d15N of lipids in marine animals of the Dutch Wadden Sea

Lipid extraction of biomass prior to stable isotope analysis is known to cause variable changes in the stable nitrogen isotopic composition (d15N) of residual biomass. However, the underlying factors causing these changes are not yet clear. Here we address this issue by comparing the d15N of bulk and residual biomass of several marine animal tissues (fish, crab, cockle, oyster, and polychaete), as well as the d15N of the extracted lipids. As observed previously, lipid extraction led to a variable offset in d15N of biomass (differences ranging from -2.3 to +1.8 per mil). Importantly, the total lipid extract (TLE) was highly depleted in 15N compared to bulk biomass, and also highly variable (differences ranging from -14 to +0.7 per mil). The TLE consisted mainly of phosphatidylcholines, a group of lipids with one nitrogen atom in the headgroup. To elucidate the cause for the 15N-depletion in the TLE, the d15N of amino acids was determined, including serine because it is one of the main sources of nitrogen to N-containing lipids. Serine d15N values differed by -7 to +2 per mil from bulk biomass d15N, and correlated well with the 15N depletion in TLEs. On average, serine was less depleted (-3 per mil) than the TLE (-7 per mil), possibly due to fractionation during biosynthesis of N-containing headgroups, or that other nitrogen-containing compounds, such as urea and choline, or recycled nitrogen contribute to the nitrogen isotopic composition of the TLE. The depletion in 15N of the TLE relative to biomass increased with the trophic level of the organisms.

Sulfur-isotope analyses of gypsium samples from the Southeast Greenland margin, southern Alaska and Gulf of Alaska (Table 1)

Gypsum grains were identified in Miocene-Pleistocene sediment cores from two deep-water ODP sites, Site 918 off the SE Greenland margin and Site 887 in the Gulf of Alaska, and in Holocene sediment cores from shallow-water localities in Disenchantment Bay and Muir Inlet in southern Alaska. Although initial morphologic and textural observations suggested a complex system in which the gypsum may have had more than one origin, quantitative sulfur isotope analyses of the gypsum provide evidence of its detrital nature. d34S values in gypsum from southern Alaska range between +0.0 and +7.1 per mil. Gypsum has d34S values between -27.1 and -27.5 per mil in the Gulf of Alaska and values between -28.5 and +0.2 per mil off the SE Greenland margin. All of these isotopic signatures are too highly depleted in d34S to have precipitated from seawater, present or past. In addition there is no significant change in d34S values for gypsum crystals with differing physical characteristics (abraded vs. unabraded) from the same stratigraphic horizon, suggesting all the gypsum is detrital regardless of the degree of abrasion. The isotopic and physical evidence, in combination with the onshore geology the environmental setting, and site characteristics of the gypsum-bearing marine localities, lead us to propose that the ultimate source of the gypsum is precipitation from freeze-induced terrestrial sediment or soil brines. Furthermore the combined evidence suggests that the subsequent occurrence of gypsum in glacimarine sediments results from ice-rafting (by icebergs or sea ice) of the frozen regolith and/or, in the proximal glacimarine setting of southern Alaska, very rapid burial via turbidity currents.

Stable carbon and oxygen isotope record of live benthic foraminifera from Swedish fjords

In a previous 16-month seasonal study on living (stained) benthic foraminifera from two fjords on the Swedish west coast, it was reported that foraminifera proliferated in response to phytodetritus input; the strongest response came from the opportunistic species Stainforthia fusiformis. In this study, our objective was to find out if that phytodetritus input resulted in a change in the carbon isotopic composition of the foraminiferal tests. We also wanted to examine if variations in salinity and temperature (due to seasonality or deep-water exchanges) were reflected in the delta18O values. From S. fusiformis that were obtained from the Havstens Fjord (20 m) and the Gullmar Fjord (119 m) during the 16-month study, we developed a time series of delta18O and delta13C. After the spring blooms in the Havstens and the Gullmar Fjord, decreases of about 0.2 per mil to 0.3 per mil in the foraminiferal delta13C values were noted; in the Gullmar Fjord after the autumn blooms, decreases of the same order were also noted. Comparing the Havstens and the Gullmar Fjord, we found a 1 per mil difference in both delta13C and delta18O; we attribute this to hydrographic differences between the two fjords. Using calculated values of delta18O, together with the measured ones, we noticed that S. fusiformis in the Gullmar Fjord seems to calcify close to equilibrium with respect to the oxygen isotopes. During autumn, water temperatures were relatively high in the Havstens Fjord, and foraminiferal abundance in the fjord was also high after a phytodetritus input; but, the measured delta18O values do not reflect these higher temperatures. This apparently contradictory combination of results might be explained by a varying delta18O composition of the water during the year, which counterbalances the temperature effect.

