(Table 1) Composition of clay minerals in DSDP Hole 75-532

An investigation of the quantitative composition of the coarse (> 40 µm) and clay (< 2 µm) fraction of HPC 532, DSDP Leg 75, in 1300 m water depth on the eastern Walvis Ridge off Southwest Africa yielded the following results: (1) The sediments reflect a complete Latest Miocene to Recent depositional history. Sedimentation rates vary between 2.3 and 7.8 cm/ka. (2) Preservation of calcium carbonate is subject to strong variations: short-term (< 100,000 years) and long-term (about 1 m.y.) cycles in carbonate dissolution have been observed, with strongest dissolution occurring during periods of lowered sea level. (3) Upwelling influence from the near-coastal upwelling centre has been detected by means of the opal content: interglacial periods show high opal contents, because the Benguela Current turned westward at about 20°S and carried opal-laden upwelled water to the west. Sediments from glacial periods, however, show opal minima. Besides these short-term cyclic variations in opal content, long-term cycles have been found, with maximum upwelling influence in the latest Pliocene/early Quaternary. (4) Each CaCO3 dissolution minimum (maximum) is correlated with an opal maximum (minimum) throughout the sediment sequence. (5) The oceanographic system off southwest Africa remained essentially unchanged since the latest Miocene: sea level rose and fell periodically on a small and on a large scale, and the Benguela Current flowed southeast-northwest and turned to the west at the latitude of Site 532 during interglacial periods, when sea level was high. (6) The climate in the near-coastal area of southwest Africa in the latitude of Site 532 has probably been arid throughout the investigated period.

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Thermal diagenesis of clay minerals within volcanogenic material from ODP Site 135-841

Clay minerals are examined in detail in the sediment from the Tonga Trench margin at Site 841 (Leg 135 ODP). The changes in amount and nature of secondary clays with depth provide an alternative explanation for the intensive alteration of volcanogenic material at convergent margins. A characteristic distribution of clay minerals with depth shows four distinct zones unexplainable by simple burial diagenesis processes. These are named the upper, reactive, lower and rhyolitic zones. The reactive zone is intercalated with numerous sills and is characterized by the dominant iron-rich clays such as saponite, corrensite and chlorite associated with analcime. The occurrence of such iron-rich clays, mostly associated with a large amount of analcime, yields chemical and mineralogical evidence for thermal diagenesis. The required heat for the diagenetic process was transferred from recently intruded basaltic andesite sills. In the vicinity of these intrusions, the iron-rich clay minerals may have formed at temperatures up to 200°C. A zoning with respect to clay and zeolite minerals indicates that the influence of the palaeoheat flow decreased with the distance from the intrusion. The formation of interlayered I/S, illite, kaolinite and aluminous chlorite, which are recognized as major secondary minerals within the rhyolitic complex, was mainly controlled by both early diagenesis at moderately elevated temperatures, and since the Eocene by burial diagenesis at low temperatures. The occurrence of a steam zone in an early stage of the intrusion is restricted to Miocene tuffs and has overprinted the early alteration of the volcanogenic material within the tuffs and has changed the originally pristine composition of the pore fluids.