Mineral and chemical composition of hydrothermally altered rocks and sediments from the Middle Valley, ODP Leg 139 data

The Middle Valley segment at the northern end of the Juan de Fuca Ridge is a deep extensional rift blanketed with 200-500 m of Pleistocene turbiditic sediment. Sites 857 and 858 were drilled during Ocean Drilling Program Leg 139 to determine whether these two sites were hydrologically linked end members of an active hydrothermal circulation system. Site 858 was placed in an area of active hydrothermal discharge with fluids up to 270°C venting through anhydrite-bearing mounds on top of altered sediment. The shallow basement of fine-grained basalt that underlies the vents at Site 858 is interpreted as a seamount that was subsequently buried by turbidites. Site 857 was placed 1.6 km south of the Site 858 vents in a zone of high heat flow and numerous seismically imaged ridge-parallel faults. Drilling at Site 857 encountered sediments that are increasingly altered with depth and that overlie a series of mafic sills at depths of 460-940 m below sea floor. Sill margins and adjacent baked sediment are highly altered to magnesian chlorite and crosscut with veins filled with quartz, chlorite, sulfides, epidote, and wairakite. The sill interiors vary from slightly altered, with unaltered plagioclase and clinopyroxene in a mesostasis replaced by chlorite, to local zones of intense alteration and brecciation. In these latter zones, the sill interiors are pervasively replaced by chlorite, epidote, quartz, pyrite, titanite, and rare actinolite. The most complete replacement is associated with brecciated horizons with low recovery and slickensides on fracture surfaces, which we interpret as intersections between faults and the sills. Geochemically, the alteration of the sill complex is reflected in significant whole-rock depletions in Ca, Sr, and Na with corresponding enrichments in Mg, Al, and most metals. The latter results from the formation of conspicuous sulfide poikiloblasts. In contrast, metamorphism of the Site 858 seamount includes incomplete albitization of plagioclase phenocrysts and replacement of sparse mafic phenocrysts. Much of the basement alteration at Site 858 is confined to crosscutting veins except for a highly altered and veined horizon at the contact between basaltic basement and the overlying sediment. The sill complex at Site 857 is more highly depleted in 18O (d18O = 2.4 per mil - 4.7 per mil) and more pervasively replaced by secondary minerals relative to the extrusives at Site 858 (d18O = 4.5 per mil - 5.5 per mil). There is no evidence of significant albitization of the plagioclase at Site 857, suggesting high Ca/Na in the pore fluids. Fluid-inclusion data from hydrothermal minerals in altered mafic rocks and veins at Sites 857 and 858 show a consistency of homogenization temperatures, varying from 245 to 270°C, which is within the range of temperatures observed for the fluids venting at Site 858. The consistency of the fluid inclusion temperatures, the lack of albitization within the Site 857 sills, and the apparently low water/rock ratio collectively suggest that the sill complex at Site 857 is in thermal equilibrium and being altered by a highly evolved Ca-rich fluid similar to the fluids now venting at Site 858. The alteration evident in these two deep crustal drillsites is a result of the ongoing hydrothermal circulation and is consistent with downhole logging results, instrumented borehole results, and hydrothermal fluid chemistry. The pervasive alteration of the laterally extensive sill-sediment complex at Site 857 determines the chemistry of the fluids that are venting at Site 858. The limited alteration of the Site 858 lavas suggests that this basement edifice acts as a penetrator or ventilator for the regional hydrothermal reservoir with much of the flow focussed at the highly altered and veined sediment-basalt contact.

