Fertility tracers and monsoon forcing at an equatorial site of the Somali Basin (Northwest Indian Ocean)

Temporal changes in biological and isotopic tracers have successfully been used to monitor monsoon variability in the Arabian Sea. Convincing evidence that fertility indicators, such as the relative abundance of the planktic foraminifer Globigerina bulloides, and SiO₂ and Ba fluxes, can monitor monsoon changes, has also been published. Time series of the ¹³C content of the thermocline foraminifer Neogloboquadrina dutertrei, and of an Upwelling Radiolarian Index (URI), have been used to reconstruct upwelling changes in the Somali Basin at 5 °N for the last 160 kyr. In order to establish a reference site for comparison with other upwelling and/or fertility records from the same area, a time series of 8 climatic and fertility proxies (¹³C content of N. dutertrei and Globorotalia menardii, percentages of G. bulloides and of a thermocline foraminiferal group, minimal δ¹⁸ values of Globigerinoides sacculifer, N. dutertrei and G. menardii) are investigated in the spectral domain for the last 360 kyr, at a site located at the equator and outside the Somali upwelling centers (Core MD 85668).Chronostratigraphies for these records are developed by correlation of oxygen isotope record of G. sacculifer to the Martinson standard stacked benthic oxygen isotope record. The temporal resolution of the data, is between 2 and 5 kyr.Cross spectral comparisons with ETP (Eccentricity + Tilt + Precession-composite signal) were used to estimate coherences in conjunction with phase relationships and to quantify relationships between fertility and climatic indicators. The timing of fertility indicator cycles at the equator shows little (obliquity band) or no (other orbital bands) coincidence with monsoon proxies of the Arabian Sea. At the equator, fertility responses are dissociated, and present important leads or lags with ETP signal at the three orbital bands (with the exception of the thermocline foraminifera, in phase with maximum eccentricity). Due to significant leads with ETP in the timing of ¹³C minima and URI cycles, no relationships with the Northern Hemisphere radiation can be deduced. At the obliquity and precessional frequency bands, thermocline foraminifera cycles display significant lag with ETP and ice volume minima, which suggests that radiation is not the sole forcing mechanism. Global climatic and ice volume changes may be an important forcing mechanism for these fertility proxies. The G. bulloides record is more complicated with cycles in phase with Arabian Sea monsoon proxies at the obliquity band, and ¹⁸O minima at the precession frequency.It appears that, at the equator, the southwest monsoon winds are not the main force driving radiolarian and foraminiferal productivity.     

Using species-specific paleotemperature equations with foraminifera: a case study in the Southern California Bight

Species-specific paleotemperature equations were used to reconstruct a record of temperature from foraminiferal δ¹⁸O values over the last 25 kyr in the Southern California Bight. The equations yield similar temperatures for the δ¹⁸O values of Globigerina bulloides and Neogloboquadrina pachyderma. In contrast, applying a single paleotemperature equation to G. bulloides and N. pachyderma δ¹⁸O yields different temperatures, which has been used to suggest that these species record the surface-to-thermocline temperature gradient. In Santa Barbara Basin, an isotopically distinct morphotype of G. bulloides dominates during glacial intervals and yields temperatures that appear too cold when using a paleotemperature equation calibrated for the morphotype common today. When a more appropriate paleotemperature equation is used for glacial G. bulloides, we obtain more realistic glacial temperatures. Glacial–interglacial temperature differences (G–I ΔT) calculated in the present study indicate significant cooling (8–10°C) throughout the Southern California Bight during the last glacial maximum (LGM). The magnitude of glacial cooling varies from 8°C near the middle of the Southern California Bight (Tanner Basin and San Nicolas Basin) to 9°C in the north (Santa Barbara Basin) and 9.5–10°C in the south (Velero Basin and No Name Basin). Our temperature calculations agree well with previous estimates based on the modern analog technique. In contrast, studies using N. pachyderma coiling ratios, U^k′₃₇ indices, and transfer functions estimate considerably warmer LGM temperatures and smaller G–I ΔT.     

Isotopic composition and morphology of living Globorotalia scitula: a new proxy of sub-intermediate ocean carbonate chemistry?

