Oxygen and hydrogen isotope ratios of pore waters from ODP sites in the Mediterranean Sea

Pore fluids from two ODP sites at Eastern Mediterranean mud volcanoes have been analyzed for their Cl concentration and their delta18O and deltaD isotopic composition. The Cl data span a wide range of concentrations, from extremely depleted with respect to seawater (as low as 60 mM) at the crest of Milano dome (site 970) to strongly enriched (up to 5.4 M) at Napoli dome (site 971). Chloride enrichment is known to be due to dissolving Messinian evaporites, whereas the source of the low-Cl fluid is deduced from stable isotope data presented here. The isotopic composition of the endmember fluid is found to be +10? for delta18O and -32? for deltaD for low- as well as for high-Cl waters. From this signature it can be concluded that neither gas hydrates nor meteoric water play a significant role in the freshening of the pore water. Several other processes altering the delta18O/deltaD composition of pore waters are discussed and considered to be of only negligible influence. The process characterizing the isotopic composition of the fluid is found to be clay mineral dehydration (mainly smectite-illite transformation), corresponding to a depth range of 3.5-7 km and an elevated temperature of about 120-165°C. A quantitative estimate shows that this reaction is capable of producing the observed extreme Cl depletion.

Impact of CO2 enrichment on organic matter dynamics during nutrient induced coastal phytoplankton blooms

A mesocosm experiment was conducted to investigate the impact of rising fCO2 on the build-up and decline of organic matter during coastal phytoplankton blooms. Five mesocosms (~38 m³ each) were deployed in the Baltic Sea during spring (2009) and enriched with CO2 to yield a gradient of 355-862 µatm. Mesocosms were nutrient fertilized initially to induce phytoplankton bloom development. Changes in particulate and dissolved organic matter concentrations, including dissolved high-molecular weight (>1 kDa) combined carbohydrates, dissolved free and combined amino acids as well as transparent exopolymer particles (TEP), were monitored over 21 days together with bacterial abundance, and hydrolytic extracellular enzyme activities. Overall, organic matter followed well-known bloom dynamics in all CO2 treatments alike. At high fCO2, higher dPOC:dPON during bloom rise, and higher TEP concentrations during bloom peak, suggested preferential accumulation of carbon-rich components. TEP concentration at bloom peak was significantly related to subsequent sedimentation of particulate organic matter. Bacterial abundance increased during the bloom and was highest at high fCO2. We conclude that increasing fCO2 supports production and exudation of carbon-rich components, enhancing particle aggregation and settling, but also providing substrate and attachment sites for bacteria. More labile organic carbon and higher bacterial abundance can increase rates of oxygen consumption and may intensify the already high risk of oxygen depletion in coastal seas in the future.

Responses of three tropical seagrass species to CO2 enrichment

Increased atmospheric carbon dioxide leads to ocean acidification and carbon dioxide (CO2) enrichment of seawater. Given the important ecological functions of seagrass meadows, understanding their responses to CO2 will be critical for the management of coastal ecosystems. This study examined the physiological responses of three tropical seagrasses to a range of seawater pCO2 levels in a laboratory. Cymodocea serrulata, Halodule uninervis and Thalassia hemprichii were exposed to four different pCO2 treatments (442-1204 µatm) for 2 weeks, approximating the range of end-of-century emission scenarios. Photosynthetic responses were quantified using optode-based oxygen flux measurements. Across all three species, net productivity and energetic surplus (PG:R) significantly increased with a rise in pCO2 (linear models, P < 0.05). Photosynthesis-irradiance curve-derived photosynthetic parameters-maximum photosynthetic rates (P max) and efficiency (alpha) also increased as pCO2 increased (linear models, P < 0.05). The response for productivity measures was similar across species, i.e. similar slopes in linear models. A decrease in compensation light requirement (Ec) with increasing pCO2 was evident in C. serrulata and H. uninervis, but not in T. hemprichii. Despite higher productivity with pCO2 enrichment, leaf growth rates in C. serrulata did not increase, while those in H. uninervis and T. hemprichii significantly increased with increasing pCO2 levels. While seagrasses can be carbon-limited and productivity can respond positively to CO2 enrichment, varying carbon allocation strategies amongst species suggest differential growth response between species. Thus, future increase in seawater CO2 concentration may lead to an overall increase in seagrass biomass and productivity, as well as community changes in seagrass meadows.

