The fate of marine lipids: Biotic vs. abiotic degradation of particulate sterols and alkenones in the Northwestern Mediterranean Sea

Sterol and alkenone compositions in suspended particle and surface sediment samples collected in the Northwestern Mediterranean Sea during the MEDFLUX program were used to evaluate the relative importance of biotic and abiotic degradation processes on marine organic matter. Alkenone concentrations decreased much more rapidly (~ 500 fold) between 5 and 800 m than Δ⁵-sterols (~ 100-fold) or POC (~ 100-fold). The diverse functional groups attached to the stable tetracyclic carbon skeleton of Δ⁵-sterols appeared to be useful for estimating the relative effects of biotic vs. abiotic (photooxidation and autoxidation) degradation. Products of abiotic degradation predominated over products of biotic degradation in suspended particles in the NW Mediterranean. For alkenones, the U₃₇^K′ index increased from 0.43 to 0.55 with increasing water depth, and a good correlation between variations of U₃₇^K′ and concentrations of specific Δ⁵-sterol autoxidation products points to selective autoxidation of alkenones in suspended particles. Stereomutated alkenones (with cis double bonds) were detected in the surface sediment, allowing us to estimate that stereomutation resulted in a + 0.05 increase in U₃₇^K′. Therefore, abiotic degradation may be another factor effect on alkenone-derived paleothermometry.     

Seasonal record for alkenones in sedimentary particles from the Gulf of Maine

C_37–39 alkenones and C₃₆ alkenoates, biomarkers of haptophyte origin, were measured in a 10-month sediment trap times series from the Wilkinson Basin in the Gulf of Maine (GOM). Highest biomarker flux to the seabed was observed in summertime, the period when surface waters are stratified and a persistent, subsurface chlorophyll maximum (SCM) exists within the upper thermocline and at the base of the euphotic zone throughout the GOM. Comparison of biomarker content and composition of sediment trap particles and underlying surface sediments indicates significant loss (>50%) of signal due to the impact of early diagenesis. Despite such loss, however, C₃₇ alkenone unsaturation patterns (U₃₇^K′) are not altered. Estimates of algal growth temperature made from analysis of U₃₇^K′ in these sedimentary materials correspond with water temperature measured at the SCM, identifying this biological oceanographic feature as a key site of alkenone export production to the GOM sediment record. Given the common occurrence of SCM in surface waters of the world ocean, particularly the expansive oligotrophic regions of the subtropical to temperate ocean, export of alkenones produced within such features is a potentially widespread biological oceanographic phenomenon which shapes the sediment record for these biomarkers.     

Time-series sediment trap record of alkenones from the western Sea of Okhotsk

C₃₇–C₃₉ alkenones were measured in time-series sediment trap samples collected from August 1998 to June 2000 at two depths in the seasonal sea ice region of the western Sea of Okhotsk, off Sakhalin, in order to investigate alkenone production and water-column processes in the region. Measurable export fluxes of alkenones are ranged from < 0.1 to 5.8 μg/m²/day and clearly showed that the alkenone production was restricted to autumn. In 1998, maximum export flux of alkenones occurred in September when surface water column was well stratified with low nutrients in the surface mixing layer. In the next year, the maximum flux is observed in October. Comparison between alkenone temperature and satellite based sea surface temperature (SST) shows that the estimated alkenone temperatures in August 1998 were found to be  10 °C lower than the temporal satellite SST, suggesting that alkenones are produced in surface to subsurface thermocline layers during the period. Annual mean flux of alkenones is lower in the lower traps than that of the upper traps, suggesting rapid degradation of alkenones in water column, but the U^K₃₇′ value is not significantly altered. This study indicates that U^K₃₇′ values preserved in the surface sediments off Sakhalin reflect the seasonal temperature signal of near surface water, rather than annual mean surface temperature.     

Seasonal variations of alkenones and U37 in the Chesapeake Bay water column

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.     