Rb-Sr systematics of volcanic rocks and alteration minerals of ODP Hole 104-642E

Subaerially erupted tholeiites at Hole 642E were never exposed to the high-temperature seawater circulation and alteration conditions that are found at subaqueous ridges. Alteration of Site 642 rocks is therefore the product of the interaction of rocks and fluids at low temperatures. The alteration mineralogy can thus be used to provide information on the geochemical effects of low temperature circulation of seawater. Rubidium-strontium systematics of leached and unleached tholeiites and underlying, continentally-derived dacites reflect interactions with seawater in fractures and vesicular flow tops. The secondary mineral assemblage in the tholeiites consists mainly of smectite, accompanied in a few flows by the assemblage celadonite + calcite (+/- native Cu). Textural relationships suggest that smectites formed early and that celadonite + calcite, which are at least in part cogenetic, formed later than and partially at the expense of smectite. Smectite precipitation occurred under variable, but generally low, water/rock conditions. The smectites contain much lower concentrations of alkali elements than has been reported in seafloor basalts, and sequentially leached fractions of smectite contain Sr that has not achieved isotopic equilibrium. 87Sr/86Sr results of the leaching experiments suggest that Sr was mostly derived from seawater during early periods of smectite precipitation. The basalt-like 87Sr/86Sr of the most readily exchangeable fraction seems to suggest a late period of exposure to very low water /rock. Smectite formation may have primarily occurred in the interval between the nearly 58-Ma age given by the lower series dacites and the 54.5 +/- 0.2 Ma model age given by a celadonite from the top of the tholeiitic section. The 54.5 +/- 0.2 Ma Rb-Sr model age may be recording the timing of foundering of the Voring Plateau. Celadonites precipitated in flows below the top of the tholeiitic section define a Rb-Sr isochron with a slope corresponding to an age of 24.3 +/- 0.4 Ma. This isochron may be reflecting mixing effects due to long-term chemical interaction between seawater and basalts, in which case the age provides only a minimum for the timing of late alteration. Alternatively, inferrential arguments can be made that the 24.3 +/- 0.4 isochron age reflects the timing of the late Oligocene-early Miocene erosional event that affected the Norwegian-Greenland Sea. Correlation of 87Sr/86Sr and 1/Sr in calcites results in a two-component mixing model for late alteration products. One end-member of the mixing trend is Eocene or younger seawater. Strontium from the nonradiogenic endmember can not, however, have been derived directly from the basalts. Rather, the data suggest that Sr in the calcites is a mixture of Sr derived from seawater and from pre-existing smectites. For Site 642, the reaction involved can be generalized as smectite + seawater ++ celadonite + calcite. The geochemical effects of this reaction include net gains of K and CO2 by the secondary mineral assemblage. The gross similarity of the reactions involved in late, low-temperature alteration at Site 642 to those observed in other sea floor basalts suggests that the transfer of K and C02 to the crust during low-temperature seawater-ocean crust interactions may be significant in calculations of global fluxes.

Stable oxygen isotope and Mg/Ca ratios of planktonic foraminifera from the Caribbean and North Atlantic

Variations in the strength of the North Atlantic Ocean thermohaline circulation have been linked to rapid climate changes during the last glacial cycle through oscillations in North Atlantic Deep Water formation and northward oceanic heat flux. The strength of the thermohaline circulation depends on the supply of warm, salty water to the North Atlantic, which, after losing heat to the atmosphere, produces the dense water masses that sink to great depths and circulate back south. Here we analyse two Caribbean Sea sediment cores, combining Mg/Ca palaeothermometry with measurements of oxygen isotopes in foraminiferal calcite in order to reconstruct tropical Atlantic surface salinity during the last glacial cycle. We find that Caribbean salinity oscillated between saltier conditions during the cold oxygen isotope stages 2, 4 and 6, and lower salinities during the warm stages 3 and 5, covarying with the strength of North Atlantic Deep Water formation. At the initiation of the Bølling/Allerød warm interval, Caribbean surface salinity decreased abruptly, suggesting that the advection of salty tropical waters into the North Atlantic amplified thermohaline circulation and contributed to high-latitude warming.

Seawater Nd and Pb isotopic record in central Pacific and Caribbean sediments

The shoaling and final closure of the Central American Seaway (CAS) resulted in a major change of the global ocean circulation and has been suggested as an essential driver for strengthening of Atlantic Meridional Overturning Circulation (AMOC). The exact timing of CAS closure is key to interpreting its importance. Here we present a reconstruction of deep and intermediate water Nd and Pb isotope compositions obtained from fossil fish teeth and the authigenic coatings of planktonic foraminifera in the eastern equatorial Pacific (Ocean Drilling Program (ODP) Site 1241) and the Caribbean (ODP Sites 998, 999, and 1000) covering the final stages of CAS closure between 5.6 and 2.2 Ma. The data for the Pacific site indicate no significant Atlantic/Caribbean influence over this entire period. The Caribbean sites show a continuous trend to less radiogenic Nd isotope compositions during the Pliocene, consistent with an enhancement of Upper North Atlantic Deep Water (UNADW) inflow and a strengthening of the AMOC. Superimposed onto this long-term trend, shorter-term changes of intermediate Caribbean Nd isotope signatures approached more UNADW-like values during intervals when published reconstructions of seawater salinity suggested complete closure of the CAS. The data imply that significant deep water exchange with the Pacific essentially stopped by 7 Ma and that shallow exchange, which still occurred at least periodically until approximately 2.5 Ma, may have been linked to the strength of the AMOC but did not have any direct effect on the intermediate and deep Caribbean Nd isotope signatures through mixing with Pacific waters.

