Organic chemical characterization of sediment-trap particulates from San Nicolas,Santa Barbara,Santa Monica and San Pedro Basins,California

Particulate matter was collected during September–October, 1977, in particle traps suspended 30–60 m above the floor of San Nicolas, Santa Barbara, Santa Monica and San Pedro Basins, off the coast of southern California. The trap particulates were analyzed for C₁₅–C₃₅ hydrocarbons using gas chromatography (GC) and GC-mass spectrometry. Kerogens and humic acids were characterized by H/C, N/C, δ¹³C, δ¹⁵N and δ³⁴S ratios, and by electron-spin resonance. Hydrocarbons arising from fresh and weathered petroleum, marine autochthonous and terrestrial sources were identified. The rates of petroleum deposition during the collection period followed the order: San Nicolas Basin < Santa Barbara Basin ~ Santa Monica Basin < San Pedro Basin, with the largest amount of weathered petroleum being deposited in San Pedro Basin. The rates of petroleum deposition are correlated more strongly with human activities such as shipping, and the discharge of municipal and industrial wastes, than with natural submarine oil seepage. Analyses of kerogens and humic acids indicate that the majority of the organic matter in the trap particulates is of marine origin. The water column overlying Santa Barbara Basin appears to have the highest marine productivity of the four basins studied.     

Metal accumulation rates in northwest Atlantic pelagic sediments

Measurements of ²³⁰Th, ${}^{87}\text{Sr}{}^{86}\text{Sr}$ and twenty-four metals were made on cores from the Nares Abyssal Plain. The sediment is characterized by slowly-accumulating (0.3–0.7 g/cm² 10³ yr) pelagic red clays and rapidly deposited grey clays transported by turbidity currents. Despite their colour differences and the enrichment of Mn, Fe, Cu, Co, Ni, Zn, V and, to a lesser degree, the rare earths in the red clays, Sr isotope evidence demonstrates that the clays have the same terrigenous origin. The excesses of metals in the red clays have been attributed to metal removal from the water column and a comparison with the grey clays has enabled the authigenic fluxes of metals to be estimated. The fluxes obtained are in the ranges 20–50 μmol/cm² 10³ yr for Mn and Fe, 0.1–0.4 μmol/cm² 10³ yr for Cu, Co, Ni, Zn, V, Sr and Ce, 10–20 nmol/cm² 10³ yr for La and Nd, and 0.5-3 nmol/cm² 10³ yr for Sm, Eu, Gd, Dy, Er and Yb. Authigenic fluxes of Y, Nb, Cr, Zr, Rb, U and Th were not resolvable. Fluxes appear to be near constant on the Plain but comparison with other areas shows that they are quite variable both between and within ocean basins. The chief factor controlling authigenic fluxes is the geochemical abundances of the elements but fractionation within both the transition element and rare earth series can be recognized from inter-element comparisons and from differences in fluxes between Atlantic and Pacific red clays corresponding to the oceanic reactivities of the elements.     

Budgets and behaviors of uranium and thorium series isotopes in Santa Monica Basin sediments

Nine natural decay-series isotopes were measured in six box cores collected from a transect across the Santa Monica Basin. The ²¹⁰Pb-derived sedimentation rate decreases from ~80 mg/cm²-yr at the slope to ~20 mg/cm²-yr in the deep central basin. Sediment mixing prevails in sites underlying oxic waters, but is subdued in the anoxic deep basin below the sill depth. Uranium contents in sediments are controlled by levels of authigenic U, which are higher in the more reduced condition in the deep basin. Most of the authigenic U results from precipitation within the sediments.The ²³²Th-²²⁸Th disequilibrium in sediments indicates that ²²⁸Ra is lost from the sediments from a depth of ~ 10 cm upward. Modelling the distribution of excess ²²⁸Th and ²³⁴Th in the surficial layers of the deep basin sediments results in a mean sediment mixing coefficient of 0.2 cm²/yr and a sedimentation rate close to that based on ²¹⁰Pb. There is no evidence of changing sedimentation rate in the central basin during the past century. Fluxes of excess ²¹⁰Pb, ²³⁰Th and ²³¹Pa to the central Santa Monica Basin sediments are much higher than what can be predicted from local supply. Advective input of open ocean waters coupled with enhanced scavenging of these reactive nuclides at the ocean margin is considered to be the primary cause.     