Alkenones and particulate fluxes in sediment traps from the central equatorial Pacific

We investigated a year-long (September 1992 to August 1993) time series of total mass, calcium carbonate, organic carbon, opal, and alkenone fluxes in sinking particles collected with sediment traps moored at 1770 and 4220 m in the central equatorial Pacific. The total mass fluxes varied from 14.7 to 68.7 mg/m²/day at 1770 m, with greater fluxes in October–November and February–April, and from 14.6 to 50.4 mg/m²/day with peak fluxes during October–November at 4220 m. High flux in the spring season shown at 1770 m was not indicated at 4220 m; instead, a slight increase was shown during a broad period from March to June. The calcium carbonate fluxes varied from 10.8 to 49.1 mg/m²/day with higher fluxes in October–November and March–April at 1770 m, and from 8.9 to 37.0 mg/m²/day with a higher flux in October–November at 4220 m. The organic carbon fluxes varied from 0.36 to 5.91 mg/m²/day, with higher fluxes in October–November and March–April at 1770 m, and from 0.72 to 2.58 mg/m²/day at 4220 m. The annual mean organic carbon flux was 1.84 and 1.28 mg/m²/day at 1770 and at 4220 m, respectively. These values were less than half of those reported for the EqPac sediment trap experiment. The opal fluxes varied from 0.55 to 4.4 mg/m²/day at 1770 m and from 1.23 to 2.95 mg/m²/day at 4220 m. Alkenone fluxes varied significantly from 0.05 to 0.84 μg/m²/day, with high values in November, February–March, and June at 1770 m. For the 4220 m trap, these values ranged from 0.05 to 0.25 μg/m²/day, with slightly higher fluxes in April–May and June–July, which followed periods of high alkenone fluxes observed in February–April and June–July, respectively, at 1770 m depth. These values were remarkably low compared with those reported by the previous studies at other sites. U₃₇^K′ values were constantly high >0.95 throughout the collection period. However, relatively low U₃₇^K′ values (0.92 and 0.93) were occasionally observed during February to March. Estimated alkenone temperatures from those U₃₇^K′ values were about 27–29°C and consistent with the observed temperature of the upper layer at ca.100 m depth. The seasonal change of the U₃₇^K′ values could be affected by not only water temperature but also the relative amount of ‘warm’ and ‘cold’ types of alkenone producer in the central equatorial Pacific.     

Production and transport of long-chain alkenones and alkyl alkenoates in a sea water column in the northwestern Pacific off central Japan

Sinking particles collected from year-long time-series sediment traps at 1674, 4180, 5687 and 8688 m depths, the underlying bottom sediment at 9200 m depth, and suspended particles from surface and subsurface waters in the northwestern North Pacific off Japan were analyzed for long-chain alkenones and alkyl alkenoates (A&A) which are derived mainly from Gephyrocapsacean algae, especially Emiliania huxleyi and Gephyrocapsa oceanica. Alkenone temperature records in sediment trap samples at 1674 m were almost similar to observed sea surface temperatures (SST) with a time delay of one half to one full month. However, alkenone temperatures in trap samples were about slightly lower than measured SST in late spring to early fall. The lowering might be caused by formation of the seasonal thermocline. Nevertheless, these temperature drops observed in trap samples were smaller than those actually observed in a subsurface layer off central Japan. Vertical profiles of A&A concentrations and alkenone temperatures in suspended particles collected from the subsurface waters in early fall indicated that these compounds were produced mostly in a surface mixed layer above the depth of the chlorophyll maximum even in warm seasons. These results suggested that alkenone temperatures strongly reflected SST rather than the temperatures of thermocline waters in these study areas even in such a warm season. Pronounced maxima in A&A fluxes found in sediment trap samples at 1674 m in late spring to summer showed that A&A productions were highest during the periods of spring bloom, according to a time delay between alkenone temperatures and observed SST. Seasonal patterns of alkenone records in trap samples at 4180 and 5687 m could also preserve SST signals well, suggesting that A&A in deep sea waters were mainly derived from primary products in the surface layer. A&A fluxes tended to decrease with water depth, and the ratios of A&A to particulate organic carbon (POC) rapidly decreased in underlying bottom sediment. This clearly indicates that A&A were decomposed and diluted by other refractory organic materials in either the water column or the sediment–water interface. However, A&A compositions were consistently uniform between the trap samples and the underlying bottom sediments, so that A&A could not qualitatively alter during early diagenetic processes.     

