Mineralogical, chemical, and isotopic results from seven drilling legs that visited DSDP/ODP Hole 504B over 14 years are compiled here to present an integrated view of hydrothermal alteration of oceanic crust at Site 504. Hole 504B reaches to 2111 mbsf, through 274.5 m sediment, 571.5 m of volcanic rocks, a 209 m transition zone, and 1050 m into a sheeted dike complex. The volcanic section was altered through a series of processes involving interaction with seawater at low temperatures, with the effects of cold, oxidizing seawater decreasing downward. These processes and their effects on the volcanic section are generally similar to those in other oceanic upper crustal sections.The transition zone and upper dikes were altered in a subsurface mixing zone, where hydrothermal fluids upwelling through the dikes mixed with cooler seawater circulating in the overlying more permeable volcanic rocks. Alteration of the transition zone and upper dikes (down to 1500 mbsf) occurred in a series of stages, reflecting the thermal and chemical evolution of the hydrothermal system from (1) early chlorite, actinolite, albite-oligoclase, and titanite, to (2) quartz, epidote and sulfides, to (3) anhydrite, and finally to (4) zeolites and local calcite. The maximum temperature estimated for the first two stages is 350°-380°C, and the inferred mineral assemblages for these early stages are typical of the greenschist facies.The lower dikes (1500-2111 mbsf) underwent an early, high-temperature (>400°C) alteration stage, resulting in the formation of hornblende and calcic secondary plagioclase, consistent with reactions inferred to occur in deep subsurface reaction zones, where hydrothermal vent fluids acquire their final compositions. Much of the subsequent reactions produced greenschist assemblages at ~300°-400°C. The lower dikes have lost metals and sulfur and are a source of these elements to hydrothermal vent fluids and seafloor sulfide deposits. The lower dikes underwent subsequent alteration stages similar to the upper dikes, with rare epidote + quartz veins recording the presence of upwelling hydrothermal fluids, and limited late off-axis effects (zeolites and prehnite). Anhydrites in the lower dikes indicate more reacted fluid compositions than in the upper dikes.Alteration of the sheeted dikes from Hole 504B is heterogeneous, with recrystallization controlled by fracturing and access of fluids. Defining the position of the seismic Layer 2/3 transition depends upon the scale of observation, but the change at Site 504 occurs within the sheeted dikes and is correlated with progressive changes in porosity and hydrothermal alteration. However, we still do not know the nature of the transition from sheeted dikes to gabbros in in situ ocean crust, or the nature of the inferred fault at the base of Hole 504B and its role in fluid flow and alteration.
A new version of the ''modified total evaporation'' (MTE) method for isotopic analysis of uranium samples by multi-collector thermal ionization mass spectrometry (TIMS), with high analytical performance and designed in a more user-friendly and routinely applicable way, is described in detail. It is mainly being used for nuclear safeguards measurements, but can readily be applied in other scientific areas like geochemistry. The development of the MTE method was organized in collaboration of several ''key nuclear mass spectrometry laboratories'', namely the New Brunswick Laboratory (NBL), the Safeguards Analytical Laboratory (SAL, now SGAS-Safeguards Analytical Services) of the International Atomic Energy Agency (IAEA), the Institute for Transuranium Elements (ITU/JRC), and the Institute for Reference Materials and Measurements (IRMM/JRC), with IRMM taking the leading role. Due to the use of the ''total evaporation'' (TE) principle the measurement of the ''major'' ratio n( 235 U)/n( 238 U) is routinely being performed with an accuracy of 0.02%. In contrast to the TE method, in the MTE method the total evaporation process is interrupted on a regular basis to allow for correction for background from peak tailing, internal calibration of a secondary electron multiplier (SEM) detector versus the Faraday cups, peak-centering, and ion source re-focusing. Therefore, the most significant improvement using the MTE method is in the measurement performance achieved for the ''minor'' ratios n( 234 U)/n( 238 U) and n( 236 U)/n( 238 U). The n( 234 U)/n( 238 U) ratio is measured using Faraday cups only with the