the source area. Further, the studied sediments are affected by reworking and recycling processes and, as consequence, it is likely these proxies monitor cumulative effect of weathering. The climate in the early Jurassic favoured recycling and weathering occurred under hot, episodically humid climate with a prolonged dry season. The source-area is the low-grade Paleozoic metasedimentary basement. Mafic supply is minor but not negligible as suggested by provenance proxies.     

Rare earth elements in carbonatite and cogenetic alkaline rocks: Examples from Seabrook Lake and Callander Bay,Ontario

Associated rocks from the Seabrook Lake, carbonatite complex in Ontario show an increase in total REE (rare earth element) content and in light REE enrichment in the following order: fenite quartz monzohite 2 and H₂O-rich fluids.     

Mineralogical and chemical changes of soil and stream sediment formed by intense weathering of the Danburg granite, Georgia, U.S.A.

A series of soil and stream sediments developed during intense weathering on the metaluminous Danburg granite, northeastern Georgia, U.S.A., have been analyzed mineralogically and chemically. The concentrations of Ba, Na, Rb and Cs in the silt and coarser fractions are controlled mainly by feldspars and biotite. Hf is controlled by zircon, and the REE (rare-earth elements) and Th are largely controlled by sphene. Variations in feldspar, sphene and zircon may produce small variations in Eu/Sm and La/Lu ratios. Ferromagnesian minerals control Ta, Fe, Co, Sc and Cr concentrations.

The mineralogical and chemical composition of the Danburg granite is more closely reflected in the silt than in the sand or gravel fractions of stream sediments. In the silt, the contents of Rb, REE, Th, Ta, Fe, Co and Sc and the ratios of La/Sc, Th/Sc, La/Co, Th/Co, Eu/Sm and La/Lu are similar to those in the unweathered granite. In contrast, these element contents or ratios in the sands and gravels are 0.05−3× the concentration in the unweathered granite. Ta and Ba contents are an exception to the above. The Ta and Ba contents of the sands and gravels are similar to those of the granite.

In the kaolinite-halloysite clays, the content of Na is depleted relative to the source. Rb, Cs, Ba, Hf and Ta are depleted or enriched in the clays relative to the source, while the REE, Th, Fe, Co, Sc and Cr are enriched. The Eu/Sm (Eu anomaly size) and La/Lu ratios, and the REE patterns of the clays are similar to those of the source.

Thus, the mineralogy and element contents of a siltstone developed from metaluminous, granitic sources during intense weathering would be expected to be more similar to the source rock than the sandstones and conglomerates. Claystones should contain similar REE patterns and Eu/Sm ratios as the source rock, but such fine-grained sediments might represent much larger areas of source rocks than the more locally derived sandstones or conglomerates.     

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.     

Anorogenic metaluminous and peraluminous granite plutonism in the mid-proterozoic of Wisconsin,USA

A magmatic gap from 1.82 to 1.76 b.y. in the Lake Superior region represents the transition from synorogenic calc-alkaline igneous activity of the Penokean Orogeny to anorogenic potassic granophyric granite and ignimbrite. This paper deals with the petrogenetic evolution of 1.76 b.y. granites which represent a major change in source material and conceivably tectonic setting. Although perhaps related to a termination of the Penokean Orogeny by melting of a tectonically thickened crust during collision, these post-Penokean granites may represent the initial appearance of anorogenic, potentially rift-related igneous activity that was widespread throughout North America during late Precambrian time.These post-Penokean granites are too iron-rich and Al-poor to be considered calc-alkaline, a compositional feature shared with most anorogenic igneous activity of continental regions. Within this suite in central and northern Wisconsin, regional differences in composition indicate at least two different granite magma types: one a metaluminous suite of biotite and biotite-hornblende granite and a peraluminous suite of two-mica granite. The systematic compositional differences (Al, Fe/Mg, Ba/Sr, REE) in the two magma suites are likely the result of small differences in residue mineralogy and/or source composition. In general, the degree of fusion was small (10%) and probably of relatively young Penokean material. Both suites have a range of composition due to feldspar dominated fractional crystallization. Removal of the accessory minerals apatite, zircon, and allanite resulted in the REE depletion with differentiation of the two-mica granites.The granites intruded into the upper levels of the crust, and the appearance of primary celadonitic muscovite and subsolvus alkali feldspars (silicic members only) in the two mica granites indicate crystallization at depths of 10–11 km. The biotite granites contain both hypersolvus and subsolvus members and are intruded at depths less than 6 km with the more shallow members generating major volumes of ignimbrite. As a marked departure from the characteristics of most anorogenic granites, these melts crystallized at fairly oxidizing conditions (higher for the two-mica suite) as reflected in the composition of biotite, predominance of magnetite over ilmenite, and early appearance of the Fe-Ti oxides in the crystallization sequence.