Alkenone distribution in surface sediments of the southern Yellow Sea and implications for the {\text{U}}^{{{\text{K}}\prime}}_{{37}} thermometer

The \textU^\textK￠₃₇ {\text{U}}^{{{\text{K}}\prime}}_{{37}} index has been widely applied for sea surface temperature (SST) reconstruction in open ocean environments, but has inherently limited applications at smaller, regional scales including some marginal seas where both historical and reconstructed SST records are urgently needed for understanding regional climate evolution. We determined the spatial distribution of alkenone contents in surface sediments from the southern Yellow Sea to assess the regional \textU₃₇^\textK￠ {\text{U}}_{{{37}}}^{{{\text{K'}}}} —SST relationship for paleo-SST reconstructions. C_37:2 and C_37:3 alkenones were detected at all 36 sites covering most of the southern Yellow Sea. Alkenone content ranges from 17 to 1,063 ng/g, with high values (ca. 400 to 1,000 ng/g) at deep water sites and a decreasing trend shoreward. For six samples at shallower depths near the coast and further offshore, the values were too low for statistical evaluation. This spatial pattern of alkenone contents is consistent with existing knowledge on the spatial distribution and productivity of alkenone-producing coccolithophorid species in the region. There is a significant positive relationship ( \textU₃₇^\textK￠ = 0.059\textSST - 0.350 {\text{U}}_{{{37}}}^{{{\text{K'}}}} = 0.059{\text{SST}} - 0.350 , R = 0.912, n = 30) between the \textU₃₇^\textK￠ {\text{U}}_{{{37}}}^{{{\text{K'}}}} values and satellite-derived annual mean SSTs (0 m) for the last 27 years, providing support for the application of a region-specific \textU₃₇^\textK￠ {\text{U}}_{{{37}}}^{{{\text{K'}}}} index as paleothermometer in the southern Yellow Sea. However, the slope of the southern Yellow Sea calibration (0.059) is considerably larger than that of the well-known global core-top calibration (0.033). This implies that global SST trends may not adequately encompass regional SST patterns and/or that environmental factors other than temperature may gain importance in explaining coccolithophore dynamics in marginal seas.     

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.     

Lipid biomarkers in surface sediments from the Gulf of Genoa,Ligurian sea (NW Mediterranean sea) and their potential for the reconstruction of palaeo-environments

A series of molecular organic markers were determined in surface sediments from the Gulf of Genoa (Ligurian Sea) in order to evaluate their potential for palaeo-environmental reconstructions. Allochthonous input can be characterized by the distributions of n-C₂₉ and n-C₃₁ alkanes, n-C₂₆ and n-C₂₈ alkanols and branched glycerol dialkyl glycerol tetraethers (GDGTs), whose concentrations are generally highest near the river mouths. In the open basin however, terrestrial n-alkanes and n-alkanols may have an additional, eolian source. Autochthonous input is represented by crenarchaeol and isoprenoid GDGTs. Their concentrations are highest in the open basin showing the preference of Thaumarchaeota for oligotrophic waters. Indications of a significant degradation of sterols and C₃₇ alkenones exclude these lipids as reliable productivity proxies. Using terrestrial and aquatic lipids as end-members allows estimating the percentage of terrestrial organic matter between 20% and 58% in the coastal area decreasing to 1–30% in the deep basin. The spatial distribution of sea surface temperature (SST) estimates using the alkenone-based U^K′₃₇ index is very similar to the autumnal (November) mean satellite-based SST distribution. Conversely, TEX^H₈₆-derived SST estimates are close to winter SSTs in the coastal area and summer SSTs in the open basin. This pattern reflects presumably a shift in the main production of Thaumarchaeota from the coastal area in winter to the open basin in summer. This study represents a major prerequisite for the future application of lipid biomarkers on sediment cores from the Gulf of Genoa.     