result that the (relative) measurement uncertainty (k ¼ 2) is better than 0.12%, which is an improvement by a factor of about 5-10 compared to TE measurements. Furthermore, the IAEA requirement for the ''measurement performance'', defined here as the sum of the (absolute) deviation of the measured from the true (certified) value plus the (absolute) measurement uncertainty (k ¼ 2), for n( 236 U)/n( 238 U) ratio measurements is 1 Â 10 À6 , but the MTE method provides a measurement performance which is, depending on the ratio, by several orders of magnitude superior compared to this limit and to the TE method. For routine MTE measurements a detection limit of 3 Â 10 À9 was achieved using an SEM detector for detecting the isotope 236 U. The MTE method is now routinely being used at all collaborating laboratories with the hope that more laboratories will implement this capability in the future as well. Additional applications for the MTE method are presented in this paper, e.g., for absolute Ca isotope measurements. 238U are usually considered as the major isotopes, whereas 234 U and 236 U are called minor isotopes. Natural uranium variations
In order to address the correct reporting and therefore comparison of isotopic measurements across different instrument types and instrumental techniques a prepared set of synthetic standards was sent to 28 laboratories for boron (B) isotopic analyses. Standards were prepared from enriched and purified isotopic salts to avoid any sample preparation fractionation. The range in uncertainties of the analyses between different instrumental analytical techniques is as large as the differences within an instrumental analytical technique obscuring any systematic offset. We conclude that uncertainties in the measurement of d 11 B values were often underestimated and a procedure is suggested to allow a better comparison of the different techniques. Two new standards (JABA and JABB) have been quantified and these are available to all laboratories for testing their analyses. The d 11 B values of these new standards are 10.0& and À23.7&. The results from this exercise impact on the way all isotope measurements are performed and reported. Guidelines are defined to aid the comparison of measurements between different laboratories.
Drilling during Legs 137 and 140 of the Ocean Drilling Program deepened Hole 504B, the only hole to penetrate through the volcanic section and into the underlying hydrothermally altered sheeted dike complex, by 438.1 m to a total depth of 2000.4 meters below seafloor. This paper presents the secondary mineralogy, bulk-rock sulfur contents, and stable isotopic (O, S) compositions, plus oxygen isotopic compositions of secondary minerals from the lower sheeted dike complex drilled during Legs 137 and 140. Various evidence indicates higher temperatures of hydrothermal alteration in the lower dikes than in the upper dikes, including: the local presence of secondary clinopyroxene in the lower dikes; secondary anorthite and hornblende in the lower dikes vs. mainly actinolite and albite-oligoclase in the upper dikes; generally increasing Al and Ti contents of amphibole downward in the dike section; and greater 18 O depletions of the lower dikes (δ 18 θ = 3.6-5.0‰) compared with the upper dikes. Early high-temperature alteration stages (T = 350°-500°C) resulted in 18 O depletions and losses of metals (Cu, Zn) and sulfur from the rocks. Local incorporation of reduced seawater sulfate led to elevated δ 34 S values of sulfide in the rocks (up to 2.5‰). Quartz + epidote formed in crosscutting veins at temperatures of 310°-320°C from more evolved fluids (δ 18 θ = l‰). Late-stage lower-temperature (~250°C) reactions producing albite, prehnite, and zeolites in the rocks caused slight 18 O enrichments, but these were insufficient to offset the 18 O depletions caused by earlier higher-temperature reactions. Addition of anhydrite to the rocks during seawater recharge led to increased S contents of rocks that had previously lost S during axial hydrothermal alteration, and to further increases in δ 34 S values of total S in the rocks (up to 12‰). Despite the evidence for seawater recharge to near the base of the sheeted dike complex, the paucity of late zeolites in the lower dikes suggests that late-stage, off-axis circulation was mainly restricted to the volcanics and shallowest dikes, or to localized high-permeability zones (faults) at depth.
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