Chemical and strontium isotopic compositions of interstitial waters from sediments of ODP Site 135-841

The depth variations in the major chemical components dissolved in interstitial waters from the Tonga margin (ODP Site 841) are much more pronounced than those usually observed in deep-sea sediments. The extensive alteration of volcanic Miocene sediments to secondary minerals such as analcime, clays, and thaumasite forms a CaCl2-rich brine. The brine results from a high exchange of Ca to Na, K, and Mg and an increase in Cl concentrations due to removal of H2O from the fluid during the authigenesis of hydrous minerals. The formation of thaumasite could have partly controlled the concentration of dissolved SO4, HCO3, and Ca in the Miocene sediments. The strontium isotopic signature of the interstitial water suggests that alteration of the volcanic Miocene sediments occurred a long time after sedimentation. A transient diffusion model indicates that molecular diffusion was not prevented by lithologic barriers and that the formation of secondary minerals in the Miocene sediment occurred over a short period of time (e.g.,

Geochemistry of felsic rocks and minerals of ODP Hole 135-841B

A felsic volcanic series (605-825 mbsf) overlain by upper Eocene shallow-water sediments (500-605 mbsf) and basalticandesitic sills that intruded into sediments of Holocene to Miocene age (0-500 mbsf) was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The volcanic sequence at Site 841 includes altered and mineralized calc-alkaline rhyolites and dacites, dacitic tuffs, lapilli tuffs, flow breccias, and welded tuffs. These rocks formed subaerially or in a very shallow-water environment suffering a subsidence of >5000 m since Eocene times. Calculations of gains and losses of the major components during alteration show most pronounced changes in the uppermost 70 m of the volcanic sequence. Here, Al, Fe, Mg, and K are enriched, whereas Si and Na are strongly depleted. Illite, vermiculite, chlorite, and hematite predominate in this part of the hole. Throughout the section, quartz, plagioclase, kaolinite, and calcite are present. Sulfide mineralization (up to 10 vol%) consisting mainly of disseminated pyrite (with minor pyrrhotite inclusions) and marcasite together with minor amounts of chalcopyrite is pervasive throughout. Locally, a few sulfide-bearing quartz-carbonate veins as well as Ti-amphibole replacement by rutile and then by pyrite were observed. Strong variations in the As content of sulfides (from 0 to 0.69 wt%) from the same depth interval and local enrichments of Co, Ni, and Cu in pyrite are interpreted to result from fluctuations in fluid composition. Calculations of oxygen and sulfur fugacities indicate that fO2 and fS2 were high at the top and lower at the bottom of the sequence. Sulfur isotope determinations on separated pyrite grains from two samples give d34S values of +6.4ë and +8.4ë, which are close to those reported from Kuroko and Okinawa Trough massive sulfide deposits and calc-alkaline volcanic rocks of the Japanese Ryukyu Island Arc. Calculated chlorite formation temperatures of 265°-290°C at the top of the sequence are consistent with minimum formation temperatures of fluid inclusions in secondary quartz, revealing a narrow range of 270°-297°C. Chlorite formation temperatures are constant downhole and do not exceed 300°C. The presence of marcasite and 4C-type pyrrhotite indicates a formation temperature of <= 250°C. At a later stage, illite was formed at the top of the volcanic series at temperatures well below 200°C.

Magnetic properties of basalts and sediments of ODP Leg 135 sites

Paleomagnetic and rock-magnetic investigations of basalts from Hole 834B in the Lau backarc basin and of sediments from Holes 841A and 841B at the Tonga Ridge are reported. Three groups of blocking temperatures in the basalts suggest the presence of at least three magnetic phases: pure magnetite, a Ti-poor titanomagnetite, and a Ti-rich phase. The drill-string-induced remanence in the basalts is typically between three and six times the original normal remanent magnetization intensity, but it is mostly removed by alternating-field (AF) cleaning in 5 mT. Volume susceptibility values range from 0.04 * 10**-3 to 4 * 10**-3 cgs. The modified Q-ratio J5/sus ranges from 0.5 to 10. The drill-string-induced remanence behaves different in the two sediment cores from Holes 841A and 841B, which may be the result of differences in the sediment or caused by the different drilling equipment used. The AF-cleaned inclinations of the sediment in Holes 841A and 841B suggest a slight flattening with increasing depth (up to 6° under a load of 400 m of sediment) to be present. This flattening is likely to be caused by the differential rotation of detrital particles under compaction during diagenesis.

