Mineral chemistry of basalts at DSDP Leg 55 Holes

Microprobe mineral compositions of olivine, plagioclase, clinopyroxene, chrome spinel, ilmenite, and titanomagnetite are presented for 7 samples from 4 flows of hawaiite and one flow of tholeiitic basalt from Hole 430A at Ojin Seamount, 4 samples from 3 flows of alkalic basalt from Hole 432A at Nintoku Seamount, and 29 samples from 2 flows of alkalic basalt and 24 flows of tholeiitic basalt from Holes 433A, 433B, and 433C at Suiko Seamount. The four hawaiite flows from Hole 430A on Ojin Seamount have nearly identical mineralogy. The plagioclase phenocrysts and calculated equilibrium olivine appear to have crystallized at about 1175°C; the groundmass plagioclase crystallized from about 1135° to 1010°C; and the Fe-Ti oxides equilibrated at temperatures from 1000°C to 720°C under oxygen fugacities of 10**-11 to 10**-17. The single tholeiitic flow contains glomerocrysts of plagioclase (An80 to An65) and clinopyroxene (Wo43En46Fsn to Wo42En45Fs13). The plagioclase phenocrysts give calculated temperatures as high as 1400°C, indicating that they were not equilibrated with a magma having the bulk rock composition. The plagioclase groundmass crystallized at 1120° to 1070°C, and the Fe-Ti oxides equilibrated at 1070° to 930°C under oxygen fugacities of 10**-10 to 10**-12. Using mineral compositions of Hawaiian basalts as a guide, we infer that the hawaiite flows were erupted during the post-caldera alkalic eruptive stage and the tholeiite was erupted during the shield-building or caldera collapse stage. The three alkalic basalt flows from Hole 432A on Nintoku Seamount have similar mineralogy, although Flow Units 1 and 2 contain much more abundant plagioclase phenocrysts. The groundmass plagioclase crystallized at temperatures between 1175° and 1000°C. The olivine and plagioclase phenocrysts do not appear to be in equilibrium with the enclosing magmas. The mineral compositions suggest that these samples are intermediate between alkalic basalt and hawaiite; they probably erupted during the post-caldera alkalic stage of eruption. The two analyzed alkalic basalt flows are the two youngest flows recovered at Holes 433A, 433B, and 433C. Flow Unit 1 contains abundant sector-zoned clinopyroxene, and Flow Unit 2 contains rare kink-banded olivine xenocrysts. The plagioclase phenocrysts yield calculated temperatures of 1440° to 1250°C, indicating that they are probably not cognate. Calculated-equilibrium olivine indicates crystallization of olivine at about 1170°C. The Fe-Ti oxides equilibrated at temperatures of 1140° to 870°C under oxygen fugacities of 10**-9 to 10**-14. The groundmass plagioclase crystallized at temperatures of 1178° to 1035 °C. The mineral compositions indicate that these alkalic basalts erupted during the post-caldera alkalic eruptive stage. The 24 analyzed tholeiitic basalts are subdivided on the basis of phenocryst abundances into olivine tholeiites, plagioclase tholeiites, and tholeiites. The crystallization sequence appears to have been chrome spinel, olivine, plagioclase, and clinopyroxene as phenocryst phases, followed by and overlapping with groundmass crystallization of plagioclase (1180° to 920°C), clinopyroxene, and Fe-Ti oxides (1140° to 670°C). At least three flows contain pigeonite. The mineral compositions indicate that all the samples from Flow Unit 4 downward are tholeiitic basalts, although Flow Unit 64 has mineral compositions transitional to those in alkalic basalts.

Carbon chemistry of oceanic crust

Carbonate mineral precipitation in the upper oceanic crust during low-temperature, off-axis, hydrothermal circulation is investigated using new estimates of the bulk CO2 content of seven DSDP/ODP drill cores. In combination with previously published data these new data show: (i) the CO2 content of the upper ~ 300 m of the crust is substantially higher in Cretaceous than in Cenozoic crust and (ii) for any age of crust, there is substantially more CO2 in Atlantic (slow-spreading) than Pacific (intermediate- to fast-spreading) crust. Modelling the Sr-isotopic composition of the carbonates suggests that > 80% of carbonate mineral formation occurs within < 20 Myr of crust formation. This means that the higher CO2 content of Cretaceous crust reflects a secular change in the rate of CO2 uptake by the crust. Oxygen isotope derived estimates of carbonate mineral precipitation temperatures show that the average and minimum temperature of carbonate precipitation was ~10 °C higher temperatures in the Cretaceous than in the Cenozoic. This difference is consistent with previous estimates of secular change in bottom seawater temperature. Higher fluid temperature within the crust will have increased reaction rates potentially liberating more basaltic Ca and hence enhancing carbonate mineral precipitation. Additionally, if crustal fluid pH is controlled by fluid-rock reaction, the higher Ca content of the Cretaceous ocean will also have enhanced carbonate mineral precipitation. New estimates of the rate of CO2 uptake by the upper ocean crust during the Cenozoic are much lower than previous estimates.