(Appendix) Oxygen isotope record and carbonate mineralogy of the top part of ODP Hole 101-633A

Hole 633A was drilled in the southern part of Exuma Sound on the toe-of-slope of the southeastern part of Great Bahama Bank during ODP Leg 101. The top 55 m, collected as a suite of six approximately 9.5-m-long hydraulic piston cores, represents a Pliocene-Pleistocene sequence of periplatform carbonate ooze, a mixture of pelagic calcite (foraminifer and coccolith tests), some pelagic aragonite (pteropod tests), and bank-derived fine aragonite and magnesian calcite. A 1.6-m.y.-long hiatus was identified at 43.75 mbsf using calcareous nannofossil biostratigraphy and magnetostratigraphy. The 43.75-m-thick periplatform sequence above the hiatus is a complete late Pliocene-Quaternary record of the past 2.15 m.y. The d18O curve, primarily based on Globigerinoides sacculifera, clearly displays high-frequency/low-amplitude cycles during the early Pleistocene and low-frequency/high-amplitude cycles during the middle and late Pleistocene. Variations in aragonite content in the fine fraction of the periplatform ooze show a cyclic pattern throughout the Pleistocene, as previously observed in piston cores of the upper Pleistocene. These variations correlate well with the d18O record: high aragonite corresponds to light interglacial d18O values, and vice versa. Comparison of the d18O record and the aragonite curve helps to identify 23 interglacial and glacial oxygen-isotope stages, corresponding to 10.5 aragonite cycles (labeled A to K) commonly established during the middle and late Pleistocene (0.9 Ma-present). Strictly based on the aragonite curve, another 11 aragonite cycles, labeled L to V, were identified for the early Pleistocene (0.9 to 1.6 Ma). Mismatches between the d18O record and the aragonite curve occur mainly at some of the glacial-to-interglacial transitions, where aragonite increases usually lag behind d18O depletion. When one visually connects the minima on the Pleistocene aragonite curve, low-frequency (0.4 to 0.5 m.y.) supercycles seem to be superimposed on the high-frequency cycles. The timing of this supercycle roughly matches the timing of the Pleistocene carbonate preservation supercycles described in the Pacific, Indian, and Atlantic oceans. Mismatches between aragonite and d18O cycles are even more obvious for the late Pliocene (1.6 to 2.15 Ma). Irregular aragonite variations are observed for the late Pliocene, although after the onset of late Pleistocene-like glaciations in the North Atlantic Ocean 2.4 m.y. ago the d18O record has shown a mode of high-frequency/low-amplitude cycles. Initiation of climatically induced aragonite cycles occurs only at the Pliocene-Pleistocene transition, 1.6 m.y. ago. After that time, aragonite cycles are fully developed throughout the Quaternary. The 11-m-thick periplatform sequence below the hiatus represents a lower Pliocene interval between 3.75 and 4.45 Ma. The bottom half (4.25-4.45 Ma) has a fairly constant, high aragonite content (averaging 60%) and high sedimentation rates (28 m/m.y.) and corresponds to the end of the prolonged early Pliocene interglacial interval (4.1-5.0 Ma), established as a worldwide high sea-level stand. The second half (3.75-4.25 Ma), in which aragonite content decreases by successive steps, paralleled by a gradual 5180 enrichment in Globigerinoides sacculifera and low sedimentation rates (10 m/m.y), corresponds to the climatic deterioration established worldwide between 4.1 and 3.8 Ma, to a decrease of carbonate preservation observed in the equatorial Pacific Ocean, and to a global sea-level decline. Dolomite, a ubiquitous secondary component in the lower Pliocene, is interpreted as being authigenic and possibly related to diagenetic transformation of primary bank-derived fine magnesian calcite. Transformation of the primary mineralogical composition of the periplatform ooze was evidently minor, as the sediments have retained a detailed record of the Pliocene-Pleistocene climatic evolution. Clear evidence of diagenetic transformations in the periplatform ooze includes (1) the disappearance of magnesian calcite in the upper 20 m of Hole 633A, (2) the occurrence of calcite overgrowths on foraminiferal tests and microclasts at intermittent chalky core levels, and (3) the ubiquitous presence of authigenic dolomite in the lower Pliocene.