Rapid lateral particle transport in the Argentine Basin: Molecular 14C and 230Thxs evidence

Recent studies have revealed that lateral transport and focusing of particles strongly influences the depositional patterns of organic matter in marine sediments. Transport can occur in the water column prior to initial deposition or following sediment re-suspension. In both cases, fine-grained particles and organic-rich aggregates are more susceptible to lateral transport than coarse-grained particles (e.g., foraminiferal tests) because of the slower sinking velocities of the former. This may lead to spatial and, in the case of redistribution of re-suspended sediments, temporal decoupling of organic matter from coarser sediment constituents. Prior studies from the Argentine Basin have yielded evidence that suspended particles are displaced significant distances (100–1000 km) northward and downslope by strong surface and/or bottom currents. These transport processes result in anomalously cold alkenone-derived sea-surface temperature (SST) estimates (up to 6 °C colder than measured SST) and in the presence of frustules of Antarctic diatom species in surface sediments from this area. Here we examine advective transport processes through combined measurements of compound-specific radiocarbon ages of marine phytoplankton-derived biomarkers (alkenones) from core tops and excess ²³⁰Th (²³⁰Th_xs)-derived focusing factors for late Holocene sediments from the Argentine Basin. On the continental slope, we observe ²³⁰Th_xs-based focusing factors of 1.4–3.2 at sites where alkenone-based SST estimates were 4–6 °C colder than measured values. In contrast, alkenone radiocarbon data suggest coeval deposition of marine biomarkers and planktic foraminifera, as alkenones in core tops were younger than, or similar in age to, foraminifera. We therefore infer that the transport processes leading to the lateral displacement of these sediment components are rapid, and hence probably occur in the upper water column (<1500 m).     

Sinking Particle Flux in the Subtropical Oligotrophic Northwestern Pacific from a Short-term Sediment Trap Experiment

Time-series sediment traps were deployed in the subtropical oligotrophic northwestern Pacific (SONP) at three depths from August to September 2015 to better understand vertical flux of sinking particles. Sinking particles were collected at 5-day intervals over the sediment trap deployment period. The average total mass flux at water depths of 400 m, 690 m, and 1,710 m was 9.1, 4.4, and 4.1 mg m^-2day^-1, respectively. CaCO₃ materials constituted 50 to 70% of sinking particles while in comparison particulate organic carbon (POC) constituted up to 20%. A synchronous variation of total mass flux was observed at the three depths, indicating that calcite-dominated particles sank from 400 to 1,710 m within a 5-day period. POC flux at these water depths was 2.4, 0.38, and 0.31 mg m^-2day^-1, respectively. Our results indicate low transfer efficiencies of 16% from 400 to 690 m and 13% for the 400 to 1,710 m depth range. The estimated transfer efficiencies were significantly lower than those observed at the K2 station in the northwest Pacific subarctic gyre, presumably because of a prevalence of pico-cyanobacteria in the SONP. Because cyanobacteria have a semi-permeable proteinaceous shell, they are more readily remineralized by bacteria than are siliceous phytoplankton in the northwest Pacific subarctic gyre. Continued surface water warming and expansion of the SONP will likely have a profound impact on ocean acidification in the northwest Pacific, possibly affecting the transfer efficiency of sinking POC to the deep-sea.     