Abundance, isotopic composition and morphological imprints of the planktonic foraminifera Globorotalia scitula (Brady) were closely examined for possible use as a novel reconstruction tool of chemical environments in sub-intermediate depth seawater in the past. Based on the MOCNES plankton tow observation of dwelling depths of G. scitula and the isotopic compositions together with hydrochemistry data, the empirical relations between isotopic disequilibria in carbon (Δδ¹³C=δ¹³C_{G. scitula}−δ¹³C_DIC) and oxygen (Δδ¹⁸O=δ¹⁸O_{G. scitula}−δ¹⁸O_w) isotopes in the carbonate tests and the seawater δ¹⁸O and δ¹³C of dissolved inorganic carbon (DIC), respectively, are introduced. The morphological information such as pore density and porosity is also examined for significant relations to carbonate chemistry. Shell porosity is strongly correlated saturation state of calcite. The dissolution of living G. scitula tests may promote the observed isotopic differences as well as the increases in porosity. Δδ¹⁸O of G. scitula is found effectively to be linear function of both water temperature and calcite saturation state (Ω), and thereby temperature equation for G. scitula is provided, while Δδ¹³C of G. scitula is a linear function of only calcite saturation state.The equation was validated by using Globorotalia scitula collected by a sediment trap in intermediate water depths. Satisfactory agreements were found between observed and calculated Δδ¹⁸O from the empirical equations based on temperature and hydrochemistry data at sediment trap deployment site, indicating that the equation may be useful in paleo-environmental reconstruction of sub-intermediate water. The sediment trap observation further suggests that the abundance of G. scitula does not necessarily correspond to surface water productivity and to POC flux, but instead, it correlates well with the supply of fine organic matter, which appears to be a result of water convection. Thus, G. scitula may be an unambiguous and excellent paleo-environmental recorder for carbonate chemistry and for fine organic matter transport to the depths, if isotopic and morphological observations are combined.     

Foraminiferal oxygen and carbon isotopes during the last 34 kyr off northern Japan, northwestern Pacific

Oxygen and carbon isotopes of foraminifera were analyzed in core PC4, water depth 1366 m, off northern Japan, near the east side of the Tsugaru Strait (130 m depth) between the open northwestern Pacific Ocean and the Japan Sea. At present, the site is at the confluence of the Tsugaru Warm Current which flows eastwards out of the Sea of Japan through the Tsugaru Strait, the subarctic Oyashio Current and the subtropic Kuroshio Current. During the Last Glacial Maximum (LGM), the Oyashio Current penetrated further to the South and outflow from the Japan Sea was restricted by glacio-eustatic sea level lowering.The isotopic values of the planktic foraminifer Neogloboquadrina pachyderma (sinistral) and the benthic foraminifer Uvigerina akitaensis reflect rapid millennial-scale paleoceanographic changes between 34 and 6 ka. Hydrographic changes during deglaciation were related to events at high northern latitudes, but Holocene hydrographic changes were dominated by local effects, such as the development of the outflow of the Tsugaru Warm Current. High values of planktic δ¹⁸O during the LGM reflect the southward advance of the Oyashio Current. These values decreased by 0.3‰ from 19.4 to 18.9 ka, then increased by 0.5‰ at 18 ka, with highest values between 17.5 and 15 ka. The δ¹⁸O oscillations between 19.4 and 15 ka may reflect millennial-scale warm–cold oscillations during Heinrich event 1. Planktic microfossil data indicate that cold Oyashio waters flowed from the northwestern Pacific into the Japan Sea via the Tsugaru Strait between 17 and 16 ka, consistent with the occurrence of the highest planktic δ¹⁸O values in core PC4. Planktic δ¹⁸O values rapidly decreased by 0.9‰ at 15 ka, possibly reflecting the effects of both a rapid increase in fresh water flux and rising temperatures in the subarctic North Pacific. During the Younger Dryas, cold event planktic δ¹⁸O values increased by 0.5‰, followed by a gradual decrease by 1‰ from the early to middle Holocene, reflecting a gradual increase in eastward outflow via the Tsugaru Strait with sea level rise. Both planktic and benthic foraminiferal δ¹³C values oscillated between 34 and 10 ka, at relatively large amplitudes (about 0.5‰), then remained relatively stable during the last 10 kyr. Several negative planktic and benthic ( − 0.7‰) δ¹³C excursions were present in sediment dated between the precipitation of secondary carbonates during episodic methane release possibly associated with methane release from continental margin sediments.     