Preservation of particulate non-lithogenic uranium in marine sediments

Particulate non-lithogenic uranium (PNU), excess U above detrital background levels found in marine particulate matter, is formed in surface waters throughout the ocean. Previous studies have shown that PNU is regenerated completely prior to burial of particles in sediments within well-oxygenated open-ocean regions. However, the fate of PNU has never been examined in ocean margin regions or in anoxic basins. Here we evaluate the preservation of PNU in ocean margin sediments and within semi-enclosed basins using samples from sediment traps deployed at multiple depths and surface sediments. Organic carbon fluxes at the sediment trap locations ranged from 0.1 to 4.3 g/cm² kyr, while the dissolved oxygen concentration in the water column ranged from <3 μM to ∼ 270 μM. Preservation of PNU increases with decreasing dissolved oxygen concentration, approaching 100% preservation at oxygen concentration < 25 μM. PNU contributes as much as 40 to 70% of the total authigenic U in sediments in the Santa Barbara Basin and seasonally anoxic Saanich Inlet, and some 10% to 50% of the total authigenic U in sediments off the central California Margin.     

Plutonium and americium in anoxic marine sediments: Evidence against remobitization

^{239 + 240}Pu activities of 100–450dpm/kg are found down to 15–18 cm in anoxic Saanich Inlet sediments, with a subsurface maximum in undisturbed deposits. Integrated ^{239 + 240}Pu inventories which overlap delivery estimates are present both in two cores of anoxic sediments from Saanich Inlet and in one core of oxic sediments 65 km away in Dabob Bay, Washington. ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ ratios in Saanich Inlet sediments overlap ratios in unfractionated midnorthern latitude fallout, in oxic sediments from the Washington continental shelf, and in anoxic sediments from two basins off southern California and Mexico. The ${}^{\mathrm{239\; +\; 240}}\text{Pu}{}^{137}\text{Cs}$ ratios in three intervals of Saanich Inlet sediments are also in agreement with ratios previously reported for oxic coastal marine sediments. The Pu inventories, the $\text{Am}\text{Pu}$ and $\text{Pu}\text{Cs}$ ratios, and the Saanich Inlet Dabob Bay comparison all argue that Pu is not rapidly remobilized in anoxic sediments.The subsurface ^{239 + 240}Pu activity maximum is not in agreement with the historical record of peak Pu fallout in 1963–1964 unless our ²¹⁰Pb-derived sedimentation rates are incorrectly high. However, they are in good agreement with previous ²¹⁰Pb and varve chronologies in Saanich Inlet, and also give reasonable dates for times when ^{239 + 240}Pu and SNAP-9A supplied ²³⁸Pu first appear in the sediments. We conclude they properly date the maximum in sedimentary ^{239 + 240}Pu activity at 1970–1973, and seek explanations for the 7–10yr time lag after peak fallout.^{239 + 240}Pu inventories in one core from the eastern basin of the Cariaco Trench and in two cores from Golfo Dulce. an anoxic basin off the Pacific coast of Costa Rica, are also in reasonable agreement with fallout delivery to these latitudes when excess ²¹⁰Pb inventories and fluxes are used to verify recovery of at least a major fraction of the most recently deposited sediments.     

Chronological variations in concentrations and isotopic compositions of anthropogenic atmospheric lead in sediments of a remote subalpine pond

