Diffusion transport of water in basalts

Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -> D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Primary composition, alteration, and origin of Cretaceous volcaniclastic rocks at DSDP Site 89-585

An upper Aptian to middle Albian series of volcaniclastic rocks more than 300 m thick was drilled at Site 585 in the East Mariana Basin. On the basis of textural and compositional (bulk-rock chemistry, primary and secondary mineral phases) evidence, the volcaniclastic unit is subdivided into a lower (below 830 m sub-bottom) and an upper (about 670-760 m) sequence; the boundary in the interval between is uncertain owing to lack of samples. The rocks are dominantly former vitric basaltic tuffs and minor lapillistones with lesser amounts of crystals and basaltic lithic clasts. They are mixed with shallow-water carbonate debris (ooids, skeletal debris), and were transported by mass flows to their site of deposition. The lower sequence is mostly plagioclase- and olivine-phyric with lesser amounts of Ti-poor clinopyroxene. Mineralogical and bulk-rock chemical data indicate a tholeiitic composition slightly more enriched than N-MORB (normal mid-ocean ridge basalt). Transport was by debris flows from shallow-water sites, as indicated by admixed ooids. Volcanogenic particles are chiefly moderately vesicular to nonvesicular blocky shards (former sideromelane) and less angular tachylite with quench plagioclase and pyroxene, indicating generation of volcanic clasts predominantly by spalling and breakage of submarine pillow and/or sheet-flow lavas. The upper sequence is mainly clinopyroxene- and olivine-phyric with minor plagioclase. The more Ti-rich clinopyroxene and the bulk-rock analyses show that the moderately alkali basaltic composition throughout is more mafic than the basal tholeiitic sequence. Transport was by turbidity currents. Rounded epiclasts of crystalline basalts are more common than in the lower sequence, and, together with the occurrence of oxidized olivine pseudomorphs and vesicular tachylite, are taken as evidence of derivation from eroded subaerially exposed volcanics. Former sideromelane shards are more vesicular than in the lower sequence; vesicularity exceeds 60 vol.% in some clasts. The dominant clastic process is interpreted to be by shallow-water explosive eruptions. All rocks have undergone low-temperature alteration; the dominant secondary phases are "palagonite," chlorite/smectite mixed minerals, analcite, and chabazite. Smectite, chlorite, and natrolite occur in minor amounts. Phillipsite is recognized as an early alteration product, now replaced by other zeolites. During alteration, the rocks have lost up to 50% of their Ca, compared with a fresh shard and fresh glass inclusions in primary minerals, but have gained much less K, Rb, and Ba than expected, indicating rapid deposition prior to significant seafloor weathering.

39Ar/40Ar ratios of whole rock samples from ODP Hole 107-655B and 107-651A (Table 1)

Six whole rocks from the basaltic lava series drilled in the Vavilov basin have been analyzed by 39Ar-40Ar stepwise heating method. One sample from the upper part of the Hole 655B basement gave a plateau-age at 4.3 ± 0.3 Ma whereas the other ones showed disturbed age spectra caused by alteration processes. The weighted averages of ages measured at low and intermediate temperatures on these five samples are concordant (1) one to each other and (2) with independent estimates deduced from paleontological and paleomagnetical arguments. Ages of 4.3 ± 0.3 Ma and from 3 to 2.6 Ma may represent reasonable estimates of the crystallization ages of the basaltic lava series of the Holes 655B and 651A, respectively. These ages must be taken with caution because they correspond to argon released from secondary phases characterized by low argon retention.

Geochemistry of oceanic crust of the North Atlantic

87Sr/a6Sr ratios, Sr, K, Rb and Cs contents and the petrology of basalts and secondary phases recovered from deep basement drilling at DSDP Sites 332B, 417A, 417D and 418A show that the oceanic crust alters in four distinct stages characterized by formation of palagonite, smectite and calcite (Stages I, II and III, respectively). Stage IV represents the final compaction of the crust, including a dehydration of the crust without major chemical changes. Isotopic age determinations by Hart and Staudigel (1978, doi:10.1029/GL005i012p01009) and Richardson et al. (doi:10.1029/JB085iB12p07195), show that, at least for Atlantic-type crustal regimes, Stage I and II last for a maximum of 3 m.y., and Stage III lasts beyond Stage I and II, but is probably completed in significantly less than 10 m.y. Stage IV is long-lived and may still be active at 100 m.y. Stages I and II, the phase of halmyrolysis, include geochemically significant interactions between seawater and basalt for the upper 500 m of layer II and involve volumes of seawater containing a large basaltic component. Stage III solutions show evidence of less seawater-basalt interaction, at least to depths of 500 m; calcites deposited from these solutions have Sr isotopic ratios close to seawater values; but also have very low Sr/Ca ratios indicating a large basalt Ca component in the solutions. Smectite formation is the result of the interaction of seawater and basalt. The initial 87Sr/a6Sr ratios of smectites represent the Sr isotopic composition of the solution when the smectite is being formed. Thereafter, alkalies may be continuously added to interlayer positions in the smectite in order of decreasing hydration energy (Cs is more enriched than Rb, Rb more than K). The later-formed carbonates have very low alkali concentrations, and 87Sr/86Sr ratios identical to contemporaneous seawater. Therefore, since the alkali concentrations in a whole rock sample are affected by different alteration processes, the alkali concentrations alone are not reliable indicators of the degree of alteration.

(Table 1) B content, d11B, d18O, degree of alteration, and lithology of basalts from ODP Hole 504B

Boron contents and boron isotopic compositions were determined for the uppermost 1.3 km section of typical 6.2 Ma oceanic crust from DSDP/ODP Hole 504B, Costa Rica Rift, Galapagos Spreading Center. Both the boron content and the d11B value in the oceanic crust are controlled by two types of alteration: 1. (1) low-temperature alteration (0 to 60°C; Zones I and II) and 2. (2) high-temperature hydrothermal alteration (200 to 400°C; Zones III and IV). Basalts subjected to the low-temperature alteration are characterized by their relatively high boron contents (0.69 to 19.3 ppm) and high d11B values (+2.2 to +10.6?), indicating uptake of boron into secondary phases in equilibrium with seawater or evolved seawater. Hydrothermally altered basalts contain less abundant boron (0.17 to 0.52 ppm) and relatively constant d11B values (?0.1 to +1.0?). Although basalts from the upper part of these hydrothermal zones (<1300 mbsf) show equilibrated boron content and d11B value with aqueous fluid, effective leaching of boron from basalt is predominant in the lower part (>1300 mbsf). Original boron content and d11B value of the Hole 504B MORB were 0.35 ppm and +0.2?, respectively. The present data provide fundamental information in understanding of the distribution of boron and boron isotopes in the oceanic crust.