The Holocene Pulleniatina Minimum Event revisited: Geochemical and faunal evidence from the Okinawa Trough and upper reaches of the Kuroshio current

The Holocene Pulleniatina Minimum Event (PME) is characterized by a very low abundance of the planktonic foraminifer Pulleniatina obliquiloculata between  4.5 and 3 ka. The PME occurs widely in the Okinawa Trough and the South China Sea, and can be correlated throughout this area; it has been related to variability in the Kuroshio current. To further explore the nature of the PME, we studied cores obtained from the southern Okinawa Trough and the upper reaches of the Kuroshio current. Faunal census data indicate that all cores record the PME between  4.5 and  3 ka. The relative abundance of Neogloboquadrina dutertrei is negatively correlated to that of P. obliquiloculata in the southern Okinawa Trough, but not in the sites at the upper reaches. Mg/Ca and δ¹⁸O measurements on Globigerinoides ruber shells from the southern Okinawa Trough indicate that there was no change in sea surface temperature or sea surface salinity during the PME. The vertical structure of the water column as reconstructed by multispecies δ¹⁸O and δ¹³C profiles shows no consistent anomalies in the southern Okinawa Trough and western Philippine Sea during the PME. These observations suggest that: (1) the PME was not restricted to marginal seas, but widespread in the western North Pacific. (2) The high abundance of N. dutertrei during the PME in the Okinawa Trough may be a result of higher food-availability in the absence of P. obliquiloculata. (3) No distinctive, consistent anomalies in the paleoceanographic proxies are associated with the PME, implying there were no changes in hydrography and productivity. The absence of a linkage between faunal variation and paleoceanographic proxies indicates that we do not yet understand what causes changes in planktonic foraminiferal assemblages. This lack of understanding implies that we cannot always trust fauna-based paleothermometry at millennial timescales.     

Spatial and temporal variability of surface water in the Kuroshio source region, Pacific Ocean, over the past 21,000 years: evidence from planktonic foraminifera

The Kuroshio Current is the major western boundary current of the North Pacific Ocean and has had a large impact on surface water character and climate change in the northwestern Pacific region. The Kuroshio Current becomes a distinctive surface flow in the Ryukyu Arc region after diverging from the North Equatorial Current and passing through the Okinawa Trough. Therefore, the Ryukyu Arc area can be called the Kuroshio source region. We reconstructed post-21-ka time–space changes in surface water masses in the Ryukyu Arc region using 15 piston cores which were dated by planktonic δ¹⁸O stratigraphy and AMS ¹⁴C ages. Our analysis utilized spatial and temporal changes in planktonic foraminiferal assemblages which were classified into the Kuroshio, Subtropical, Coastal, and Cold water groups on the basis of modern faunal distributions in the study region. These results indicate that the Kuroshio Current and adjacent surface water masses experienced major changes during: (1) the Last Glacial Maximum (LGM), and (2) the so-called Pulleniatina minimum event (PME) from 4,500 to 3,000 yr BP. The Kuroshio LGM event corresponds to severe global cooling and is marked by decreases in planktonic δ¹⁸O values and estimated sea-surface temperature (SST) with the dominance of the Cold water group of planktonic foraminifera. Cooling within the Kuroshio source region was enhanced during the LGM event because the Kuroshio Current was forced eastward due to the formation of a land bridge between Taiwan and the southern Ryukyu Arc which prohibited its flow into the Okinawa Trough. Except for the severe reduction and disappearance of the Pulleniatina group, no clear cooling signal was identified during the PME based on δ¹⁸O values, estimated SST values and variations in the composition of planktonic foraminiferal faunas. The PME assemblages are marked by high abundances of Neogloboquadrina dutertrei, a distinctive Kuroshio type species, along with other species assigned to the Coastal and Central water groups. Subtle ecological differences exist between Pulleniatina obliquiloculata and N. dutertrei; i.e. P. obliquiloculata exhibits lower rates of reproduction under conditions of lower primary productivity in the central Equatorial Pacific Ocean. El Niño-like conditions in the Equatorial Pacific Ocean result in lower rates of surface transport in the Kuroshio Current. In turn, this response triggers lower rates of primary productivity in central equatorial surface waters as well as in the upstream Kuroshio source region, ultimately resulting in a lower abundance of P. obliquiloculata. Thus, we interpret the PME as a possible proxy signal of El Niño-like conditions and enhancement of the El Niño Southern Oscillation climate system after the PME in the tropical and sub-tropical Pacific Ocean.     