Stable oxygen and carbon isotope of foraminifera from DSDP Leg 90 sites

High-resolution oxygen and carbon isotope stratigraphy is presented for Miocene to early Pliocene sequences at three DSDP sites from the Lord Howe Rise, southwest Pacific, at water depths ranging from 1,300 to 2,000 m. Site 588 is located in the warm subtropics (~26°S), whereas Sites 590 and 591 are positioned in transitional (northern temperate) water masses (~31°S). Benthic foraminiferal oxygen and carbon isotope analyses were conducted on all sites; planktonic foraminiferal isotope data were generated for Site 590 only. Sample resolution in these sequences is on the order of 50,000 yr. or better. The chronological framework employed in this study is based largely upon ages assigned to Neogene calcareous nannoplankton boundaries. The benthic oxygen isotope record exhibits several major features during the Neogene. During most of the early Miocene, delta18O values were relatively low, reaching minimum values in the late early Miocene (19.5 to 16.5 Ma), and recording the climax of Neogene warmth. This was followed by a major increase in benthic delta18O values between ~16.5 and 13.5 Ma, which is interpreted as representing major, permanent accumulation of the East Antarctic ice sheet and cooling of bottom waters. During the 3 m.y. 18O enrichment, surface waters at these middle latitudes warmed between 16 and 14.5 Ma. During the remainder of the middle and late Miocene, benthic delta18O values exhibit distinct fluctuations, but the average value remained unchanged. The isotopic data show two distinct episodes of climatic cooling close to the middle/late Miocene boundary. The earliest of these events occurred between 12.5 and 11.5 Ma in the latest middle Miocene. The second cooling event occurred from 11 to 9 Ma, and is marked by some of the highest delta18O values of the entire Miocene. This was followed by relative warmth during the middle part of the late Miocene. The latest Miocene and earliest Pliocene (6.2 to 4.5 Ma) were marked by relatively high delta18O values, indicating increased cooling and glaciation. During the middle Pliocene, at about 3.4 Ma, a 0.4 per mil increase in benthic delta18O documents a net increase in average global ice volume and cooling of bottom waters. During this interval of increased glaciation, surface waters warmed by 2-3°C in southern middle-latitude regions. During the late Pliocene, between 2.6 and 2.4 Ma, a further increase in delta18O occurred; this has been interpreted by previous workers as heralding the onset of Northern Hemisphere glaciation. Surface-water warming in the middle latitudes occurred in association with major high-latitude glacial increases in the early middle Miocene (16-14 Ma), middle Pliocene (-3.5 Ma), and late Pliocene (~2.4 Ma). These intervals were also marked by increases in the vertical temperature gradient in the open ocean. Intersite correlation is enhanced by using carbon isotope stratigraphy. The great similarity of the delta13C time-series records within and between ocean basins and with water depth clearly indicates that changes in oceanwide average delta13C of [HCO3]- in seawater dominated the records, rather than local effects. Broad changes in the Neogene delta13C record were caused largely by transfer of organic carbon between continental and oceanic reservoirs. These transfers were caused by marine transgressions and regressions on the continental margins. The dominant feature of Neogene delta13C stratigraphy is a broad late early to early middle Miocene increase of about lâ between ~19 and 14.5 Ma. This trend occurred contemporaneously with a period of maximum coastal onlap (transgression) and maximum Neogene climatic warmth. The delta13C trend terminated during the expansion of the Antarctic ice sheet and associated marine regression. The latest Miocene carbon isotope shift (of up to - 0.75 per mil) at 6.2 Ma is clearly recorded in all sites examined and was followed by relatively low values during the remainder of the Neogene. This shift was caused by a glacioeustatic sealevel lowering that exposed continental margins via regression and ultimately increased the flux of organic carbon to the deep sea. An increase in delta13C values during the early Pliocene (~5 to 4 Ma) resulted from marine transgression during a time of global warmth.