Particle dynamics in the deep water column of Sagami Bay, Japan. I: origins of apparent flux of sinking particles

Temporal variations of sinking particle flux, together with their organic chemical properties, were monitored in the deep basin of Sagami Bay, Japan, using sediment traps with very high time resolutions from March 1997 to August 1998. At a height of 350 m above the bottom (about 1200 m water depth), the averaged total mass flux was more than 1000 mg/m²/day, which is about 10 times higher than those obtained for open ocean regions near Sagami Bay. While large amounts of phytodetritus, derived from phytoplankton blooms in the surface water, were transported downward in spring, the following extraordinary patterns in the temporal variability of sinking particle flux were also observed: (1) A sustained large flux of sinking particles during low productive periods from summer to winter in 1997. (2) An episodic increase of sinking particle flux in June 1998. (3) A difference in the temporal variability of sinking particles between the spring bloom periods of 1997 and 1998. The content of total organic carbon (TOC) and the stable carbon isotopic ratio (δ¹³C) of TOC demonstrated that the large fluxes observed in (1) and (2) could be attributed to the resuspension of phytodetritus deposited on the sea floor during the spring bloom period, and the abrupt erosion of surface sediment on the continental slope, respectively. The concentration of suspended particles in the deep water column affect the apparent flux of sinking particles. At the same time, sinking particles exported from surface waters during the spring bloom both decrease and increase suspended particle concentration through scavenging and rebound processes, respectively. Finally, the apparent difference in sinking particle flux between 1997 and 1998, (3), could be explained by differences in the extent of the scavenging process, which depend on the flux and quality of exported particles from the surface waters.     

Use of lipids and their degradation products as biomarkers for carbon cycling in the northwestern Mediterranean Sea

Changes in phytoplankton composition and degradation of particulate organic matter (POM) in the northwestern Mediterranean Sea were studied using time-series sediment trap samples collected during the spring of 2003 at the DYFAMED station. Lipid biomarkers (pigments, fatty acids, sterols, acyclic isoprenoids, alkenones and n-alkanols) were used to identify the main contributors to the POM produced during two phytoplankton blooms, while the effects of photooxidation, autoxidation and biodegradation were differentiated using characteristic lipid degradation products. Traps collected material corresponding to pre-bloom, bloom and post-bloom periods. Pigment analyses in the integrated (0-200 m) water column samples indicated that diatoms dominated the initial stages of the bloom event, with smaller amounts of haptophytes and pelagophytes. During the second part of bloom event there was a switch to haptophyte dominance with significant contributions from diatoms and pelagophytes, and an increased contribution from cryptophytes. Fatty acid distributions in the trap samples reflected contributions from marine bacteria, phytoplankton and zooplankton. Photooxidation and autoxidation products of monounsaturated oleic, cis-vaccenic and palmitoleic acids were detected along with photooxidation products from the chlorophyll side-chain. The relatively good correlation between the variation of U₃₇^K′ index and specific phytol autoxidation product percentage allowed us to attribute the alterations of U₃₇^K′ observed during the pre-bloom period and in the deeper traps to the involvement of selective autoxidative degradation processes. A variety of sterol oxidation products formed by biohydrogenation, autoxidation and photooxidation were detected. Sterol degradation products appeared to be less suited than oxidation products of monounsaturated fatty acids for the precise monitoring of the degradation state of POM, but their stable functionalized cyclic structure constitutes a useful tool to estimate the part played by biotic and abiotic processes. In these waters, biotic degradation generally predominates, but abiotic degradation is not negligible and, as expected, the extent of biotic degradation increases with depth. To obtain a more complete picture of POM degradation, the use of a pool of lipid degradation products (i.e. from unsaturated fatty acids, the phytyl side-chain and sterols) should be employed.     

Distribution of glycerol dialkyl glycerol tetraethers, alkenones and polyunsaturated fatty acids in suspended particulate organic matter in the East China Sea