Linear analysis of carbon-13 chemical shift differences and its application to the detection and correction of errors in referencing and spin system identifications

Statistical analysis reveals that the set of differences between the secondary shifts of the α- and β-carbons for residues i of a protein (Δδ¹³C^α_i- Δδ¹³C^β_i) provides the means to detect and correct referencing errors for ¹H and ¹³C nuclei within a given dataset. In a correctly referenced protein dataset, linear regression plots of Δδ¹³C^α_i,Δδ¹³C^β_i, or Δδ¹H^α_i vs. (Δδ¹³C^α_i- Δδ¹³C^β_i) pass through the origin from two directions, the helix-to-coil and strand-to-coil directions. Thus, linear analysis of chemical shifts (LACS) can be used to detect referencing errors and to recalibrate the ¹H and ¹³C chemical shift scales if needed. The analysis requires only that the signals be identified with distinct residue types (intra-residue spin systems). LACS allows errors in calibration to be detected and corrected in advance of sequence-specific assignments and secondary structure determinations. Signals that do not fit the linear model (outliers) deserve scrutiny since they could represent errors in identifying signals with a particular residue, or interesting features such as a cis-peptide bond. LACS provides the basis for the automated detection of such features and for testing reassignment hypotheses. Early detection and correction of errors in referencing and spin system identifications can improve the speed and accuracy of chemical shift assignments and secondary structure determinations. We have used LACS to create a database of offset-corrected chemical shifts corresponding to nearly 1800 BMRB entries: 300 with and 1500 without corresponding three-dimensional (3D) structures. This database can serve as a resource for future analysis of the effects of amino acid sequence and protein secondary and tertiary structure on NMR chemical shifts.Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s10858-005-1717-0     

Size-related isotopic trends in some Maastrichtian planktic foraminifera: methodological comparisons, intraspecific variability, and evidence for photosymbiosis

The serial test dissection and sieve fraction methods for determining the pattern of size-related change in oxygen and carbon isotopic ratios are compared using four Late Cretaceous planktic foraminifer species (Racemiguembelina fructicosa, Planoglobulina acervulinoides, Planoglobulina multicamerata, and Pseudoguembelina palpebra) from a subtropical site in the North Atlantic (DSDP Hole 390A). Despite the extra labor required, we identify several clear advantages of the dissection method, including: (1) it provides a means of obtaining size-dependent changes in isotopic signatures that are unequivocally ontogenetic, whereas isotopic variation observed from sieve-separated size fractions could be ontogenetic or ecotypic; (2) the taxonomic identity of smaller sized specimens using the dissection method is unequivocal, whereas species identification is increasingly ambiguous in smaller size fractions using the sieve method; (3) it reveals a greater total range and a greater complexity in the pattern of ontogenetic change in stable isotopic values, whereas the sieve method averages the isotopic signal across the entire ontogenetic range preserved within the whole tests that are used. Our results from serial dissections demonstrate that among the species analyzed, R. fructicosa and P. acervulinoides yield relatively negative adult δ¹⁸O values, a large size-related change in δ¹³C values (1.32 and 2.05‰, respectively), and virtually no correlation between size-related δ¹³C and δ¹⁸O values. On this basis we suggest that these were photosymbiotic species that inhabited relatively shallow surface waters. Evidence for photosymbiosis is not as compelling for P. palpebra, as this species yields a 1.06‰ shift in δ¹³C and relatively negative δ¹⁸O values in adult chambers, but much stronger correlation between size-related δ¹³C and δ¹⁸O values (r²=0.40) than in R. fructicosa and P. acervulinoides. Planoglobulina multicamerata yields the most positive adult δ¹⁸O values of the species studied, a strong covariance between size-related δ¹³C and δ¹⁸O values (r²=0.77), and a 0.97‰ shift in δ¹³C composition during ontogeny. We conclude that this species lacked photosymbionts and migrated to a deeper surface water paleohabitat as it increased in size. Single specimen analyses of tightly constrained size fractions reveal a high degree of intraspecific variation. δ¹³C and δ¹⁸O values vary by up to 0.70 and 0.28‰ in R. fructicosa, 1.41 and 0.80‰ in P. acervulinoides, 0.66 and 0.82‰ in P. palpebra, and 0.18 and 0.33‰ in P. multicamerata, respectively. Such a range of isotopic variation has been observed in modern day planktic foraminifer assemblages, and likely results from growth of individuals during different phases of the seasonal cycle and/or the kinetic effect of intraspecific variation in shell calcification rates. As suggested by other investigators, large sample sizes should be analyzed to provide the most reliable correlation of stable isotopic stratigraphic records.     