Stable oxygen isotope ratios of benthic and planktonic foraminifera from early Miocene sediments of DSDP Site 90-593 on the Challenger Plateau, Pacific Ocean (Table 1)

Oxygen isotope data are compared with relative abundances of selected planktic foraminifera through a ca. 15 m interval at DSDP Site 593 (Tasman Sea, southwest Pacific, 40°S) in which there are prominent changes in population sizes, as well as several evolutionary events. We focus on the relation between faunal and climatic histories. The base of early Miocene oxygen isotope Zone Mi1b (uppermost planktic foraminiferal Zone N.6) is identified from closesampled (c. 14 kyr) isotope records of Globigerina woodi and Cibicides kullenbergi. Chronostratigraphic interpolations, using the first occurrences of Globorotalia praescitula, G. mimea and Praeorbulina curva give an age estimate of ca. 18.4 Ma (cf. 18.1 -18.3 Ma for the base of the zone at DSDP Site 608 (type level, north Atlantic, 43°N) ). Another significant benthic delta18O enrichment event, informally designated as the base of zone "Mi1c", is identified 10 m higher in the sequence at ca. 17.8 Ma. Populations of Globoquadriau dehiscens and Globigerinoides trilobus (inferred to be near the southern margin of their distributions) either reduced considerably or withdrew, particularly in the vicinity of zone "Mi1c". A bioseries linking Globorotalia incognita with G. zealandica developed following the benthic delta18O enrichment spike at the base of Zone Mi1b; the latter species became extinct (at least regionally) just above the base of zone "Mi1c". In contrast, the apparently opportunistic Globorotlia praescitula increased dramatically in abundance at this time; there were also transformations in its architecture, leading to the evolutionary appearance of G. miozea. While planktic foraminifera abundances often do not closely covary with the detailed isotope records and tend to be more stable through time, the near coincidence of evolutionary and biogeographic events with isotopic events suggests at least indirect adaptive responses to climatic changes. Early Miocene middle-latitude planktic foraminiferal evolution, biogeography, and biostratigraphy, may be intimately connected with climatic history.

Effects of in situ CO2 enrichment on structural characteristics, photosynthesis, and growth of the Mediterranean seagrass Posidonia oceanica

Seagrass is expected to benefit from increased carbon availability under future ocean acidification. This hypothesis has been little tested by in situ manipulation. To test for ocean acidification effects on seagrass meadows under controlled CO2/pH conditions, we used a Free Ocean Carbon Dioxide Enrichment (FOCE) system which allows for the manipulation of pH as continuous offset from ambient. It was deployed in a Posidonia oceanica meadow at 11 m depth in the Northwestern Mediterranean Sea. It consisted of two benthic enclosures, an experimental and a control unit both 1.7 m**3, and an additional reference plot in the ambient environment (2 m**2) to account for structural artifacts. The meadow was monitored from April to November 2014. The pH of the experimental enclosure was lowered by 0.26 pH units for the second half of the 8-month study. The greatest magnitude of change in P. oceanica leaf biometrics, photosynthesis, and leaf growth accompanied seasonal changes recorded in the environment and values were similar between the two enclosures. Leaf thickness may change in response to lower pH but this requires further testing. Results are congruent with other short-term and natural studies that have investigated the response of P. oceanica over a wide range of pH. They suggest any benefit from ocean acidification, over the next century (at a pH of 7.7 on the total scale), on Posidonia physiology and growth may be minimal and difficult to detect without increased replication or longer experimental duration. The limited stimulation, which did not surpass any enclosure or seasonal effect, casts doubts on speculations that elevated CO2 would confer resistance to thermal stress and increase the buffering capacity of meadows.

(Table 1) Oxygen isotopic composition of interstitial waters from ODP Hole 161-976

Interstitial waters recovered from Ocean Drilling Program, Leg 161, site 976 in the western Mediterranean Sea are used in conjunction with a numerical model to constrain the delta18O of seawater in the basin since the Last Glacial Maximum, including Sapropel Event 1. To resolve the oxygen isotopic composition of the deep Mediterranean, we use a model that couples fluid diffusion with advective transport, thus producing a profile of seawater delta18O variability that is unaffected by glacial-interglacial variations in marine temperature. Comparing our reconstructed seawater delta18O to recent determinations of 1.0 per mil for the mean ocean change in glacial-interglacial delta18O due to the expansion of global ice volume, we calculate an additional 0.2 per mil increase in Mediterranean delta18O caused by local evaporative enrichment. This estimate of delta18O change, due to salinity variability, is smaller than previous studies have proposed and demonstrates that Mediterranean records of foraminiferal calcite delta18O from the last glacial period include a strong temperature component. Paleotemperatures determined in combination with a stacked record of foraminiferal calcite depict almost 9°C of regional cooling for the Last Glacial Maximum. Model results suggest a decrease of ~1.1 per mil in seawater delta18O relative to the modern value caused by increased freshwater input and reduced salinity accompanying the formation of the most recent sapropel. The results additionally indicate the existence of isotopically light water circulating down to bottom water depths, at least in the western Mediterranean, supporting the existence of an 'anti-estuarine' thermohaline circulation pattern during Sapropel Event 1.

