Oxygen isotope fractionation in decarbonation metamorphism: the Mottled Zone event

Calculated univariant equilibria and oxygen isotope compositions of silicates and carbonates support the proposal that the “Mottled Zone Event” is a low-pressure (1–25 atm), high-temperature (200° < T < 1300°C) metamorphism of calcareous siliceous sediments in which the thermal energy is provided by combustion of organic matter. δ¹⁸O of silicates decreases systematically with increasing metamorphic grade from averages of 18.1‰ in protolith shales, to 16.6‰ in grossular-diopside-zeolite rocks, 15.6‰ in wollastonite and anorthite-diopside-gehlenite-grossular fels, 14.1‰ in spurrite-brownmillerite marbles and 11.7‰ in the highest-grade larnite-gehlenite-brownmillerite assemblages. Decarbonation is the principal mechanism influencing the oxygen isotope compositions. The progressive decrease of δ¹⁸O in silicates can be modelled as a Rayleigh distillation of CO₂ approximately 16‰ enriched in ¹⁸O relative to whole rock assemblages i.e., of initial isotopic composition 8.5‰ heavier than the parent carbonates. The mineral assemblage of one sample with an unusual granoblastic texture is in apparent isotopic equilibrium at a temperature of 540°C.     

Early diagenesis in a reducing fjord,Saanich Inlet,British Columbia—II. Trace element distribution in interstitial water and sediment

Sediment and interstitial water from four cores in Saanich Inlet were analyzed for total iron, manganese, nickel, cobalt, copper, molybdenum, zinc, lithium and strontium. In addition, three separate sediment fractions were analyzed:

1.

(i) dilute acid soluble     

Geochemistry of a chert breccia

A complex history of diagenetic interactions between a siliceous sediment, seawater and fresh water is revealed by intraformational chert breccias. Chert breccias were formed in the Campanian Mishash Formation in Israel, by “practically contemporaneous” fracturing of lithified cherty layers followed by silicification and lithification of the matrix. Pairs of fragments and matrix were compared with respect to their chemical (Ca, Sr, Na, K, Mg, Li, B, SO₄, Ba) and isotopic (δ¹⁸O, δD, δ¹¹B) composition. δ¹¹B was analyzed by ion-probe and includes a profile across a fragment-matrix contact. The epicontinental cherts of the Mishash Fm. are enriched by a factor of 10 to 50 in all elements other than O and Si in comparison with Deep-Sea cherts. All results are compatible with the proposition that the lithification of the matrix occurred in contact with fresh-water, as opposed to seawater in which the fragments, as well as most of the Mishash sediments were formed. The strongest evidence for this difference is in the higher concentration of B in the fragments (27-70 ppm vs. 11-21ppm in the matrix) and higher δ¹⁸O (29 to 35‰ vs. 21 to 33‰). δD is a less efficient discriminator, though compatible with fresher water diagenesis of the matrix: −115‰ to −76‰ for hydrogen in the chert of the fragments, compared to −141 to −85‰ for the matrix. δ¹¹B in the matrix shows some of the lowest values recorded in sediments (δ¹¹B = −33‰), but varies strongly, suggesting that the source of boron in the matrix is a mixture of a freshwater and a marine component. Both seawater and the freshwater that has equilibrated with the cherts underwent varying degrees of evaporation. Ca, Sr and SO₄ are carried by apatite, trapped as detritus in the matrix. The concentration of lithium in the matrix is high (11-16 ppm), whereas in the adjacent fragments it is mostly only within 1-2 ppm. Li probably enters the matrix from the interstitial solution, during the opal → quartz transformation. The second, prolonged, transformation takes place in a (freshwater) flow-through, open system. This allows a much larger mass of Li to be scavenged by the transforming silica despite its low concentration in freshwater.     

Oxygen isotopic composition and U-Pb discordance in zircon

We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution δ¹⁸O measurement by ion microprobe. δ¹⁸O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) δ¹⁸O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in ¹⁸O, but the relationship between discordance and δ¹⁸O is not systematic. δ¹⁸O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and δ¹⁸O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of ¹⁸O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in ¹⁸O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in δ¹⁸O, leave their imprint on both the texture and U-Pb systematics of zircon.     