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.

Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

Paleomagnetic and stable isotope measurements and distribution of benthic foraminifera in sediment core PS1388-3 from the Antarctic continental margin in the eastern Weddell Sea

A stable isotope record from the eastern Weddell Sea from 69°S is presented. For the first time, a 250,000-yr record from the Southern Ocean can be correlated in detail to the global isotope stratigraphy. Together with magnetostratigraphic, sedimentological and micropalaeontological data, the stratigraphic control of this record can be extended back to 910,000 yrs B.P. A time scale is constructed by linear interpolation between confirmed stratigraphic data points. The benthic d18O record (Epistominella exigua) reflects global continental ice volume changes during the Brunhes and late Matuyama chrons, whereas the planktonic isotopic record (Neogloboquadrina pachyderma) may be influenced by a meltwater lid caused by the nearby Antarctic ice shelf and icebergs. The worldwide climatic improvement during deglaciations is documented in the eastern Weddell Sea by an increase in production of siliceous plankton followed, with a time lag of approximately 10,000 yrs, by planktonic foraminifera production. Peak values in the difference between planktonic and benthic d13C records, which are 0.5 per mil higher during warm climatic periods than during times with expanded continental ice sheets, also suggest increased surface productivity during interglacials in the Southern Ocean.

Benthic and planktic foraminiferal stable isotope record and coccolith abundance spanning the last 500,000 years of ODP Hole 121-758C

The Indian Summer Monsoon (ISM) is an inter-hemispheric and highly variable ocean-atmosphere-land interaction that directly affects the densely populated Indian subcontinent. Here, we present new records of palaeoceanographic variability that span the last 500,000 years from the eastern equatorial Indian Ocean, a relatively under-sampled area of ISM influence. We have generated carbon and oxygen stable isotope records from three foraminiferal species from Ocean Drilling Program Site 758 (5°N, 90°E) to investigate the oceanographic history of this region. We interpret our resultant Dd18O (surface-thermocline) record of upper water-column stratification in the context of past ISM variability, and compare orbital phase relationships in our Site 758 data to other climate and monsoon proxies in the region. Results suggest that upper water-column stratification at Site 758, which is dominated by variance at precession and half-precession frequencies (23, 19 and 11 ka), is forced by both local (5°N) insolation and ISM winds. In the precession (23 ka) band, stratification minima at Site 758 lag northern hemisphere summer insolation maxima (precession minima) by 9 ka, which is consistent with Arabian Sea ISM phase estimates and suggests a common wind forcing in both regions. This phase implicates a strong sensitivity to both ice volume and southern hemisphere insolation forcing via latent heat export from the southern subtropical Indian Ocean. Additionally, we find evidence of possible overprinting of millennial-scale events during glacial terminations in our stratification record, which suggests an influence of remote abrupt climate events on ISM dynamics.

(Table 1) Stable carbon isotope record and calculated recycled DIC for sediment core ANDRA_HTM102