Lead concentrations decrease 4-fold in going from the surface of sediments in a mountain pond to relatively small values in layers 130 yr old. There is a corresponding change in the $\text{Pb}{}^{206}\text{Pb}{}^{207}$ ratio in the sediments from industrial-like values of 1.18 near the surface to natural values of 1.24 at depth. Concentrations of Ca, Sr, and Ba remain relatively constant with depth. The excess Pb is shown to be of eolian anthropogenic origin, through isotopic, chemical, and mass balance relationships with metals in aerosols, dry deposition, and precipitation. This proves that inputs of contamination Pb were nearly absent centuries ago in a remote non-domesticated subalpine canyon, but are present today in that ecosystem in amounts more than 20 times the natural inputs and are irrefutably linked with industrial sources. As a consequence of these inputs, present Pb concentrations have been elevated 5-fold in plants and 50-fold in animals above natural levels. These Pb contamination effects are being caused by present-day atmospheric concentrations of ~10 ng Pb/m³. The ecosystem studied here characterizes the vast remote non-domesticated regions of North America, and these findings indicate that such regions are highly polluted by industrial Pb aerosols.     

On the age of the Onverwacht Group,Swaziland Sequence,South Africa

Some rocks of the Onverwacht Group, South Africa, have been analyzed for Rb and Sr concentrations and Sr isotopie composition. These rocks include volcanic rocks, layered ultramafic differentiates and cherty sediments. Whole rock data indicate that the Rb-Sr isotopie systems in many samples were open and yield no reasonable isochron relationships. However, the data of mineral separates from a basaltic komatiite define a good isochron of $\text{t = 3.50 ± 0.20}$ (2δ) b.y. with an initial Sr⁸⁷/Sr⁸⁶ ratio of $\text{0.70048 ± 5}$(2δ). The orthodox interpretation of this age is the time of the low grade metamorphism. Since the basaltic komatiite is stratigraphically lower than the Middle Marker Horizon (dated as $\text{3.36 ± 0.07}$ b.y. Hurley et al., 1972), and since it is commonly found that volcanism, sedimentary deposition, metamorphism and igneous intrusion in many Archean greenstone-granite terrain all took place in a relatively short time interval (less than 100 m.y.), it is reasonable to assume that the age of 3.50 b.y. might also represent the time of initial Onverwacht volcanism and deposition. The initial Sr⁸⁷/Sr⁸⁶ ratio obtained above is important to an understanding of the Sr isotopic composition of the Archean upper mantle. If the komatiite represents a large degree of partial melt (40–80 per cent) of the Archean upper mantle material, then the initial ratio obtained from the metamorphic komatiite should define an upper limit for the Sr isotopic composition of the upper mantle under the African crustal segment.     

A 560-Year Record of Santa Ana Fires Reconstructed from Charcoal Deposited in the Santa Barbara Basin, California

Microscopic charcoal from varved Santa Barbara Basin sediments was used to reconstruct a 560-yr record (A.D. 1425 to 1985) of Santa Ana fires. Comparison of large (>3750 μm²) charcoal with documented fire records in the Santa Barbara Ranger District shows that high accumulations correspond to large fires (>20,000 ha) that occurred during Santa Ana conditions. The charcoal record reconstructed a minimum of 20 large fires in the Santa Barbara region during the study period. The average time between fires shows no distinct change across three different land use periods: the Chumash period, apparently characterized by frequent burning, the Spanish/Early American period with nominal fire control, and the 20th century with active fire suppression. Pollen data support the conclusion that the fire regime has not dramatically changed during the last 500 yr. Comparison of large charcoal particle accumulation rates and precipitation reconstructed from tree rings show a strong relationship between climate and fire history, with large fires consistently occurring at the end of wet periods and the beginning of droughts.     

Importance of alteration of volcanic material in the sediments of deep sea drilling site 323: chemistry, 18O16O and 87Sr86Sr

A downhole decrease in ¹⁸O, Mg²⁺ and K⁺, an increase in Ca²⁺ and a low ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of 0.7067 in the pore fluids of DSDP site 323 were caused principally by the alteration of volcanic material. These chemical and isotopic patterns were produced by the alteration, in order of decreasing importance of: a 60-m thick basal layer of volcanic ash; the underlying basalts; and igneous components in the 640-m thick upper sequence composed largely of terrigenous material. A significant portion of the alteration of the ash in the basal sequence must have occurred before the deposition of the upper sediments, perhaps under the influence of advecting solutions. The rest of the alteration occurred during the deposition of the thick upper sediments. Mass balance considerations and the low δ¹⁸O values of most of the alteration products suggest that much of the later alteration occurred progressively over the last 13 Myr. The principal alteration products were smectite, potassium feldspar, clinoptilolite and calcite.     

