Mössbauer characterisation of sediments from ODP Sites 128-798 and 128-799

57Fe Mössbauer spectra for 26 sediment and 6 carbonate concretion samples from Sites 798 and 799 were recorded at 293 K. Most spectra were deconvolved to two quadrupole doublets without magnetic hyperfine structure. Typical Mössbauer parameters were: isomer shift (I.S.) = 0.34 mm/s and quadrupole splitting (Q.S.) = 0.64 mm/s for the paramagnetic Fe3+ component (partly, pyrite); I.S. = 1.13 mm/s and Q.S. = 2.64 mm/s for the high-spin Fe2+ component derived from iron-bearing aluminosilicates. A few spectra included other high-spin Fe2+ components ascribed to iron-bearing carbonate minerals (e.g., ferroan magnesite), according to the Mössbauer parameters for Fe2+ in the carbonate concretions. We present the distribution of iron among different chemical forms as a function of depth. These data might indicate changes of depositional and diagenetic conditions.

Organic geochemistry of sediments of the Gulf of California

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material. The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter. Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (d13C) values of kerogens decrease by 1-1.5 per mil near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.

Chemical composition of a manganese nodule from the Pacific Ocean

By means of spectrographic analysis 96 samples of marine sediments were analyzed quantitatively for V, Ti, Zr, Co, Ni, Sc, Cr, and La, and semi-quantitatively for Ba and Sr. Ca has been estimated by visual comparison of spectrographic plates, and several Fe values have also been determined in the same way. Geographically 40 of these samples are from the Pacific Ocean basin, one of which is a manganese nodule, 21 from the Gulf of Mexico, 11 from Atchafalaya Bay, 8 from American Devonian to Miocene sedimentary rocks, 4 from the Mississippi Delta, 3 from the San Diego trough, 3 from off Grand Isle, 3 from Lake Pontchartrain, from Bay Rambour, 1 from Laguna Madre off the Texas coast, and 1 from the Guadalupe River, Texas. The afore-mentioned elements were sought using PdCl2 as an internal standard, after the method developed by Ahrens (1950) and his co-workers. Samples were run in duplicate, and standard deviations varied from 5 to 14 percent. Working curves, from which final values were obtained, were constructed with the use of standard granite, G1, and the standard diabase, W1, as standards. See Fairbairn and others (1951). An experiment was carried out to determine the effect of matrix change, involving CaCO3, on the spectral line intensities of the quantitatively analyzed elements. The distribution of each of the elements is discussed separately, and particular emphasis is given to oceanic "red clay", in which many elements are enriched. A general discussion is given to mineralogy of the sediments, cation exchange in its bearing on this thesis, and a brief recount of the two hypotheses of origin of oceanic "red clay". An application of the findings of this thesis to aid in the choice of the more likely hypothesis is made.

Mössbauer study at DSDP Hole 95-612

57Fe Mössbauer spectra of 15 oceanic sediment samples collected from Site 612 (Deep Sea Drilling Project Leg 95) were recorded. These spectra showed that most of the iron in the sediments was present as high-spin, paramagnetic Fe2+ and Fe3+. The ferrous iron was mainly distributed in terrigenous clays and biogenic carbonates. The variation of the Mössbauer parameters for Fe2+ with sub-bottom depth suggests that the main Fe2+-bearing component changed with geologic time. The amount of iron in each iron-bearing phase as estimated from the corresponding peak areas in the spectra also changed with depth. These variations in the Mössbauer parameters and peak areas are correlated with lithologic changes in the sediment column.

Spectral reflectance library of selected biotic and abiotic coral reef features in Heron Reef

Underwater spectral reflectance was measured for selected biotic and abiotic coral reef features of Heron Reef from June 25-30, 2006. Spectral reflectance's of 105 different benthic types were obtained in-situ. An Ocean Optics USB2000 spectrometer was deployed in an custom made underwater housing with a 0.5 m fiber-optic probe mounted next to an artificial light source. Spectral readings were collected with the probe(bear fibre) about 5 cm from the target to ensure that the target would fill the field of view of the fiber optic (FOV diameter ~4.4 cm), as well as to reduce the attenuating effect of the intermediate water (Roelfsema et al., 2006). Spectral readings included for one target included: 1 reading of the covered spectral fibre to correct for instrument noise, 1 reading of spectralon panel mounted on divers wrist to measure incident ambient light, and 8 readings of the target. Spectral reflectance was calculated for each target by first subtracting the instrument noise reading from each other reading. The corrected target readings were then divided by the corrected spectralon reading resulting in spectral reflectance of each target reading. An average target spectral reflectance was calculated by averaging the eight individual spectral reflectance's of the target. If an individual target spectral reflectance was visual considered an outlier, it was not included in the average spectral reflectance calculation. See Roelfsema at al. (2006) for additional info on the methodology of underwater spectra collection.

(Table 1) Stable oxygen and carbon isotopic ratios of tree rings, and tree ring width of white spruce (Picea glauca), Ennadai Lake

Stable isotope ratios from tree rings and peatland mosses have become important proxies of past climate variations. We here compare recent stable carbon and oxygen isotope ratios in cellulose of tree rings from white spruce (Picea glauca), growing near the arctic tree line; and cellulose of Sphagnum fuscum stems, growing in a hummock of a subarctic peatland, in west-central Canada. Results show that carbon isotopes in S. fuscum correlate significantly with July temperatures over the past ~20 yr. The oxygen isotopes correlate with both summer temperature and precipitation. Analyses of the tree-ring isotopes revealed summer temperatures to be the main controlling factor for carbon isotope variations, whereas tree-ring oxygen isotope ratios are controlled by a combination of spring temperatures and precipitation totals. We also explore the potential of combining high-frequency (annual) climate signals derived from long tree-ring series with low-frequency (decadal to centennial) climate signals derived from the moss remains in peat deposits. This cross-archive comparison revealed no association between the oxygen isotopes, which likely results from the varying sensitivity of the archives to different seasons. For the carbon isotopes, common variance could be achieved through adjustments of the Sphagnum age model within dating error.