The prominent negative stable carbon isotope excursion in both carbonate and organic carbon recorded in organic-rich sediments deposited during the Toarcian oceanic anoxic event (OAE) has commonly been explained by recycling of 13C-depleted CO2 (the so-called Küspert model). More recently, the massive release of 13C-depleted methane or other forms of 13C-depleted carbon was also proposed to account for the observed negative d13C excursions in organic carbon of terrigenous as well as of marine origin. The occurrence of diagenetic products of the carotenoid isorenieratene (isorenieratane and other aryl isoprenoids) in Toarcian black shales has been regarded as supporting evidence for the Küspert hypothesis as they point to strong stratification of the epicontinental seas. A section of a drill core straddling the Toarcian of the Paris Basin (Cirfontaine-en-Ornois) contained intact isorenieratane, providing evidence that photosynthetic green sulphur bacteria were present at the time of deposition, even prior to the OAE. However, the isorenieratane abundances are very low in the section where the negative d13C excursion in organic carbon and phytane, a chemical fossil derived from chlorophyll, occurs. The abundance of the isorenieratene derivatives increases, once the d13C records have shifted to more positive values. The d13C of isorenieratane (generally circa -13.1 ± 0.5 per mil) indicates that the respired CO2 contribution at the chemocline was low and is thus not likely to be the main cause of the prominent up to 7per mil negative d13C shift recorded in Toarcian organic carbon records.

(Table 2) Stable isotopes in foraminifers at DSDP Leg 78

Analyses of stable isotopes of monospecific planktonic foraminifers (G. quadrilobatus group) and monogeneric benthic foraminifers (Cibicidoides spp.) from late Neogene Atlantic Site 502 and Pacific Site 503 were conducted in order to determine the paleoceanographic changes resulting from the late Neogene uplift of the Panama Isthmus and from climatic cooling. In general, results at each site are similar to those from previous studies for the late Miocene and late Pliocene time interval, documenting the late Miocene (6 Ma) shift in carbon isotopes and the inferred growth of permanent Northern Hemisphere continental ice sheets beginning about 3.2 Ma. Comparison of Atlantic-Pacific planktonic-benthic isotope data for four stratigraphic intervals (~6-8, ~5-6, ~3-5, and ~2-3 Ma) suggests that increasing isolation of Atlantic and Pacific low-latitude waters may be related to the emergence of the Panama Isthmus. The contrast between Atlantic and Pacific benthic foraminiferal d13C increased in two steps from 0.60 per mil to 1 per mil (the modern contrast) at about 6 Ma and 3 Ma. The first increase (0.15 per mil) may represent the end of previously limited deep-water communication between the Atlantic and Pacific at the present location of Panama. The second increase (0.25 per mil) may be due to increased production of North Atlantic Deep Water. This probably reflects the development of modern deep-sea circulation. The d18O of planktonic foraminifers begins to increase in Atlantic Site 502 at 4.2 Ma and may reflect the increasing salinity of the North Atlantic Ocean arising from diminishing surface-water exchange across Panama. This increase is clearly shown by contrasting the d18O of Atlantic and Pacific planktonic foraminifers, as well as the d18O of planktonic and benthic foraminifers at Site 502. This inferred increase in surface-water salinity begins at the time of increasing provinciality of Atlantic and Pacific planktonic foraminifers.

(Table 1) Age determination of western North Atlantic sediment cores

Foraminiferal abundance, 14C ventilation ages, and stable isotope ratios in cores from high deposition rate locations in the western subtropical North Atlantic are used to infer changes in ocean and climate during the Younger Dryas (YD) and Last Glacial Maximum (LGM). The d18O of the surface dwelling planktonic foram Globigerinoides ruber records the present-day decrease in surface temperature (SST) of ~4°C from Gulf Stream waters to the northeastern Bermuda Rise. If during the LGM the modern d18O/salinity relationship was maintained, this SST contrast was reduced to 2°C. With LGM to interglacial d18O changes of at least 2.2 per mil, SSTs in the western subtropical gyre may have been as much as 5°C colder. Above ~2.3 km, glacial d13C was higher than today, consistent with nutrient-depleted (younger) bottom waters, as identified previously. Below that, d13C decreased continually to -0.5 per mil, about equal to the lowest LGM d13C in the North Pacific Ocean. Seven pairs of benthic and planktonic foraminiferal 14C dates from cores >2.5 km deep differ by 1100 ± 340 years, with a maximum apparent ventilation age of ~1500 years at 4250 m and at ~4700 m. Apparent ventilation ages are presently unavailable for the LGM < 2.5 km because of problems with reworking on the continental slope when sea level was low. Because LGM d13C is about the same in the deep North Atlantic and the deep North Pacific, and because the oldest apparent ventilation ages in the LGM North Atlantic are the same as the North Pacific today, it is possible that the same water mass, probably of southern origin, flowed deep within each basin during the LGM. Very early in the YD, dated here at 11.25 ± 0.25 (n = 10) conventional 14C kyr BP (equal to 12.9 calendar kyr BP), apparent ventilation ages <2.3 km water depth were about the same as North Atlantic Deep Water today. Below ~2.3 km, four YD pairs average 1030 ± 400 years. The oldest apparent ventilation age for the YD is 1600 years at 4250 m. This strong contrast in ventilation, which indicates a front between water masses of very different origin, is similar to glacial profiles of nutrient-like proxies. This suggests that the LGM and YD modes of ocean circulation were the same.