Kinetics and mechanism of CO substitution of [η-CpFe(CO)3]PF6 with PPh3 in the presence of substituted pyridine N-oxide

The kinetics of substitution reactions of [η-CpFe(CO)₃]PF₆ with PPh₃ in the presence of R-PyOs have been studied. For all the R-PyOs (R = 4-OMe, 4-Me, 3,4-(CH)₄, 4-Ph, 3-Me, 2,3-(CH)₄, 2,6-Me₂, 2-Me), the reactions yeild the same product [η⁵-CpFe(CO)₂PPh₃]PF₆, according to a second-order rate law that is first order in concentrations of [η⁵-CpFe(CO)₃]PF₆ and of R-PyO but zero order in PPh₃ concentration. These results, along with the dependence of the reaction rate on the nature of R-PyO, are consistent with an associative mechanism. Activation parameters further support the bimmolecular nature of the reactions: ΔH^≠ = 13.4 ± 0.4 kcal mol⁻¹, ΔS^≠ = −19.1 ± 1.3 cal k⁻¹ mol⁻¹ for 4-PhPyO; ΔH^≠ = 12.3 ± 0.3 kcal mol⁻¹, ΔS^≠ = 24.7 ±1.0 cal K⁻¹ mol⁻¹ for 2-MePyO. For the various substituted pyridine N-oxides studied in this paper, the rates of reaction increase with the increasing electron-donating abilities of the substituents on the pyridine ring or N-oxide basicities, but decrease with increasing ¹⁷O chemical shifts of the N-oxides. Electronic and steric factors contributing to the reactivity of pyridine N-oxides have been quantitatively assessed.     

Specific growth rate as a determinant of the carbon isotope composition of the temperate seagrass Zostera marina

The seasonal variability of specific growth rate and the carbon stable isotope ratio (δ¹³C) of leaf blades (δ¹³C_leaf) of a temperate seagrass, Zostera marina (within 10 days old) were measured simultaneously, together with the δ¹³C of dissolved inorganic carbon (δ¹³C_DIC) at three sites in the semi-closed Akkeshi estuary system, northeastern Japan, in June, September, and November 2004. The δ¹³C_leaf ranged from −16.2 to −6.3‰ and decreased from summer to winter. The simultaneous measurement of the δ¹³C_leaf, growth rate, and morphological parameters (mean leaf length and width, mean number of leaves per shoot, and sheath length) of the seagrass and δ¹³C_DIC in the surrounding water allowed us to compare directly the δ¹³C_leaf and specific growth rate of seagrass. The difference in the δ¹³C of seagrass leaves relative to the source DIC (Δδ¹³C_{leaf − DIC}) was the least negative (−11 to −7‰) in June at all three sites and became more negative (−17 to −8‰) as the specific growth rate decreased. This positive correlation between Δδ¹³C_{leaf − DIC} and specific growth rate can be used to diagnose the growth of seagrasses. Δδ¹³C_{leaf − DIC} changed by −1.7 ± 0.2‰ when the leaf specific growth rate decreased by 1% d⁻¹.     

Establishment of the western Pacific warm pool during the Pliocene: Evidence from planktic foraminifera, oxygen isotopes, and Mg/Ca ratios

This study presents new evidence of when and how the Western Pacific Warm Pool (WPWP) was established in its present form. We analyzed planktic foraminifera, oxygen isotopes, and Mg/Ca ratios in upper Miocene through Pleistocene sediments collected at Deep Sea Drilling Program (DSDP) Site 292. These data were then compared with those reported from Ocean Drilling Program (ODP) Site 806. Both drilling sites are located in the western Pacific Ocean. DSDP Site 292 is located in the northern margin of the modern WPWP and ODP Site 806 near the center of the WPWP. Three stages of development in surface-water conditions are identified in the region using planktic foraminferal data. During the initial stage, from 8.5 to 4.4 Ma, Site 806 was overlain by warm surface water but Site 292 was not, as indicated by the differences in faunal compositions and sea-surface temperature (SST) between the two sites. In addition, the vertical thermal gradient at Site 292 was weak during this period, as indicated by the small differences in the δ¹⁸O values between Globigerinoides sacculifer and Pulleniatina spp. During stage two, from 4.4 to 3.6 Ma, the SST at Site 292 rapidly increased to 27 °C, but the vertical thermal gradient had not yet be strengthened, as shown by Mg/Ca ratios and the presence of both mixed-layer dwellers and thermocline dwellers. Finally, a warm mixed layer with a high SST ca. 28 °C and a strong vertical thermal gradient were established at Site 292 by 3.6 Ma. This event is marked by the dominance of mixed-layer dwellers, a high and stable SST, and a larger differences in the δ¹⁸O values between G. sacculifer and Pulleniatina spp. Thus, evidence of surface-water evolution in the western Pacific suggests that Site 292 came under the influence of the WPWP at 3.6 Ma. The northward expansion of the WPWP from 4.4 to 3.6 Ma and the establishment of the modern WPWP by 3.6 Ma appear to be closely related to the closure of the Indonesian and Central American seaways.     

