A geochemical hypothesis for dolomitization by ground water

B.B. Hanshaw; W. Back; R.G. Deike

doi:10.2113/gsecongeo.66.5.710

Home/Archive/USGS

USGS · 70207070

A geochemical hypothesis for dolomitization by ground water

B.B. Hanshaw·W. Back·R.G. Deike

View original source ↗Export metadata ↓

Abstract

Most modern disordered dolomite has been found in dynamic environments. However, solutions associated with modern dolomite formation do not have a common Mg/Ca ratio; the ratio ranges from about 3 to 100. Ground-water circulation may have a significant role in formation of regional dolomites; one of the primary requirements for regional dolomite formation is a large supply of magnesium ions. An X-ray study of well cuttings from the Tertiary limestone aquifer of central Florida indicates that it is composed primarily of calcite and dolomite with minor amounts of quartz and apatite. The magnesium content of the calcite is slightly lower (0-2 percent MgC03) in the recharge areas than in the deeper confined parts of the aquifer system (2-4 percent MgC03). Our data support other recent work and indicate an equilibrium constant for dolomite of 2 X 10-17. Inasmuch as this value is exactly the square of the calcite equilibrium constant (10~8-35), the Mg/Ca ratio must be unity for the three-phase equilibrium, calcite-dolomite-water. The Mg/Ca ratio in water from the aquifer is as low as 0.05 in the recharge area where the water is also undersaturated with respect to both calcite and dolomite. With time and length of travel path in the system, the water increases systematically in Mg/Ca ratio, which approaches unity; saturation with respect to the two carbonates also increases downgradient until the solution apparently becomes over-saturated with respect to both carbonates. In Tertiary limestones of the Yucatan Peninsula, the Mg/Ca range in water is similar to that for Florida. The small amount of magnesium available from the solution of magnesium calcites and dolomite in the potable zone of active circulation is insufficient to provide the amount required for extensive dolomitization unless enormous quantities of rock are available for dissolution. However, dolomite may be forming in the zones of brackish water that underlie the Florida and Yucatan Peninsulas. The required magnesium may be derived from the readily available ocean water or reflux brines as the hydrologic regimen is changed because of relative fluctuations of sea level.

Explore related subjects

Economic Geology Article

Source-reported bounding extent: 24.546468° to 31.000682° latitude; -87.634938° to -80.031362° longitude. This indicates report coverage, not an exact sampling location. View area on OpenStreetMap.

Keep this discovery

Explore connections, maps & timelines

BibTeX RIS

B.B. Hanshaw, W. Back, R.G. Deike. 1971-08-01. A geochemical hypothesis for dolomitization by ground water. https://doi.org/10.2113/gsecongeo.66.5.710

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related USGS reports

USGS2026

Origin of the Pd/Pt ratio of the J-M Reef, Stillwater Complex, Montana, USA

The J-M reef of the Stillwater Complex is characterized by a high Pd/Pt ratio (mean ~3.8 with a standard error of 0.03) with a homogeneous geospatial distribution at the deposit scale. In this contribution, we demonstrate that the Pd/Pt ratio of the reef is the product of equilibration of an immiscible sulfide liquid with a silicate melt rich in Pd relative to Pt. Despite the high tenors of the J-M reef sulfides (avg 2,700 ppm Pt and 770 ppm Pt), numerical modeling shows that the parental melts did not have extraordinary Pd and Pt concentrations. Instead, the initial composition of a plausible parental silicate melt can have Pd and Pt contents well within the expected range of a normal, mantle-derived partial melt (i.e., ~10–20 ppb for both Pd and Pt with Pd/Pt of ~1). The relative differences in the partitioning behavior of Pt and Pd between sulfide liquid and silicate melt are unlikely to produce a consistent Pd/Pt ratio across a wide range of silicate melt to sulfide liquid mass ratios (i.e., R factors). Instead, the pre-emplacement fractionation of Pt alloy from S-undersaturated silicate magma accounts for the homogeneous and high Pd/Pt ratio of the J-M reef. We show that batch equilibration of sulfide liquid with silicate melt can produce the high Pd/Pt ratios of the reef if the partition coefficients between sulfide liquid and silicate melt for Pd and Pt are extremely high (>10 6 ). In an alternative model, Pd enrichment could be achieved by sulfide upgrading in resident footwall mush even if the partition coefficients between sulfide liquid and silicate melt are relatively small (between 10 4 and 10 6 ) because the instantaneous mass ratio of silicate melt to sulfide liquid is small (R ≈ 100–700), so the partitioning behavior of Pt and Pd has little impact on the composition of sulfide liquid.