(Table 2, page 725) Solid phase chemistry of ferromanganese precipitates from Nova Scotian lakes

Sediments associated with freshwater ferromanganese concretions in Lake Charlotte, Nova Scotia, contained microscopic precipitates of manganese and iron. These precipitates were dispersed throughout the sediment and were as rich in nickel, cobalt, and copper as deep sea concretions. In addition, the development of the precipitates appeared to be associated with the microbial oxidation of manganese. Results from the deployment of poisoned and unpoisoned dialysis probes or peepers demonstrated that microbial manganese oxidation and nickel binding were closely associated, causing a fivefold enhancement of abiotic processes such as adsorption.

Diurnal and seasonal measurements of seawater chemistry, temperature and PAR in Hurricane Hole, U.S. Virgin Islands - 2010-2012

Risk analyses indicate that more than 90% of the world's reefs will be threatened by climate change and local anthropogenic impacts by the year 2030 under "business-as-usual" climate scenarios. Increasing temperatures and solar radiation cause coral bleaching that has resulted in extensive coral mortality. Increasing carbon dioxide reduces seawater pH, slows coral growth, and may cause loss of reef structure. Management strategies include establishment of marine protected areas with environmental conditions that promote reef resiliency. However, few resilient reefs have been identified, and resiliency factors are poorly defined. Here we characterize the first natural, non-reef coral refuge from thermal stress and ocean acidification and identify resiliency factors for mangrove-coral habitats. We measured diurnal and seasonal variations in temperature, salinity, photosynthetically active radiation (PAR), and seawater chemistry; characterized substrate parameters; and examined water circulation patterns in mangrove communities where scleractinian corals are growing attached to and under mangrove prop roots in Hurricane Hole, St. John, US Virgin Islands. Additionally, we inventoried the coral species and quantified incidences of coral bleaching, mortality, and recovery for two major reef-building corals, Colpophyllia natans and Diploria labyrinthiformis, growing in mangrove-shaded and exposed (unshaded) areas. Over 30 species of scleractinian corals were growing in association with mangroves. Corals were thriving in low-light (more than 70% attenuation of incident PAR) from mangrove shading and at higher temperatures than nearby reef tract corals. A higher percentage of C. natans colonies were living shaded by mangroves, and no shaded colonies were bleached. Fewer D. labyrinthiformis colonies were shaded by mangroves, however more unshaded colonies were bleached. A combination of substrate and habitat heterogeneity, proximity of different habitat types, hydrographic conditions, and biological influences on seawater chemistry generate chemical conditions that buffer against ocean acidification. This previously undocumented refuge for corals provides evidence for adaptation of coastal organisms and ecosystem transition due to recent climate change. Identifying and protecting other natural, non-reef coral refuges is critical for sustaining corals and other reef species into the future.

Chemistry of sulfide deposites of ODP Site 106-649

The Snake Pit active hydrothermal field was discovered at 23°22'N on the Mid-Atlantic Ridge during ODP Leg 106. Among the ten holes drilled in the mound at the foot of an active chimney, only three (649B, 649F, and 649G) had substantial recovery, and produced cores of unconsolidated hydrothermal deposit made up of porous sulfide fragments with minor talc pellets and biological debris, and a few pieces of brassy massive sulfides. Eight representative samples from the 6.5-m-long core from Hole 649B were analyzed for bulk chemistry, both by XRF (major elements) and NAA (trace elements). Major elements average compositions show high Fe (36 wt%), S (37 wt%), and Cu (12 wt%) contents, and minor Zn (6.7 wt%), reflecting a mostly high-temperature deposit. Trace elements are characterized by a high Au content (600 ppb) which could express the maturity of the mound. Mineralogical assemblages show evidence of sequential precipitation, and absence of equilibrium. Major sulfide phases are pyrrhotite, pyrite, Fe, Cu sulfides, marcasite, and sphalerite. Three types of samples are distinguished on the basis of textures and mineral assemblages: type 1, rich in pyrrhotite, with approximately equivalent amounts of Cu, Fe sulfides, and sphalerite and minor pyrite; type 2, rich in Cu, Fe sulfides, which are cubic cubanite with exsolutions and rims of chalcopyrite; and type 3, essentially made up of sphalerite. Type 2 samples likely represent fragments of the inner chimney wall. The presence of talc intergrown with cubic cubanite/chalcopyrite in one big piece from Hole 649G is probably related to mixing of the hydrothermal fluid with seawater.

Chemistry of phyllosilicates of ODP Hole 140-504B

Replacement minerals in olivine record the evolution of hydrothermal alteration between 1600 and 2000 mbsf in the sheeted dike complex in Hole 504B. 1. Talc (+ magnetite) rim on olivine represents the earliest alteration. Talc probably crystallized during initial cooling of the dikes. 2. The partial breakdown of talc to "deweylite", a chaotic mixture of serpentine and Al-free stevensite, was facilitated by further cooling and a somewhat increased fluid:rock interaction in the dikes. 3. The presence of chlorite veins and the replacement of unaltered olivine cores, talc, and deweylite and of other silicates by chlorite suggest fracturing of the rocks during cooling (shrinkage cracks) and local influx of seawater into the dikes. 4. Late amphibole veins and locally extensive amphibole alteration indicate increasing temperature and the development of new sets of fractures, possibly due to the injection of fresh magma. Several generations of chlorite and amphibole veins are present in the dikes. Offset veins and the crack-seal texture within veins in the dikes suggest that the alteration cycle was probably repeated with the injection of each set of new dikes. Presently measured temperatures (195°C) at 2000 m depth in Hole 504B indicate that deweylite, which was previously considered a low-temperature mineral, can form well above its previously estimated crystallization temperature of 50°C.