Isotopic evidence for the origin of sulfur in the Herrin (no. 6) coal member of Illinois

The sulfur isotopic composition of the Herrin (No. 6) Coal from several localities in the Illinois Basin was measured. The sediments immediately overlying these coal beds range from marine shales and limestones to non-marine shales. Organic sulfur, disseminated pyrite, and massive pyrite were extracted from hand samples taken in vertical sections.The $\text{δ}{}^{34}\text{S}$ values from low-sulfur coals (< 0.8% organic sulfur) underlying nonmarine shale were +3.4 to +7.3%₀ for organic sulfur, +1.8 to +16.8%₀ for massive pyrite, and +3.9 to +23.8%₀ for disseminated pyrite. In contrast, the $\text{δ}{}^{34}\text{S}\text{values from high-sulfur coals}$ (> 0.8% organic sulfur) underlying marine sediments were more variable: organic sulfur, ?7.7 to +0.5%₀, pyrites, ?17.8 to +28.5%₀. In both types of coal, organic sulfur is typically enriched in ³⁴S relative to pyritic sulfur.In general, δ ³⁴S values increased from the top to the base of the bed. Vertical and lateral variations in δ ³⁴S are small for organic sulfur but are large for pyritic sulfur. The sulfur content is relatively constant throughout the bed, with organic sulfur content greater than disseminated pyrite content. The results indicate that most of the organic sulfur in high-sulfur coals is derived from post-depositional reactions with a ³⁴S-depleted source. This source is probably related to bacterial reduction of dissolved sulfate in Carboniferous seawater during a marine transgression after peat deposition. The data suggest that sulfate reduction occurred in an open system initially, and then continued in a closed system as sea water penetrated the bed.Organic sulfur in the low-sulfur coals appears to reflect the original plant sulfur, although diagenetic changes in content and isotopic composition of this fraction cannot be ruled out. The wide variability of the δ ³⁴S in pyrite fractions suggests a complex origin involving varying extents of microbial H₂S production from sulfate reservoirs of different isotopic compositions. The precipitation of pyrite may have begun soon after deposition and continued throughout the coalification process.     

Benthic fluxes and the cycling of biogenic silica and carbon in two southern California borderland basins

Benthic fluxes in two southern California borderland basins have been estimated by modeling water column property gradients, by modeling pore water gradients and by measuring changes in concentration in a benthic chamber. Results have been used to compare the different methods, to establish budgets for biogenic silica and carbon and to estimate rate constants for models of CaCO₃ dissolution. In San Pedro Basin, a low oxygen, high sedimentation rate area, fluxes of radon-222 (86 ± 8 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.9 ± 0.3 mmol m⁻² d⁻¹) and nitrate (−0.8 ± 0.1 mmol m⁻² d⁻¹) measured in a benthic chamber agree within the measurement uncertainty with fluxes estimated from modeling profiles of nutrients and radon obtained in the water column. The diffusive fluxes of radon, SiO₂ and TCO₂ determined from modeling the sediment and pore water also agree with the other approaches. Approximately 33 ± 13% of the organic carbon and 37 ± 47% of the CaCO₃ arriving at the sea floor are recycled. In San Nicolas Basin, which has larger oxygen concentrations and lower sedimentation rates than San Pedro, the fluxes of radon (490 ± 16 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.7 ± 0.2 mmol m⁻² d⁻¹), oxygen (−0.7 ± 0.1 mmol m⁻² d⁻¹) and nitrate (-0.4 ± 0.1 mmol m⁻² d⁻¹) determined from chamber measurements agree with the water column estimates given the uncertainty of the measurements and model estimates. Diffusion from the sediments matches the lander-measured SiO₂ and PO₄³⁻ (0.017 ± 0.002 mmol m⁻² d⁻¹) fluxes, but is not sufficient to supply the radon or TCO₂ fluxes observed with the lander. In San Nicolas Basin 38 ± 9% of the organic carbon and 43 ± 22% of the CaCO₃ are recycled. Approximately 90% of the biogenic silica arriving at the sea floor in each basin is recycled. The rates of CaCO₃ dissolution determined from chamber flux measurements and material balances for protons and electrons are compared to those predicted by previously published models of CaCO₃ dissolution and this comparison indicates that in situ rates are comparable to those observed in laboratory studies of bulk sediments, but orders of magnitude less than those observed in experiments done with suspended sediments.     