Montana↗

USGS2025

Depth of magma crystallization and fluid exsolution beneath the porphyry-skarn Cu deposits at Santa Rita and Hanover-Fierro, New Mexico, USA

The depth level at which porphyry Cu–forming magmas fractionated and exsolved mineralizing fluids is actively debated. In the classic model, extensive magma fractionation occurs in large, upper crustal magma chambers, and concomitant fluid exsolution leads to forceful expulsion of residual magmas in the form of porphyry dikes, stocks, and breccia pipes, which subsequently serve as pathways for the mineralizing fluids. In contrast, some recent studies highlighting the role of deep crustal magma fractionation in the production of fertile magmas essentially deny the existence of upper crustal magma chambers at the time of mineralization. To address this, we conducted a detailed thermobarometric investigation of 13 intermediate to felsic, porphyritic intrusive rocks related to porphyry-skarn Cu mineralization at Santa Rita and Hanover-Fierro, New Mexico, United States, representing two premineralization magmas (61–60 Ma), seven synmineralization magmas (60–58 Ma), and four late- to postmineralization magmas (58–57 Ma). For each sample, the pressure of last magma crystallization before final magma ascent to the current exposure level was reconstructed based on Al-in-hornblende barometry of small hornblende inclusions trapped within quartz phenocrysts and through titanium-in-quartz (TitaniQ) thermobarometry of the host quartz phenocrysts themselves. Since quartz is one of the last crystallizing magmatic minerals, and no significant phenocryst growth could have occurred in small dikes and stocks after final magma emplacement, quartz phenocrysts and their contained hornblende inclusions record the depth of last magma crystallization before final magma ascent. When present, hornblende phenocrysts and hornblende inclusions within other major phenocrysts were also analyzed. Both quartz and hornblende barometers return consistent average pressures of 3.2 ± 0.4 kbar for the entire suite of pre- to postmineralization magmas, corresponding to depths of 11 to 14 km. The synmineralization magmas return even more consistent average pressures of 3.1 ± 0.2 kbar, corresponding to a depth of 12 ± 1 km. The volume of the mineralizing porphyry dikes and stocks at the emplacement level is far too small to have provided all the fluids and metals required to form the observed ore deposits. Therefore, the majority of the ore-forming fluids must have originated from the magmas that crystallized at 12 ± 1 km depth. The ore deposits, conversely, formed at ~5-km paleodepth. This implies that most of the mineralizing fluids traveled an average vertical distance of ~7 km from their magmatic source to the eventual site of ore precipitation. The relatively unaltered nature and low veining degree of deeper parts of mineralized porphyry dikes and stocks suggest that the fluid transport through these intrusive bodies occurred mostly at near-solidus conditions by means of fluid percolation along grain boundaries. In summary, our results suggest that (1) a large, upper crustal pluton exists ~7 km beneath the Santa Rita and Hanover-Fierro deposits; (2) abundant phenocryst crystallization occurred at this depth level; and (3) this pluton was the main source for the exsolution of ore-forming fluids. However, the investigated rocks have elevated whole-rock Sr/Y ratios, indicating magma fractionation at deep crustal levels. As a result, our preferred model is a combination of the two end-member models introduced above, with most magma fractionation having occurred in the deep crust and with residual, intermediate to felsic melts having ascended and accumulated at 11 to 14 km paleodepth, where they continued to crystallize with comparatively little crystal-liquid separation, before some of these magmas ascended further to shallow levels and quenched to porphyries.

New Mexico↗

USGS2025

Assimilation of reduced carbon triggers platinum alloy saturation in mafic and ultramafic magmas

It is generally observed that magmatic sulfide ores have higher ratios of Pd/Pt than the mantle-like values of their parental magmas. This discrepancy has defied simple explanation because the partitioning behavior of both elements between sulfide and silicate liquids is very similar. Assimilation of sulfur- and carbon-rich country rocks by mafic and ultramafic magmas is considered a critical, if not essential, step in the formation of magmatic base metal sulfide deposits. Although there is general consensus that the assimilation of external sulfur and carbon promotes sulfide saturation, the effect of carbon assimilation on the solubilities of platinum-group elements in natural S-bearing silicate melt has been overlooked. In this study, we investigate the variations of platinum and palladium solubilities during assimilation of graphite and methane through thermodynamic modeling, in comparison with data from an array of highly distinctive magmatic sulfide ore systems representing ages from Archean to Paleozoic, melt compositions from komatiite to basalt, and magmatic settings including lavas, hypabyssal intrusions, plutonic continental arc roots, and plutonic layered intrusions, namely: Raglan, Norilsk-Talnakh, Lac des Iles, and the J-M Reef of the Stillwater Complex. We model assimilation-fractional crystallization processes to estimate the reduction of oxygen fugacity ( ⁠fO2⁠ ) of the melt due to incorporation of graphite and methane. The simulations show that although Pd remains highly soluble during the progressive assimilation of reduced carbon, Pt solubility decreases significantly as the silicate melt becomes increasingly reduced. With less than 8 % of sediment assimilation, Pt alloy may saturate and then deviate from sulfide-undersaturated silicate melts, concomitantly increasing the Pd/Pt value of the remaining melts of the Raglan and Norilsk-Talnakh systems. For the Lac des Iles and Stillwater systems, a higher extent of assimilation is needed to reach Pt saturation because of the relatively carbon-poor nature of the lower crustal rocks. The assimilation of methane volatiles is shown to be more effective than graphite assimilation, and it provides a pathway to Pt alloy fractionation in the absence of detectable amounts of bulk host-rock assimilation. High Pd/Pt values have been documented in many world-class magmatic sulfide deposits whose parental magmas have demonstrably experienced crustal contamination. Our model suggests that although anomalous Pd/Pt values may be explained by other mechanisms such as incongruent melting of preexisting sulfide or differences in the diffusivities of the metals within achieving equilibration, the assimilation of graphite or methane may play an important role in the global occurrence of magmatic sulfide ores with elevated Pd/Pt values.

Economic Geology↗