Stable isotope geochemistry of deep sea cherts

Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. δ¹⁸O of chert ranges between 27 and 39%. relative to SMOW, δ¹⁸O of porcellanite—between 30 and 42%.. The consistent enrichment of opal-CT in porcellanites in ¹⁸O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases.δ¹⁸O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975) indicates the possibility of δ¹⁸O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of δ¹⁸O values, increasing diagenesis being reflected in a lowering of δ¹⁸O. Drusy quartz has the lowest δ¹⁸O values.On-land exposed cherts are consistently depleted in ¹⁸O in comparison to their deep sea time equivalent cherts.Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. δD of this water ranges between ?78 and ?95%. and is not a function of δ¹⁸O of the cherts (or the temperature of their formation).     

Oxygen isotope variations in phosphate of biogenic apatites,III. Conodonts

The method for measurement of the isotopic composition of oxygen in phosphates has been improved and adapted for analysis of small quantities of apatite, down to 10 mg. This extension enables one to analyze hand-picked conodont samples with an analytical reproducibility better than ±0.5‰ (1σ).46 samples of conodonts ranging from the Ordovician to the Pennsylvanian of North America were analysed. Some insoluble phosphatic residues, ichthyoliths and inarticulate brachiopods of the same time range were also measured. The range of the δ¹⁸O values of the analysed conodonts is between 15 and 19‰. It shows a general trend of decreasing d¹⁸O with increasing age, from an average value of about 19 in the Pennsylvanian to 17 in the Ordovician. This trend parallels that previously detected in marine phosphorites. For the time range between the Devonian and Pennsylvanian our data are in agreement with independent paleoclimatic information. Specifically, we detect maximum¹⁸O enrichment at the end of the Pennsylvanian, and minimum enrichment at the end of the Devonian. The difference between these two extremes is equivalent to about 10°C (from about 40° to 30°C), assuming constant isotopic composition of ocean water.The success of oxygen isotopic analysis of conodonts raises the possibility of their use in Paleozoic paleo-oceanography in a similar way to foraminifera in the Mesozoic-Cenozoic.     

Stable isotopes, chemistry and petrology of carbonate concretions (Mishash formation, Israel)

Carbonate concretions of variable sizes occur in the upper member of the Senonian (Upper Cretaceous) Mishash formation in Israel. Eight concretions and their surrounding country rocks were examined in the field, in thin sections and by X-rays. The isotopic composition of carbon and oxygen in the carbonates, the amount of acid insoluble residue, as well as the concentrations of P₂O₅, Ca, Mg, Sr and Fe were determined. Other concretions and country rocks were analyzed for oxygen and carbon isotopes only.

The concretions are composed of almost pure, microsparitic calcite, whereas the country rocks are porcellanitic-phosphoritic chalks. Compared with the surrounding rocks, the concretions are strongly enriched in ¹²C and are depeleted in insoluble residue, P₂O₅, SiO₂, Fe, Sr and Mg.

It is postulated that the concretions were formed by addition of CaCO₃ to sites of anaerobic decomposition of organic matter, while CaCO₃ was mobilized in the surrounding sediments, in which aerobic decomposition of organic matter prevailed.

Several consequences of this model are considered, concerning the quantitative volume changes, as well as the distribution of SiO₂ and Mg between concretions and country rocks.     

Estimating location and size of historical earthquake by combining archaeology and geology in Umm-El-Qanatir,Dead Sea Transform

We study the Byzantine-to-Ummayad (6th–8th century) archaeological site of Umm-El-Qanatir, located 10 km east of the Dead Sea Transform (DST) in northern Israel. The site was damaged by an earthquake-induced landslide, and in this work we use slope stability analysis to constrain the historical seismic acceleration that occurred along the northern segment of the DST. Umm-El-Qanatir archaeological site is located on a slope of a canyon and contains evidence for earthquake-related damage, including fallen columns and walls, horizontal shift of heavy masonry blocks, and complete burial of ceramic pots and farming tools beneath fallen ceilings. A water pool that collected spring water is displaced nearly one meter by the landslide. The artifacts from the village and the spring area indicate that people inhabited the site until the middle of the 8th century. We argue that the destruction, which forced the abandonment of Umm-El-Qanatir together with nearby settlements, was associated with the earthquake of January 18, 749 CE. In order to evaluate the ground acceleration related to the above earthquake, we back-analyze the stability of a failed slope, which cut and displaced the water-pool, using slope stability software (Slope/W). The results show that the slope is statically stable and that high values of horizontal seismic acceleration (>0.3 g) are required to induce slope failure. Subsequently, we use the Newmark displacement method to calculate the earthquake magnitude needed to cause the slope failure as a function of distance from the site. The results (attributed to the 749 CE earthquake) show that a M_W > 7.0 earthquake up to 25 km from the site could have induced the studied landslide.