Pb,Sr and 10Be isotopic studies of volcanic rocks from the Northern Mariana Islands. Implications for magma genesis and crustal recycling in the Western Pacific

We report Sr and Pb isotope analyses for an extensive suite of volcanic rocks from the N. Mariana arc together with Sr and Pb isotope analyses of sediments from the nearby Mariana and Nauru basins. In addition ten of the most recent volcanic samples were analysed for ¹⁰Be.The Sr isotope compositions cluster tightly around ${}^{87}\text{Sr}{}^{86}\text{Sr}$ = 0.7035 being slightly but significantly higher than the Pacific ocean floor basalts on either side of the arc and agreeing well with previous data. In contrast, the large number of new Pb isotopic data presented significantly extends the observed range of Pb isotope compositions for volcanic rocks from the Mariana arc to more radiogenic compositions. The concentrations of ¹⁰Be were very low (< 0.5 × 10⁶ atom g^?1).These new data require either that the Pb and Sr isotopic compositions of the Mariana sub-arc mantle be substantially different from those of the mantle source of ocean floor basalts on either side of the arc, or that the enrichment in radiogenic Pb and Sr relative to the values observed in Pacific ocean floor basalts be related to the subduction process. We prefer the latter hypothesis in which radiogenic Sr and Pb in ocean floor sediments are added to M.O.R.B. type mantle either by direct assimilation of the sediments in partial melts or, more probably, by transfer in a fluid phase into the zone of magma production. The low ¹⁰Be concentrations observed suggest the removal of at least the top few metres of sediment during subduction.     

Particle mixing rates in sediments of the eastern equatorial Pacific: Evidence from 210Pb, 239,240Pu and 137Cs distributions at MANOP sites

Particle mixing rates (D_B) calculated from excess ²¹⁰Pb gradients in sediments of the east equatorial Pacific range from 0.04 to 0.5 cm²/y, with variation of a factor of 3–4 at a single site. Diffusion of the ²³⁶Ra daughter ²²²Rn may affect ²¹⁰Pb distributions under conditions of slow mixing and low ²¹⁰Pb flux to the seafloor, as shown by a siliceous ooze-clay core which contained the fallout radionuclides ^239,240Pu and ¹³⁷Cs but no excess ²¹⁰Pb (relative to ²²⁶Ra). There is no clear relationship between ²¹⁰Pbderived mixing rates and sediment type, accumulation rate or organic carbon flux to the sediments. Comparison of ²¹⁰Pb mixing rates with those calculated from ^239,240Pu and ¹³⁷Cs distributions reveals better agreement for a pulse input of the fallout radionuclides (D_B = 0.03?0.4 cm²/y) than for continuous input at a constant rate (D_B = 0.1?1.6 cm²/y), although the Pu and ¹³⁷Cs data are better fit by the latter model. The agreement may be fortuitous because ^239,240Pu and ¹³⁷Cs appear significantly deeper than ²¹⁰Pb in at least one core. Tracer separation could be caused by particle size-selective mixing by the benthic fauna or by chemical mobilization. If the fallout radionuclides are scavenged from surface waters by large, organic-rich particles such as fecal pellets, their release and migration may result from decomposition of the carrier in surface sediments. Either a relatively unreactive form of Pu (e.g. oxidized Pu) has been released by this process or a one-dimensional model is inadequate to explain its observed penetration into the sediments. Activity ratios of ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ in the sediments decrease with increasing north latitude, and the trend reflects higher fluxes of ^239,240Pu near the weapons test site at Christmas Island (2°N). The ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ ratios and fluxes to the sediment (assuming constant input) at the siliceous ooze-red clay site are consistent with published sediment trap data from a nearby site. Thus if fallout radionuclide fluxes to the sea floor were higher in the past, both ^239,240Pu and ¹³⁷Cs have been released from sinking particles.     