Late Neogene biostratigraphy of ODP Leg 135 sites

Integration of biostratigraphic and magnetostratigraphic results from Leg 135 sites has given additional information as to the position and reliability of various bioevents compared with previously published results. Two sites (834: Gilbert to Brunhes; and 836: Brunhes) provided excellent magnetic and biostratigraphic data. From these it is suggested that some bioevents are older than previously recorded: the first appearances (FAs) of Emiliania huxleyi (within the Brunhes Chron, at the same level as the FA of Helicosphaera inversa) and Globorotalia (Truncorotalia) truncatulinoides (within the upper Gauss Chron), and the last appearance (LA) of Gr. (Tr.) tosaensis (upper Matuyama Chron). The FA of Gr. (Tr.) crassaformis hessi is variable, but the oldest occurrence is just below the Cobb Mountain Subchron. Other key bioevents, such as the LAs of Discoaster pentaradiatus (just above the Réunion Subchron), D. tamalis (within the lower reversed part of the Matuyama Chron), Sphenolithus (lower Gauss Chron), and Amaurolithus primus (topmost Gilbert Chron) appear higher than previously recorded. Some key biostratigraphic taxa, such as Globigerinoides quadrilobatus fistulosus, Pulleniatina finalis, P. primalis, and Sphaeroidinella dehiscens, are either rare or their distribution is sporadic to the extent that they are unsuitable for biostratigraphic use in the area studied. Because of the rarity of P. primalis, the FA of Globorotalia (Globorotalia) multicamerata has been used to mark the base of Zone N17B. Though levels are present at most sites in which populations of Pulleniatina are sinistrally coiled, it is difficult to equate these coiling changes with previous records.

Miocene to Pleistocene planktonic foraminifer biostratigraphy of ODP Leg 135 sites

Diverse and well-preserved planktonic foraminifers were recovered from six sites (834-839) drilled in the Lau Basin. Planktonic faunas from the Tongan Platform sites varied from those of the Lau Basin sites by being less well preserved (Site 840) to being very poorly preserved and very sparse (Site 841); at Site 841 most samples were barren. All sites penetrated a volcaniclastic sequence in which thick ash beds were encountered; foraminifer populations within the ash beds were often very small, making it difficult to obtain biostratigraphic data. No hiatuses were encountered in the upper Miocene to Pleistocene sections of the Lau Basin, but a possible break occurs at Site 840 on the Tongan Platform. Site 834 penetrated through a Quaternary-Pliocene sequence overlying basaltic basement, and topmost Miocene (Zone N17B) sediments interbedded within the volcanic sequence. Site 835 penetrated into the lower Pliocene (Zones N19 to N19-20). Site 836 penetrated the shortest section, with Zone N22 {Globorotalia (Truncorotalia) crassaformis hessi Subzone) directly overlying basalts. Site 837 penetrated into the basal part of Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone) overlying basalt. Site 838 failed to encounter basalts, with the oldest sediment being from Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone). Site 839, within the same basin as Site 838, located Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone) sediments directly overlying igneous basement. Site 840 penetrated into the upper Miocene Zone N17A without encountering any major unconformity. Site 841, studied mainly from core-catcher samples, penetrated a Quaternary to questionable upper Miocene sequence that was in fault contact with middle Miocene (Zones N8 to N9) sediments. For the Lau Basin sites, reworking was encountered only in Sites 834 and 835. Site 834 was drilled adjacent to the Lau Ridge, on which are developed numerous reef al and shallow-water environments, where erosional conditions could have been expected during sea-level lowstands. Site 835 was drilled in a narrow basin that has been remote from these erosional influences; slumping and erosion of material from the adjacent basin slopes appears to have been the source of the reworking. For the Tongan Platform sites, reworking was observed only in the lower part of the upper Miocene section at Site 841, where late Eocene larger foraminifers are present in conglomerates and grits. The presence of Globorotalia (Globorotalia) multicamerata and small specimens of Sphaeroidinellopsis spp. in the Pleistocene of Site 840 may indicate reworking, but this is not clear. Unit I, which marks a reduction in volcanic activity in the Lau Basin, ranges in age from the lower part of Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone) at Sites 834 and 835, to within Zone N22 (Globorotalia crassaformis hessi Subzone) at Sites 836 to 838, and within the upper part of Zone N22 (Bolliella praeadamsi Subzone) at Site 839. Units II and III are generally represented by thick to very thick ash beds, which generally contain low-diversity and often poorly preserved assemblages. Igneous sources seem to have remained important contributors of sediment up to the present day.

Organic geochemistry of ODP Leg 135 sediment samples

The average total organic carbon (TOC) content obtained after Rock-Eval/TOC analysis of 156 sediment samples from the eight sites cored during Leg 135 is 0.05%. Hence, the TOC content of Leg 135 sediments is extremely low. The organic matter that is present in these samples is probably mostly reworked and oxidized material. Ten sediment samples were selected for extraction and analysis by gas chromatography and gas chromatography-mass spectrometry. Very low amounts of extractable hydrocarbons were obtained and some aspects of the biomarker distributions suggest that these hydrocarbons are not representative of the organic matter indigenous to the samples. A sample of an oil seep from Pili, Tongatapu was also analyzed. The seep is a biodegraded, mature oil that shows many characteristics in common with previously published analyses of oil seeps from Tongatapu. Biomarker evidence indicates that its source is a mature, marine carbonate of probable Late Cretaceous-Early Tertiary age. The source rock responsible for the Tongatapu oil seeps remains unknown.