Centennial-scale climate variability in the Timor Sea during Marine Isotope Stage 3

We present a high-resolution ( 60–110 yr) multi-proxy record spanning Marine Isotope Stage 3 from IMAGES Core MD01-2378 (13°04.95′ S and 121°47.27′ E, 1783 m water depth), located in the Timor Sea, off NW Australia. Today, this area is influenced by the Intertropical Convergence Zone, which drives monsoonal winds during austral summer and by the main outflow of the Indonesian Throughflow, which represents a key component of the global thermohaline circulation system. Thus, this core is ideally situated to monitor the linkages between tropical and high latitude climate variability. Benthic δ¹⁸O data (Planulina wuellerstorfi) clearly reflect Antarctic warm events (A1–A4) as recorded by the EPICA Byrd and Dronning Maud Land ice cores. This southern high latitude signal is transferred by deep and intermediate water masses flowing northward from the Southern Ocean into the Indian Ocean. Planktonic δ¹⁸O shows closer affinity to northern high latitudes planktonic and ice core records, although only the longer-lasting Dansgaard–Oeschger warm events, 8, 12, 14, and 16–17 are clearly expressed in our record. This northern high latitude signal in the surface water is probably transmitted through atmospheric teleconnections and coupling of the Asian–Australian monsoon systems. Benthic foraminiferal census counts suggest a coupling of Antarctic cooling with carbon flux patterns in the Timor Sea. We relate increasing abundances of carbon-flux sensitive species at 38–45 ka to the northeastward migration of the West Australian Current frontal area. This water mass reorganization is also supported by concurrent decreases in Mg/Ca and planktonic δ¹⁸O values (Globigerinoides ruber white).     

Reconstruction of Indian monsoon variability over the past 230,000 years: Planktic foraminiferal evidence from the NW Arabian Sea open-ocean upwelling area

We determined the faunal composition and total number of tests (#/g) of planktic foraminifera (> 125 μm) in core KH00-05 GOA 6 near Oman in order to decipher monsoon-induced variability of oceanographic productivity in the open-ocean upwelling area in the northwest Arabian Sea. The core contains a continuous record of sedimentation over the last 230 kyr, with the age model based on oxygen isotope and accelerator mass spectrometry ¹⁴C dates. We focused on species (Globigerina bulloides and Globigerinita glutinata) typical for SW monsoonal upwelling and species typical for NE monsoon conditions (Neogloboquadrina incompta, Neogloboquadrina dutertrei, Globigerinoides ruber, and Globigerinoides sacculifer). The changes in relative abundance of these monsoonal indicators suggest that the open-ocean upwelling area was dominated by the SW monsoon during interglacial periods, but by the NE monsoon during glacial periods.Increases in total test abundance during glacial periods confirmed that the NE monsoon rather than SW monsoon contributes largely to planktic foraminiferal productivity in this area. We argue that three types of circumstances resulted in high productivity, with nine high productivity events occurring at a 23-kyr frequency. The first type caused high productivity events at 102 and 199 ka (interglacial periods), characterized by the dominance of upwelling species, indicating high productivity during strong SW monsoons, correlated with high July insolation at 45° N. An exceptional high productivity event occurred at 37 ka during interglacial marine isotope stage (MIS) 3, with contributions from both SW and NE monsoons. The second type of high productivity event occurred at 61, 147, and 175 ka, during glacial periods, characterized by dominance of NE monsoon species, and correlated with low January insolation at 45° N. In addition, a high productivity event at 85 ka (interglacial period) also was induced by enhanced NE monsoons. The last two high productivity events occurred during transitional periods from glacial to interglacial (MIS 6/5.5 and 2/1), were characterized by the replacement of NE monsoon species with upwelling species, and corresponded to abrupt climate warming, suggesting that they are related to both accelerated SW monsoon systems and reduced NE monsoon systems.     