Oxygen consumption rates in pelagic sediments from the Central Pacific: First estimates from microelectrode profiles

Oxygen profiles in pelagic sediments from the Manganese Nodule Program calcareous and siliceous ooze sites (MANOP sites C and S) in the central Pacific Ocean were measured with microelectrodes and are used to predict oxygen consumption rates beneath the sediment-water interface. We explain possible artifacts which occur during sample recovery and argue that minimum estimates of 0.083 and 0.025 μ moles $\text{O}{}_2\text{cm}{}^2\text{day}$ (C and S, respectively) can be calculated from the data. These oxygen consumption rates are in good agreement with in situ respirometer measurements previously reported for comparable sediments in the north Pacific, but previous estimates based on modeling of pore water nitrate profiles at both sites are two to five times smaller than our minimum fluxes. The differences in oxygen fluxes calculated by the two methods are probably in part due to uncertainty in the assumptions inherent in the nitrate model. However, non-steady state fluctuations in particulate organic matter fluxes could also be a reason for the disparity.     

The isotopic composition and concentration of Ag in iron meteorites and the origin of exotic silver

The isotopic composition of Ag and the concentration of Ag and Pd have been determined in Canyon Diablo (IA), Grant (IIIB), Hoba, Santa Clara, Tlacotepec and Warburton Range (IVB), Piñon and Deep Springs (anom.). Troilite from Grant and Santa Clara have also been analyzed. All of these meteorites, with the exception of Canyon Diablo, give ${}^{107}\text{Ag}{}^{109}\text{Ag}$ in the metal phase that is greater than the terrestrial value with the enrichments of ¹⁰⁷Ag ranging from ~2% to 212%. These data show that Ag of anomalous isotopic composition is common to all IVB and anomalous meteorites. The results on Grant suggest that the anomalies may be widespread including more common meteorite groups. There is a general correlation of ${}^{107}\text{Ag}{}^{109}\text{Ag}$ with $\text{Pd}\text{Ag}$ except for the data from FeS of Santa Clara. It is concluded that the excess ¹⁰⁷Ag is the result of decay of ¹⁰⁷Pd, a nuclide that is extinct at present with an abundance of ${}^{107}\text{Pd}{}^{108}\text{Pd}$ of about 3 × 10^?5. The troilite in Grant exhibits normal ${}^{107}\text{Ag}{}^{109}\text{Ag}$ to within errors, a high Ag concentration and a low ratio of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~0.17. Grant metal has ${}^{107}\text{Ag}{}^{109}\text{Ag}$ that is ~2% greater than normal and a high ratio of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~ 10³. The data from Grant appear to represent a ¹⁰⁷Pd-¹⁰⁷Ag isochron and indicate that the cooling rate at elevated temperatures was sufficiently rapid to preserve substantial isotopic differences between metal and troilite. Troilite in Santa Clara was found to contain Ag with a very high ${}^{107}\text{Ag}{}^{109}\text{Ag}$ ratio (108% above normal), an Ag concentration only a factor of three above the metal and a high value of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~1.3 × 10⁴. The troilite has a higher ${}^{107}\text{Ag}{}^{109}\text{Ag}$ than the metal. These data are not compatible with a simple model of in situ decay and subsequent local Ag redistribution between metal and troilite during cooling. These data suggest that Ag in Santa Clara and possibly other IVB meteorites is made up of almost pure ¹⁰⁷Ag produced from ¹⁰⁷Pd decay and ¹⁰⁹Ag produced by nuclear reactions with only a small amount of “normal” Ag. This indicates an intense energetic particle bombardment history in the early solar system (~10²⁰ p/m²) which occurred after the formation of small planetary bodies. We infer that a T-Tauri activity by the early sun contributed to some late stage “nucleosynthesis” and the heating of a dust cloud. In addition, implications on the early thermal evolution of iron meteorites are presented based on ¹⁰⁷Pd decay and models of the cooling history.     