Phenotypical responses of Fucus vesiculosus germlings to warming, acidification, nutrient enrichment and local upwelling under natural fluctuations (July - September 2014)

During summer 2014 (mid-July - mid-September 2014), early life-stage Fucus vesiculosus were exposed to combined ocean acidification and warming (OAW) in the presence and absence of enhanced nutrient levels (OAW x N experiment). Subsequently, F. vesiculosus germlings were exposed to a final upwelling disturbance during 3 days (mid-September 2014). Experiments were performed in the near-natural scenario "Kiel Outdoor Benthocosms" including natural fluctuations in the southwestern Baltic Sea, Kiel Fjord, Germany (54°27 'N, 10°11 'W). Genetically different sibling groups and different levels of genetic diversity were employed to test to which extent genetic variation would result in response variation. The data presented here show the phenotypical response (growth and survival) of the different experimental populations of F. vesiculosus under OAW, nutrient enrichment and the upwelling event. Log effect ratios demonstrate the responses to enhanced OAW and nutrient concentrations relative to the ambient conditons. Carbon, nitrogen content (% DW) and C:N ratios were measured after the exposure of ambient and high nutrient levels. Abiotic conditions the OAW x nutrient experiment and the upwelling event, are shown.

(Table 1) Oxygen and carbon isotope ratios of benthic foraminifera of DSDP Holes 82-563

Previous studies of benthic foraminiferal isotopic composition have demonstrated that a latest Eocene-earliest Oligocene benthic foraminiferal d18O increase occurred in the Pacific, Southern and Atlantic Oceans (Douglas and Savin, 1973, doi:10.2973/dsdp.proc.17.120.1973; Savin et al., 1977, doi:10.1130/0016-7606(1975)86<1499:TMP>2.0.CO;2; Shackleton and Kennett, 1975, doi:10.2973/dsdp.proc.29.117.1975; Kennett and Shackleton, 1976, doi:10.1038/260513a0; Savin, 1977, doi:10.1146/annurev.ea.05.050177.001535; Keigwin, 1980, doi:10.1038/287722a0; Boersma and Shackleton, 1979, doi:10.2973/dsdp.proc.39.139.1977; Miller and Curry, 1982, doi:10.1038/296347a0; Miller et al., 1985, doi:10.2973/dsdp.proc.80.113.1985). A Middle Miocene d18O increase has been noted in the Pacific, Southern and South Atlantic Oceans (Douglas and Savin, 1973, doi:10.2973/dsdp.proc.17.120.1973; Savin et al., 1975, doi:10.1130/0016-7606(1975)86<1499:TMP>2.0.CO;2; Shackleton and Kennett, 1975, doi:10.2973/dsdp.proc.29.117.1975; Boersma and Shackleton, 1979, doi:10.2973/dsdp.proc.39.139.1977; Woodruff et al., 1981, doi:10.1126/science.212.4495.665; Savin et al., 1981, doi:10.1016/0377-8398(81)90031-1; and tentatively identified in the North Atlantic (Blanc et al., 1980, doi:10.1038/283553a0; Blanc and Duplessy, 1982, doi:10.1016/0198-0149(82)90033-4). Due to the incomplete nature of the North Atlantic stratigraphical record, however, the Oligocene to Middle Miocene isotopic record (Moore et al., 1978, Miller and Tucholke, 1983) of this ocean is poorly understood. In the modern ocean, the North Atlantic and its marginal seas has a critical role in abyssal circulation, influencing deep- and bottom-water hydrography as far away as the North Pacific (Reid and Lynn, 1971, doi:10.1016/0011-7471(71)90094-5; Worthington, 1976; Reid, 1971, doi:10.1016/0198-0149(79)90064-5). We now report oxygen isotope measurements on Oligocene to Middle Miocene (12-36 Myr BP) benthic foraminifera in the western North Atlantic which show two periods of enriched 18O values: early Oligocene and early Middle Miocene. These enriched intervals are interpreted as resulting, in part, from the build-up of continental ice sheets. The Oligocene to Middle Miocene d13C record shows three cycles of enrichment and depletion of large enough magnitude to be useful for time-Stratigraphical correlations. Within the biostratigraphical age resolution, d18O and d13C records correlate with records from other oceans, helping to establish a useful Tertiary isotopic stratigraphy. An Atlantic-Pacific d13C contrast of 0.3-0.9 per mil during the latest Oligocene to Middle Miocene (12-26 Myr BP) indicates North Atlantic deep and bottom-water production analogous to modern North Atlantic deep water (NADW).