An integrated biostratigraphy (conodonts and foraminifers) and chronostratigraphy (paleomagnetic reversals, magnetic susceptibility, elemental chemistry, carbon isotopes and geochronology) for the Permian-Triassic strata of Guandao section

The chronostratigraphy of Guandao section has served as the foundation for numerous studies of the end-Permian extinction and biotic recovery in south China. Guandao section is continuous from the Permian-Triassic boundary to the Upper Triassic.Conodonts enable broad delineation of stage and substage boundaries and calibration of foraminifer biostratigraphy as follows. Changhsingian- Griesbachian: first Hindeodus parvus, and first appearance of foraminifers Postcladella kalhori and Earlandia sp. Griesbachian-Dienerian: first Neospathodus dieneri, and last appearance of foraminifer P. grandis. Dienerian-Smithian: first Novispathodus waageni and late Dienerian first appearance of foraminifer Hoyenella ex gr. sinensis. Smithian-Spathian: first Nv? crassatus and last appearance of foraminifers Arenovidalina n. sp. and Glomospirella cf. vulgaris. Spathian-Aegean: first Chiosella timorensis and first appearance of foraminifer Meandrospira dinarica. Aegean-Bithynian: first Nicoraella germanica and first appearance of foraminifer Pilammina densa. Bithynian-Pelsonian: after last Neogondolella regalis, prior to first Paragondolella bulgarica and first appearance of foraminifer Aulotortus eotriasicus. Pelsonian-Illyrian: first Pg. excelsa and last appearance of foraminifers Meandrospira ? deformata and Pilamminella grandis. Illyrian-Fassanian: first Budurovignathus truempyi, and first appearance of foraminifers Abriolina mediterranea and Paleolituonella meridionalis. Fassanian-Longobardian: first Bv. mungoensis and last appearance of foraminifer A. mediterranea. Longobardian-Cordevolian: first Quadralella polygnathiformis and last appearance of foraminifers Turriglomina mesotriasica and Endotriadella wirzi. The section contains primary magnetic signature with frequent reversals occurring around the Permian-Triassic, Olenekian-Anisian, and Anisian-Ladinian boundaries. Predominantly normal polarity occurs in the lower Smithian, Bithynian, and Longobardian-Cordevolian. Predominantly reversed polarity occurs in the upper Griesbachian, Induan-Olenekian, Pelsonian and lower Illyrian. Reversals match well with the GPTS. Large amplitude carbon isotope excursions, attaining values as low as -2.9 per mil d13C and high as +5.7 per mil d13C, characterize the Lower Triassic and basal Anisian. Values stabilize around +2 per mil d13C through the Anisian to Carnian. Similar signatures have been reported globally. Magnetic susceptibility and synthetic gamma ray logs show large fluctuations in the Lower Triassic and an overall decline in magnitude of fluctuation through the Middle and Upper Triassic. The largest spikes in magnetic susceptibility and gamma ray, indicating greater terrestrial lithogenic flux, correspond to positive d13C excursions. Several volcanic ash horizons occur in the Lower Triassic and Olenekian-Anisian boundary. High resolution U-Pb analysis of zircons provide a robust age of 247.2 Ma for the Olenekian-Anisian boundary.

Interstitial water chemistry, Deep Sea Drilling Project, Leg 96

On Leg 96 of the Deep Sea Drilling Project (DSDP), holes were drilled in Orca and Pigmy basins on the northern Gulf of Mexico continental slope and on the Mississippi Fan. The holes on the fan encountered interbedded sand, silt, and mud deposited extremely rapidly, most during late Wisconsin glacial time. Pore-water chemistry in these holes is variable, but does not follow lithologic changes in any simple way. Both Ca and SO4 are enriched in the pore water of many samples from the fan. Two sites drilled in the prominent central channel of the middle fan show rapid SO4 reduction with depth, whereas two nearby sites in overbank deposits show no sulfate reduction for 300 m. Calcium concentration decreases as SO4 is depleted and Li follows the same pattern. Strontium, which like Li, is enriched in samples enriched in Ca, does not decrease with SO4 and Ca. Potassium in the pore water decreases with depth at almost all sites. Sulfate reduction was active at the two basin sites and, as on the fan, this resulted in calcium carbonate precipitation and a lowering of pore water Ca, Mg, and Li. The Orca Basin site was drilled through a brine pool of 258? salinity. Pore-water salinity decreases smoothly with depth to 50 m and remains well above normal seawater values to the bottom of the hole at about 90 m. This suggests constant sedimentation under anoxic hypersaline conditions for at least the last 50,000 yr.