(Table 1) Cd/Ca and Mn/Ca ratios of benthic foraminifera from DSDP Hole 30-289

The late Miocene carbon shift (~6.2 Myr) -a 0.5-1.0 per mil, d13C decrease in benthic and planktonic foraminifera- has been ascribed to changes in global inventory, deep-ocean circulation, and/or productivity. Cadmium, d13C, and nutrients in the ocean are linked; comparison of d13C and Cd/Ca yields circulation and chemical inventory information not available from either alone. We determined Cd/Ca ratios in late Miocene benthic foraminifera from DSDP Site 289. Results include: (1) late Miocene Pacific Cd/Ca values fall between those of late Quaternary Atlantic and Pacific benthic foraminifera; (2) there are no systematic Cd/Ca offsets between Cibicidoides kullenbergi, Cibicidoides wuellerstorfi and Uvigerina spp.; and (3) there is a very slight Cd/Ca change coincident with d13C. Cd/Ca, slightly higher in younger, isotopically lighter samples, exhibits a smaller increase than predicted if circulation were the primary cause of the carbon shift. The carbon shift may have been due to a long-term shift in the steady-state carbon isotope input or to a change in the sedimentation of organic carbon relative to calcium carbonate.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

(Table 1) Age determination and isotopic signature of last glacial Patagonian caly/silt

Ice cores provide a record of changes in dust flux to Antarctica, which is thought to reflect changes in atmospheric circulation and environmental conditions in dust source areas (Forster et al., 2007; Diekmann et al. 2000, doi:10.1016/S0031-0182(00)00138-3; Winckler et al., 2008, doi:10.1126/science.1150595; Reader et al., 1999, doi:10.1029/1999JD900033; Mahowald et al., 1999, doi:10.1029/1999JD900084; Petit et al., 1999, doi:10.1038/20859; 1990, doi:10.1038/343056a0 Delmonte et al., 2009, doi:10.1029/2008GL033382; Lambert et al., 2008, doi:10.1038/nature06763). Isotopic tracers suggest that South America is the dominant source of the dust (Grousset et al., 1992, doi:10.1016/0012-821X(92)90177-W; Basile et al., 1997, doi:10.1016/S0012-821X(96)00255-5; Gaiero et al., 2007, doi:10.1016/j.chemgeo.2006.11.003), but it is unclear what led to the variable deposition of dust at concentrations 20-50 times higher than present in glacial-aged ice (Petit et al., 1990, doi:10.1038/343056a0; Lambert et al., 2008, doi:10.1038/nature06763). Here we characterize the age and composition of Patagonian glacial outwash sediments, to assess the relationship between the Antarctic dust record from Dome C (refs Lambert et al., 2008, doi:10.1038/nature06763; Wolff et al., 2006, doi:10.1038/nature04614) and Patagonian glacial fluctuations (Sugden et al., 2005; McCulloch et al., 2005, doi:10.1111/j.0435-3676.2005.00260.x; Kaplan et al., 2008, doi:10.1016/j.quascirev.2007.09.013) for the past 80,000 years. We show that dust peaks in Antarctica coincide with periods in Patagonia when rivers of glacial meltwater deposited sediment directly onto easily mobilized outwash plains. No dust peaks were noted when the glaciers instead terminated directly into pro-glacial lakes. We thus propose that the variable sediment supply resulting from Patagonian glacial fluctuations may have acted as an on/off switch for Antarctic dust deposition. At the last glacial termination, Patagonian glaciers quickly retreated into lakes, which may help explain why the deglacial decline in Antarctic dust concentrations preceded the main phase of warming, sea-level rise and reduction in Southern Hemisphere sea-ice extent (Wolff et al., 2006, doi:10.1038/nature04614).

Atlantic 231Pa/230Th and biogenic opal compilation of the Holocene and the LGM

The strength and geometry of the Atlantic meridional overturning circulation is tightly coupled to climate on glacial-interglacial and millennial timescales, but has proved difficult to reconstruct, particularly for the Last Glacial Maximum. Today, the return flow from the northern North Atlantic to lower latitudes associated with the Atlantic meridional overturning circulation reaches down to approximately 4,000 m. In contrast, during the Last Glacial Maximum this return flow is thought to have occurred primarily at shallower depths. Measurements of sedimentary 231Pa/230Th have been used to reconstruct the strength of circulation in the North Atlantic Ocean, but the effects of biogenic silica on 231Pa/230Th-based estimates remain controversial. Here we use measurements of 231Pa/230Th ratios and biogenic silica in Holocene-aged Atlantic sediments and simulations with a two-dimensional scavenging model to demonstrate that the geometry and strength of the Atlantic meridional overturning circulation are the primary controls of 231Pa/230Th ratios in modern Atlantic sediments. For the glacial maximum, a simulation of Atlantic overturning with a shallow, but vigorous circulation and bulk water transport at around 2,000 m depth best matched observed glacial Atlantic 231Pa/230Th values. We estimate that the transport of intermediate water during the Last Glacial Maximum was at least as strong as deep water transport today.