(Table 1) Oxygen and carbon isotopes for foraminiferal taxa at DSDP Hole 76-540

We analyzed the oxygen and carbon isotopic composition of planktonic and benthic foraminifers picked from 13 late Eocene to late Oligocene samples from DSDP Site 540 (23°49.73'N, 84°22.25'W, 2926 m water depth) from the Gulf of Mexico. An enrichment occurs in 18O of about 0.5 to 0.8 per mil in both benthic foraminifers and surface-dwelling planktonic foraminifers between the latest Eocene and early Oligocene. This early Oligocene maximum is followed by lower 18O values. A 1.2 per mil d13C decrease in both benthic and planktonic foraminiferal data occurs from the late Eocene to the late Oligocene. There is a correspondence of the 13C signal to deep-sea records; however, the amplitude of this change is greater than previously seen in deep-sea cores, possibly as a result of proximity to terrestrial sources of carbon. The covarying isotopic changes in both benthic and planktonic foraminifers suggest global causes, such as ice volume increases and increased terrestrial carbon input to the ocean. However, during the latter part of the record (early-late Oligocene), the increases in the benthic 18O without accompanying increases observed with planktonic foraminifers suggest that changes in only one part of the system occurred; one potential explanation being a decrease in bottom-water temperatures without concomitant changes in the surface waters. The 18O differences between species of planktonic foraminifers and the difference between planktonic and benthic 18O data indicate that diagenesis problems are minimal. These preliminary results are encouraging given that these cores are partially lithified.

(Table 2) Stable carbon and oxygen isotope ratios of foraminifera of DSDP Holes 29-277 and 31-292

Oxygen isotopic studies both of benthic formanifera (Emiliani, 1954, doi:10.1126/science.119.3103.853; Savin et al., 1975, doi:10.1130/0016-7606(1975)86<1499:TMP>2.0.CO;2; Shackleton and Kennett, 1975, doi:10.2973/dsdp.proc.29.117.1975; Savin, 1977, doi:10.1146/annurev.ea.05.050177.001535) and shallow-marine carbonates ( Dorman, 1966; Devereux, 1967; Buchart, 1978, doi:10.1038/275121a0) have provided a useful monitor of marine palaeotemperatures. The Deep Sea Drilling Project (DSDP) has provided cores from many ocean basins to conduct detailed stable isotopic and palaeoceanographic studies of the Cenozoic and late Mesozoic. DSDP Sites 277 and 292, separated by ~60° latitude in Palaeogene times, each record an 18O enrichment in benthic foraminifera of nearly 1 per mil beginning at the Eocene-Oligocene boundary. Planktonic foraminiferal trends are similar to benthic trends in the high latitude southwest Pacific Ocean, but tropical planktonics show only a minor (~0.3 per mil) increase which may reflect a change in seawater composition. These results suggest a sudden cooling of Pacific deep waters and high latitude surface waters forms a useful stratigraphic marker for the Eocene-Oligocene boundary. This boundary is particularly important because of its association with several worldwide palaeo-oceanographic and biogeographic changes. These include a sudden drop in the calcite compensation depth of 1-2 km (van Andel et al., 1975; van Andel, 1975, doi:10.1016/0012-821X(75)90086-2); a decrease in planktonic microfossil diversity (Lipps, 1970, 10.2307/2406711; Kennett, 1978, doi:10.1016/0377-8398(78)90017-8; Sancetta, 1979, doi:10.1016/0377-8398(79)90025-2); a change in planktonic biogeographic patterns (Kennett, 1978, doi:10.1016/0377-8398(78)90017-8; Sancetta, 1979, doi:10.1016/0377-8398(79)90025-2; Haq and Lohmann, 1976, doi:10.1016/0377-8398(76)90008-6); and increased erosion of deep-sea sediments over wide areas (Kennet et al., 1972; Moore et al., 1978).