Isotopic composition of carbonates from the Logachev Hydrothermal Field, MAR 14°45'N

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45' N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a d44/40Ca_HydEnd of -0.95+/-0.07 per mil relative to seawater (SW) and a 87Sr/86Sr isotope ratio of 0.7034(4). We demonstrate that d44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a d44/40Ca of -1.17+/-0.04 per mil (SW) for the host-rocks in the reaction zone and -1.45+/-0.05 per mil (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed d44/40Ca for Bulk Earth of -0.92+/-0.18 per mil (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta 61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta 62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about D44/40Ca = -0.5 per mil relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average d44/40Ca of -1.54+/-0.08 per mil (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.

Stable isotope composition of Neogene planktonic foraminifera from ODP Leg 130 sites

We produced a preliminary record for shallow-dwelling planktonic foraminifer d18O at Site 807 for the late Pleistocene, early Pliocene, and early Miocene. Site 807 d18O values between 4 and 5 Ma average 0.75 per mil more than Holocene values and show an average variation of 0.5 per mil. For the early Pliocene, peak maximum d18O at Site 807 attain values equivalent with the last glacial maximum whereas peak minimum d18O were never less than Holocene d18O. Shallow-dwelling planktonic d18O at Site 807 between 16 and 24 Ma average more than 1.0 per mil more positive than Holocene d18O and exhibit 0.5 per mil average amplitude. Assuming that the global ice budget for the early Pliocene and early Miocene was restricted to Antarctica, it is difficult to attribute the very positive Site 807 d18O for these intervals to ice on Antarctica. Site 807 d18O for these intervals more likely reflect sea-surface temperatures cooler than at present, sea-surface salinity greater than at present, increased dissolution, or some combination of these changes.

Late Paleocene to Eocene stable isotope record od ODP Site 143-865

An expanded and largely complete upper Paleocene to upper Eocene section was recovered from the pelagic cap overlying Allison Guyot, Mid-Pacific Mountains at Ocean Drilling Program (ODP) Site 865 (18°26'N, 179°33'W; paleodepth 1300-1500 m). Reconstructions show that the site was within a few degrees of the equator during the Paleogene. Because no other Paleogene sections have been recovered in the Pacific Ocean at such a low latitude, Site 865 provides a unique record of equatorial Pacific paleoceanography. Detailed stable isotopic investigations were conducted on three planktonic foraminiferal taxa (species of Acarinina, Morozovella, and Subbotina). We studied benthic foraminiferal isotopes at much lower resolution on species of Cibicidoides and Lenticulina, Nuttallides truempyi and Gavelinella beccariiformis, because of their exceptional rarity. The d18O and d13C stratigraphies from Site 865 are generally similar to those derived from other Paleocene and Eocene sections. The planktonic foraminiferal records at Site 865, however, include significantly less short-term, single-sample variability than those from higher-latitude sites, indicating that this tropical, oligotrophic location had a comparatively stable water column structure with a deep mixed layer and less seasonal variability. Low-amplitude (0.1-0.8 per mil) oscillations on timescales of 250,000 to 300,000 years correlate between the d13C records of all planktonic taxa and may represent fluctuations in the mixing intensity of surface waters. Peak sea surface temperatures of 24°-25°C occurred in the earliest Eocene, followed by a rapid cooling of 3-6°C in the late early Eocene. Temperatures remained cool and stable through the middle Eocene. In the late Eocene, surface water temperatures decreased further. Vertical temperature gradients decreased dramatically in the late Paleocene and were relatively constant through much of the Eocene but increased markedly in the late Eocene. Intermediate waters warmed through the late Paleocene, reaching a maximum temperature of 10°C in the early Eocene. Cooling in the middle and late Eocene paralleled that of surface waters, with latest Eocene temperatures below 5°C. Extinction patterns of benthic foraminifera in the latest Paleocene were similar to those observed at other Pacific sites and were coeval with a short-term, very rapid negative excursion in d13C values in planktonic and benthic taxa as at other sites. During this excursion, benthic foraminiferal d18O values decreased markedly, indicating warming of 4 to 6°C for tropical intermediate waters, while planktonic taxa show slight warming (1°C) followed by 2°C of cooling. Convergence of d18O values of planktonic and benthic foraminifera suggests that thermal gradients in the water column in this tropical location collapsed during the excursion. These data are consistent with the hypothesis that equatorial Pacific surface waters were a potential source of warm, higher salinity waters which filled portions of the deep ocean in the latest Paleocene. Oxygen isotopic data indicate that equator to high southern latitude sea surface thermal gradients decreased to as little as 4°C at the peak of the excursion, suggesting some fundamental change in global heat transport.