Experimental determination of stable isotope variability in Globigerina bulloides: implications for paleoceanographic reconstructions

We have quantified the environmental and physiological parameters responsible for stable isotopic disequilibrium in the non-symbiotic planktic foraminifera, Globigerina bulloides, via controlled experiments with living specimens. Individual test chambers secreted in the laboratory were amputated, pooled with other chambers from defined positions in the shell whorl and analyzed for their carbon and oxygen isotopic composition. When temperature, δ¹⁸O_water and δ¹³C of ΣCO₂ are kept constant, the chamber δ¹³C and δ¹⁸O values increase 2.6 and 0.8%. respectively between the smallest chambers (chs. 1–9, shell size ≈180 μm) and final chamber (ch. 14, shell size ≈500 μm). Feeding experiments with prey of different δ¹³C values show that 8–15% of the chamber δ¹³C signal is due to the incorporation of metabolic CO₂. The observed ontogenetic trend is responsible for the stable isotope size-dependency in this species and may be due to a fractionation mechanism involving the incorporation of metabolic CO₂ during calcification. Temperature experiments show that shell δ¹⁸O varies as predicted by paleotemperature equations, but is offset from equilibrium. We present correction factors that should be applied to δ¹³C and δ¹⁸O data from well constrained size ranges to yield either oxygen isotope equilibrium or ambient δ¹³C of seawater ΣCO₂. Our results suggest that for paleoceanographic applications, shells in the 270–320 μm size range are optimal for paleoenvironmental reconstructions     

Comparison of stable-carbon isotope composition in the growth rings of Isorberlinia doka, Daniella oliveri, and Tamarindus indica and West African climate

Inter-ring variations in stable-carbon isotope composition of cellulose in Daniella oliveri, Isoberlinia doka, and Tamarindus indica stumps were analyzed for nine trees in the Soudan-Sahel zone of West Africa. This pioneer isotopic study is a contribution to on-going efforts to evaluate the feasibility of extracting proxy climatic records from tree-rings in this area. Our aim is to investigate trends in individual floating δ¹³C time series to assess if patterns in variability within and between rings are consistent with those in other climatically sensitive tree-ring δ¹³C series. Samples were collected primarily from tree stumps but kill dates were unknown. Tree age was estimated from stump condition and shoot regrowth. This approach, combined with low sample replication, hindered the establishment of absolute dates. Nevertheless, δ¹³C and discrimination (Δ¹³C), absolute values and variability in the time series are similar to those often seen in tree-rings. Average δ¹³C values for individual series range from −25.90‰ to −23.72‰ and average Δ¹³C values from 16.56‰ to 18.99‰. It is well known that seasonal rainfall is inversely related to the δ¹³C in growth-season-dry environments and positively covaries with Δ. We investigate the possibility of using this relationship to temporally anchor the time series and to identify missing and false rings in wood segments with indistinct growth. The variability in these time series is consistent with expected patterns and shows promise for facilitating the development of stable carbon isotope tree-ring chronologies for West Africa.     

Planktonic foraminifera from the eastern Indian Ocean: distribution and ecology in relation to the Western Pacific Warm Pool (WPWP)

Faunal assemblages, principal component (PCA), canonical correspondence (CCA), and factor analysis are applied to planktonic foraminifera from 57 core-top samples from the eastern Indian Ocean. The foraminiferal lysocline occurs at 2400 m north of 15°S where carbonate dissolution is induced by the Java upwelling system, and occurs deeper south of 15°S where carbonate dissolution is characteristic of the oligotrophic regions in the Indian Ocean. Dissolution effects, the February standing stock at the time of collection of the plankton-tow material, and different production rates explain the different foraminiferal assemblages found between plankton-tow and core-top samples. Core-top samples are differentiated by PCA into four groups — Upwelling, Western Pacific Warm Pool (WPWP), Transitional, and Southern — that are related to environmental variables (temperature, salinity and nutrients); all environmental variables follow a strong latitudinal component as indicated by the CCA analysis. Similarly, three assemblages are recognized by factor analysis: Factor 1 (dominated by Globigerinoides sacculifer, G. ruber, Globigerinita glutinata and Globorotalia cultrata), factor 2 (dominated by Globigerina bulloides and Globorotalia inflata) and factor 3 (dominated by Neogloboquadrina dutertrei) explain more than 92% of the variance, and are related to sea-surface temperature, thermocline depth and nutrient levels. The seasonal influence of the Java upwelling system supplies nutrients, phyto- and zooplankton to the oligotrophic eastern Indian Ocean (factor 1). South of 24°S, a deep chlorophyll maximum, a deep euphotic zone, a deep thermocline, SSTs below 22°C, and brief upwelling pulses seem to explain factors 2 and 3. The ratio of G. sacculifer and N. dutertrei, two mutually excluding species, appears to indicate the southern boundary of the WPWP. This ratio is applied to core Fr10/95-11 to demonstrate past shifts of the southern boundary of the WPWP.     