(Table 3) Oxygen and carbon isotopic record of living (Rose Bengal Stained) benthic foraminifera of North Atlantic surface sediments

Variation of the d13C of living (Rose Bengal stained) deep-sea benthic foraminifera is documented from two deep-water sites (~2430 and ~3010 m) from a northwest Atlantic Ocean study area 275 km south of Nantucket Island. The carbon isotopic data of Hoeglundina elegans and Uvigerina peregrina from five sets of Multicorer and Soutar Box Core samples taken over a 10-month interval (March, May, July, and October 1996 and January 1997) are compared with an 11.5 month time series of organic carbon flux to assess the effect of organic carbon flux on the carbon isotopic composition of dominant taxa. Carbon isotopic data of Hoeglundina elegans at 3010 m show 0.3 per mil lower mean values following an organic carbon flux maximum resulting from a spring phytoplankton bloom. This d13C change following the spring bloom is suggested to be due to the presence of a phytodetritus layer on the seafloor and the subsequent depletion of d13C in the pore waters within the phytodetritus and overlying the sediment surface. Carbon isotopic data of H. elegans from the 2430 m site show an opposite pattern to that found at 3010 m with a d13C enrichment following the spring bloom. This different pattern may be due to spatial variation in phytodetritus deposition and resuspension or to a limited number of specimens recovered from the March 1996 cruise. The d13C of Uvigerina peregrina at 2430 m shows variation over the 10 month interval, but an analysis of variance shows that the variability is more consistent with core and subcore variability than with seasonal changes. The isotopic analyses are grouped into 100 µm size classes on the basis of length measurements of individual specimens to evaluate d13C ontogenetic changes of each species. The data show no consistent patterns between size classes in the d13C of either H. elegans or U. peregrina. These results suggest that variation in organic carbon flux does not preferentially affect particular size classes, nor do d13C ontogenetic changes exist within the >250 to >750 µm size range for these species at this locality. On the basis of the lack of ontogenetic changes a range of sizes of specimens from a sample can be used to reconstruct d13C in paleoceanographic studies. The prediction standard deviation, which is composed of cruise, core, subcore, and residual (replicate) variability, provides an estimate of the magnitude of variability in fossil d13C data; it is 0.27 per mil for H. elegans at 3010 m and 0.4 per mil for U. peregrina at the 2430 m site. Since these standard deviations are based on living specimens, they should be regarded as minimum estimates of variability for fossil data based on single specimen analyses. Most paleoceanographic reconstructions are based on the analysis of multiple specimens, and as a result, the standard error would be expected to be reduced for any particular sample. The reduced standard error resulting from the analysis of multiple specimens would result in the seasonal and spatial variability observed in this study having little impact on carbon isotopic records.

Oxygen isotope ratios amd Li concentrations in spilitized basaltic rocks of DSDP Hole 83-504B (Table 5)

Li-delta18O-SiO2 relationships have been examined for suites of spilitized basaltic rocks (DSDP 504B; Xigaze Ophiolite; Blanco Fracture Zone; Greater Caucasus; Rhenohercynian Fold Belt) and intra-plate evolved tholeiites (Northern Hessian Depression and Vogelsberg, W Germany; Mount Falla, Transantarctic Mountains). Relative to unaltered MORB and intra-plate primary olivine tholeiites, both the spilitic rocks and the evolved tholeiites are characterized by Li and 18O enrichment. For the spilitic rocks, Li and 18O enrichment is accompanied by a loss of SiO2 as a result of seawater hydrothermal alteration, whereas the evolved tholeiites have gained SiO2, Li and 18O from fractionation of mafic phases and assimilation of crustal rocks. On Li vs. SiO2 and delta18O vs. SiO2 diagrams, the two rock groups plot largely in distinct fields, suggesting the possibility of so distinguishing between such lithologies in the ancient rock record. Mafic granulite xenoliths from the Northern Hessian Depression have elevated Li and 18O abundances at low SiO2 contents. Even after correction for extraction of felsic components, their Li-delta18O-SiO2 signatures plot within the field of spilitic protoliths, suggesting that the lower crust in this region contains relics of spilitic rocks from a former oceanic crust.