Paleoceanography of the Santa Barbara Basin during the last 8000 years

The varved sediments of the Santa Barbara Basin off southern California, offer a unique opportunity to study the changes in oceanographic conditions of this nearshore area during the last 8000 yr. Quantitative analysis of Radiolaria found in recent surface sediment samples from the eastern North Pacific allows the identification of four “assemblages” which can be related to the physical oceanography of the California Current. Two assemblages are associated with the southerly flowing California Current, one with the main stream of the current (California Current Assemblage) and the other with the offshore flow along northern California (Central Assemblage). The two other assemblages are associated with the subtropical region of the eastern North Pacific (Subtropical Assemblage) and one found mostly off the coast of Baja California (Baja Assemblage). Analysis of the Radiolaria found in the varved sediments of a core from the Santa Barbara Basin give an 8000-yr continuous record of these four assemblages. The California and Baja Assemblages show only minor fluctuations in their importance in the sediments of the Santa Barbara Basin. The California Assemblage, however, shows a steady increase during this time period. Prior to 5400 yr B.P. the Radiolaria were predominately subtropical in character, whereas after 5400 yr B.P. the Central Assemblage becomes more important. Since 5400 yr B.P. most of the changes in the radiolarian fauna consist of fluctuations in the importance of these two assemblages. Past sea-surface temperatures for the month of February were calculated using the transfer function technique of J. Imbrie and N. G. Kipp (1971, In “The Late Cenozore Glacial Ages” L. K. Turekian, Ed.), (Chap. 5, Yale Univ. Press, New Haven, Conn.). The time series of paleotemperature estimates show major changes in the average February temperature of Santa Barbara Basin waters. The range of estimated temperatures (12°C) exceeds that of the historical observations of February temperatures in the Santa Barbara Basin but does not exceed the observed range for the California Current region. The intervals from 800 to 1800 yr B.P. 3600 to 3800 yr B.P. and 5400 to the end of the record appear to have been generally warmer than today. Comparison of the Holocene record of alpine glacial advances with the radiolarian assemblage and paleotemperature time series shows that the initiations of advances was coincident with a decrease in sea-surface temperatures and an increase in the importance of the Central Assemblage in the Santa Barbara Basin. The terminations of these advances were not marked by any consistent characteristic in the Santa Barbara Basin time series.     

Analyse isotopique de l'air piégé dans la glace pour quantifier les variations de température

Isotopic measurements in polar ice core have shown a succession of rapid warming periods during the last glacial period over Greenland. However, this method underestimates the surface temperature variations. A new method based on gas thermal diffusion in the firn manages to quantify surface temperature variations through associated isotopic fractionations. We developed a method to extract air from the ice and to perform isotopic measurements to reduce analytical uncertainties to 0.006 and 0.020$\text{‰}$ for δ¹⁵N and δ⁴⁰Ar. It led to a 16±1.5 °C surface temperature variation during a rapid warming ($\text{?70}\text{000}$ yr). To cite this article: A. Landais et al., C. R. Geoscience 336 (2004).     

The marine oxygen isotope record in Pleistocene coral,Barbados, West Indies

The reef-crest coral Acropora palmata from late Pleistocene reefs on Barbados has recorded the same global variations in oxygen isotopes as planktonic and benthonic foraminifera. Although the record of oxygen isotopes in Acropora palmata is discontinuous, it offers several advantages over the isotope records from deep-sea sediments: (1) the coral grows at water depths of less than 5 m; (2) the samples are unmixed; (3) specimens may be sampled from various elevations of paleo-sea level; and (4) aragonitic corals are suitable for ${}^{230}\text{Th}{}^{234}\text{U}$ and $\text{He}\text{U}$ dating techniques. The latter advantage means that direct dating of the marine oxygen isotope record is possible. Oxygen isotope stage 5e corresponds to Barbados III, dated at 125,000 ± 6000 yr BP. Petrographic and geochemical evidence from five boreholes drilled into the south coast of Barbados indicates a major eustatic lowering (greater than 100 m below present sea level) occurred between 180,000 and 125,000 yr BP. The age and isotopic data suggest correlation of this change in sea level to Emiliani's oxygen isotope stage 6. Acropora palmata deposited at various elevations of sea level during oxygen isotope stage 6 vary by 0.11 ‰ δ¹⁸O for each 10 m of change in sea level. We further hypothesize a minimum drop of 2°C in the average temperature occurred during the regressive phase of oxygen isotope stage 6. These data indicate that temperature lowering of surface water near Barbados lagged behind a major glacial buildup during this time period. Using the δ¹⁸O vs sea level calibration herein derived, we estimate the relative height of sea stands responsible for Barbados coral reef terraces in the time range 80,000 to 220,000 yr BP.     