Carbon and oxygen isotopic disequilibria of recent deep-sea benthic foraminifera

The carbon and oxygen isotopic compositions of 149 samples of benthic foraminifera from deep-sea core tops indicate that none of the nine species studied secrete calcium carbonate in isotopic equilibrium with ambient bottom water. Uvigerina, Pyrgo murrhina, and Oridorsalis tener are the closest to ¹⁸O equilibrium (with average deviations about −0.4‰), while Planulina wuellerstorfi and P. murrhina are the closest to ¹³C equilibrium (with average deviations about −1‰). P. wuellerstorfi shows the most systematic relationship between δ ¹³C and bottom water apparent oxygen utilization. The intraspecific variabilities in δ ¹⁸O and δ ¹³C suggest that estimates of bottom water paleotemperatures can be made to a precision of ± 0.7°C, while estimates of past apparent oxygen utilization (AOU) can be made to ± 35 μmol/kg. Based on intraspecific comparisons of the Recent samples with fossils, no temporal changes in the degree of either ¹⁸O or ¹³C disequilibrium have been detected for Planulina wuellerstorfi, Uvigerina, Oridorsalis tener and Globocassidulina subglobosa.     

Isotopic fractionation factors of intermolecular hydrogen bonds in water

Association constants for N---H⁺…⁻O hydrogen bond formation between substituted ammonium dications and phenolate ion were measured in water and deuterium oxide at 25°C and 2.0 ionic strength. In combination with isotopic fractionation factors for phenol and the conjugate diacid of 1,2-ethanediamine determined by ¹³C NMR spectroscopy, these yield isotopic fractionation factors for amine dication-phenolate ion hydrogen bonds in water: φ_AB = 0.69 for 1,2-propanediamine dication with a pK difference between donor and acceptor, ΔpK_a = −0.45, φ_AB = 0.88 for 1,2-ethanediamine dication (ΔpK_a = −2.1), and φ_AB = 1.1 for piperizine dication (ΔpK_a = −3.5). The hydrogen bond association constants follow Brønsted correlations α = 0.19 in water and α = 0.27 in deuterium oxide. The results are consistent with a double-minimum potential with a significant barrier for motion across the hydrogen bond.     

Mangrove ecosystem changes during the Holocene at Spanish Lookout Cay, Belize

Mangroves are halophytic plants living at the land–sea interface and are therefore natural trackers of sea-level. Multiple proxies of a continuous (8 m) mangrove peat core (BT-79) from Spanish Lookout Cay, Belize illustrate mangrove ecosystem changes during the Holocene. Radiocarbon measurements show this site was colonized by mangroves ~ 8000 cal. yrs BP, with a significant decrease in the peat accumulation rate from ~ 6000 to 1000 cal. yrs BP. Stratigraphic characteristics of this peat core such as bulk density, magnetic susceptibility, and loss on ignition show relative uniformity, inferring an uninterrupted mangrove ecosystem during a majority of the Holocene. This is supported by pollen data from BT-79 that show that the site has been consistently dominated by Rhizophora mangle (red mangrove), with Avicennia germinans (black mangrove) and Laguncularia racemosa (white mangrove) present as well. Subfossil R. mangle leaves are used for stable nitrogen, carbon, and oxygen isotope (δ¹⁵N, δ¹³C, and δ¹⁸O) analyses. δ¹⁵N and δ¹³C values provide a proxy of this plant's past physiology and stand structure showing that dwarf (δ¹⁵N < − 3‰) and tall (δ¹³C < − 27‰) R. mangle stands were previously present at the site, which are a result of nutrient limitations that we equate with seawater inundation. δ¹⁸O values show differences in source water of R. mangle, with higher values attributed to the source water being composed of a greater proportion of seawater relative to precipitation. A decrease in inundation at the site is shown by lower δ¹⁸O values (< 19‰) from ~ 7000 to ~ 1000 cal. yrs BP that covary with the decreased sedimentation rate. Existing Caribbean sea-level data do not show evidence of a decrease in the rate of relative sea-level rise or fluctuations that we take to be the major causes of environmental changes at site BT-79.     

Sterol composition of Linneus torquatus (Nemertini) Anopla

The sterol fraction from the marine worm Linneus torquatus Coe (phylum Nemertini, class Anopla, family Lineidae) has been isolated, separated by HPLC and preparative TLC on AgNO₃-impregnated silica gel, and sterols identified using GC, GC-MS and NMR spectroscopy. It was shown that the fraction contains at least 12 sterols belonging mainly to Δ^5,22, Δ^5,24(28) and Δ⁵ series. The major sterol components were 24-methylcholesta-5,24(28)-dien-3β-ol, cholesta-5,22E-dien-3β-ol, 24-nor-cholesta-5,22-dien-3β-ol and cholesterol.