(Table 1) Oxygen isotoic composition of interstitial watres from ODP Sites 128-798 and 128-799

Oxygen isotope compositions of the interstitial waters have been measured for 21 samples taken from the depth intervals of 1.5 to 398.9 mbsf at Site 798 (Oki Ridge) and 16.5 to 435.6 mbsf at Site 799 (Kita-Yamato Trough) in Japan Sea. The d18O values decrease with depth from -0.49 to -3.38 per mil (SMOW) at Site 798 and from -0.71 to -4.36 per mil (SMOW) at Site 799 corresponding to an average depletion gradient of -0.8 per mil per 100 m. Material balance calculations reveal that the d18O-variations at Sites 798 and 799 were principally controlled by low-temperature alteration of basement basalt and andesite, resulting in negative shifts in pore water d18O values, and by the polymorphic transformations of biogenic opal-A to opal-CT and opal-CT to microquartz, which tend to increase d18O of interstitial waters. Carbonate diagenesis and ash alteration also caused weakly negative shifts in pore water d18O values.

(Table S1) Age determination of sediment cores of the Gulf of Alaska

Oxygen isotope data from planktonic and benthic foraminifera, on a high-resolution age model (44 14C dates spanning 17,400 years), document deglacial environmental change on the southeast Alaska margin (59°33.32'N, 144°9.21'W, 682 m water depth). Surface freshening (i.e., d18O reduction of 0.8 per mil) began at 16,650 ± 170 cal years B.P. during an interval of ice proximal sedimentation, likely due to freshwater input from melting glaciers. A sharp transition to laminated hemipelagic sediments constrains retreat of regional outlet glaciers onto land circa 14,790 ± 380 cal years B.P. Abrupt warming and/or freshening of the surface ocean (i.e., additional d18O reduction of 0.9 per mil) coincides with the Bølling Interstade of northern Europe and Greenland. Cooling and/or higher salinities returned during the Allerød interval, coincident with the Antarctic Cold Reversal, and continue until 11,740 ± 200 cal years B.P., when onset of warming coincides with the end of the Younger Dryas. An abrupt 1 per mil reduction in benthic d18O at 14,250 ± 290 cal years B.P. likely reflects a decrease in bottom water salinity driven by deep mixing of glacial meltwater, a regional megaflood event, or brine formation associated with sea ice. Two laminated opal-rich intervals record discrete episodes of high productivity during the last deglaciation. These events, precisely dated here at 14,790 ± 380 to 12,990 ± 190 cal years B.P. and 11,160 ± 130 to 10,750 ± 220 cal years B.P., likely correlate to similar features observed elsewhere on the margins of the North Pacific and are coeval with episodes of rapid sea level rise. Remobilization of iron from newly inundated continental shelves may have helped to fuel these episodes of elevated primary productivity and sedimentary anoxia.