Molecular and isotopic analysis of anaerobic methane-oxidizing communities in marine sediments

Convergent lines of molecular, carbon-isotopic, and phylogenetic evidence have previously indicated (Hinrichs, K.-U., Hayes, J.M., Sylva, S.P., Brewer, P.G., DeLong, E.F., 1999. Methane-consuming archaebacteria in marine sediments. Nature 398, 802–805.) that archaea are involved in the anaerobic oxidation of methane in sediments from the Eel River Basin, offshore northern California. Now, further studies of those same sediments and of sediments from a methane seep in the Santa Barbara Basin have confirmed and extended those results. Mass spectrometric and chromatographic analyses of an authentic standard of sn-2-hydroxyarchaeol (hydroxylated at C-3 in the sn-2 phytanyl moiety) have confirmed our previous, tentative identification of this compound but shown that the previously examined product was the mono-TMS, rather than di-TMS, derivative. Further analyses of ¹³C-depleted lipids, appreciably more abundant in samples from the Santa Barbara Basin, have shown that the archaeal lipids are accompanied by two sets of products that are only slightly less depleted in ¹³C. These are additional glycerol ethers and fatty acids. The alkyl substituents in the ethers (mostly monoethers, with some diethers) are non-isoprenoidal. The carbon-number distributions and isotopic compositions of the alkyl substituents and of the fatty acids are similar, suggesting strongly that they are produced by the same organisms. Their structures, n-alkyl and methyl-branched n-alkyl, require a bacterial rather than archaeal source. The non-isoprenoidal glycerol ethers are novel constituents in marine sediments but have been previously reported in thermophilic, sulfate- and nitrate-reducing organisms which lie near the base of the rRNA-based phylogenetic tree. Based on previous observations that the anaerobic oxidation of methane involves a net transfer of electrons from methane to sulfate, it appears likely that the non-archaeal, ¹³C-depleted lipids are products of one or more previously unknown sulfate-reducing bacteria which grow syntrophically with the methane-utilizing archaea. Their products account for 50% of the fatty acids in the sample from the Santa Barbara Basin. At all methane-seep sites examined, the preservation of aquatic products is apparently enhanced because the methane-oxidizing consortium utilizes much of the sulfate that would otherwise be available for remineralization of materials from the water column.     

Experimental observations on carbon isotope exchange in carbonate-water systems

This study presents data from experiments investigating carbon isotope exchange between carbonate solution and solid calcite using carbon-13 as a tracer. All experiments were done with calcite saturated solutions and results show that a two-step adsorption-recrystallization reaction takes place. Isotope effects are caused by exchange by carbonate on the solid surface with carbon in the aqueous phase. Adsorption reactions are characterized by a maximum isotopic exchange capacity (IEC) on crystal surfaces of about 10¹¹ reaction sites per cm², following a second order rate law with respect to ¹³C concentration in solution ($\text{constant}\text{kex ? 10}{}^6\text{cm}{}^5\text{mole}{}^{\mathrm{?1}}\text{s}{}^{\mathrm{?1}}$ and $\text{half-life}\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 700}\text{s}$). The adsorption reaction was followed by a first order recrystallization which is characterized by a rate constant of the order of 10^?8 s^?1 and a $\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ of 10⁷ s. Negative isotopic gradient experiments and runs with calcite crystals in Mg²⁺ spiked solutions provided the preliminary basis for the characterization of the mechanisms of both proposed reactions.