We investigated the spatial distribution of glycerol dialkyl glycerol tetraethers (GDGTs), alkenones, and polyunsaturated fatty acids in particulate organic matter collected at four sites along a depth transect from the continental shelf to the Okinawa Trough in the East China Sea during the spring bloom in 2008. The maximum alkenone concentration appeared in the top 25?m at all sites and the $ U_{37}^{{{\text{K}}'}} $ values were consistent with in situ water temperatures in the depth interval, suggesting that the alkenones were produced mainly in surface water. At the slope and shelf sites, GDGTs in the water column showed a concentration maximum at 74?C99?m depth, and the $ {\text{TEX}}_{86}^{\text{H}} $ agreed with in situ water temperatures, suggesting the in situ production of GDGTs in the depth interval. The low-salinity surface water above 20?m depth was characterized by low GDGT concentrations and low $ {\text{TEX}}_{86}^{\text{L}} $ -based temperatures, suggesting either the production of GDGTs in winter season or the lateral advection of GDGTs by an eastward current. At the slope and Okinawa Trough sites, TEX₈₆-based temperatures were nearly constant in the water column deeper than 300?m and corresponded to temperatures at the surface and near-surface waters rather than in situ temperatures. This observation is consistent with a hypothesis that Thaumarchaeota cells produced in surface waters are delivered to deeper water and also indicates that the residence time of suspended GDGTs in the deep-water column is large enough to mix the GDGTs produced in different seasons.     

Comparison of sinking particles in the upper 200 m between subarctic station K2 and subtropical station S1 based on drifting sediment trap experiments

Drifting sediment trap experiments were conducted during various seasons to elucidate the characteristics of particles sinking through the upper 200 m of the water column in the western Pacific at subarctic station K2 and subtropical station S1. The sinking particle flux increased when primary productivity was high at each station, during June–July at K2 and during February at S1. Biogenic opal (Opal) and CaCO₃ were the major components of the fluxes at K2 and S1, respectively. Contrary to the expectation of a high flux at the eutrophic station K2 and low flux at the oligotrophic station S1, the annual average organic carbon fluxes at 100 m were comparable at both stations: 62.7 mg C m^?2 day^?1 at K2 and 56.1 mg C m^?2 day^?1 at S1. The similarity of the fluxes was perhaps a reflection of the unexpectedly high primary production at S1. At K2, the organic carbon export ratio (organic carbon flux/primary productivity) was significantly and negatively correlated with primary production and tended to decrease with depth. The magnitude of the rate of attenuation of the organic carbon flux with depth was larger at S1 than at K2. This rate of attenuation tended to decrease and increase with primary production at K2 and S1, respectively. The explanation for these patterns may be that the flux of labile organic carbon at relatively shallow depths decreased with increasing primary production at K2, and zooplankton grazing pressure increased with increasing primary productivity at S1.     

High-resolution observations of aggregate flux during a sub-polar North Atlantic spring bloom

An aggregate flux event was observed by ship and by four underwater gliders during the 2008 sub-polar North Atlantic spring bloom experiment (NAB08). At the height of the diatom bloom, aggregates were observed as spikes in measurements of both particulate backscattering coefficient (b_bp) and chlorophyll a fluorescence. Optical sensors on the ship and gliders were cross-calibrated through a series of simultaneous profiles, and b_bp was converted to particulate organic carbon. The aggregates sank as a discrete pulse, with an average sinking rate of ∼75 m d⁻¹; 65% of aggregate backscattering and 90% of chlorophyll fluorescence content was lost between 100 m and 900 m. Mean aggregate organic carbon flux at 100 m in mid-May was estimated at 514 mg C m⁻² d⁻¹, consistent with independent flux estimates. The use of optical spikes observed from gliders provides unprecedented coupled vertical and temporal resolution measurements of an aggregate flux event.     

Calibration of sediment traps and particulate organic carbon export using 234Th in the Barents Sea

Profiles of particulate and dissolved ²³⁴Th (t_1/2=24.1 days) in seawater and particulate ²³⁴Th collected in drifting traps were analyzed in the Barents Sea at five stations during the ALV3 cruise (from June 28 to July 12, 1999) along a transect from 78°15′N–34°09′E to 73°49′N–31°43′E. ²³⁴Th/²³⁸U disequilibrium was observed at all locations. ²³⁴Th data measured in suspended and trapped particles were used to calibrate the catchment efficiency of the sediment traps. Model-derived ²³⁴Th fluxes were similar to ²³⁴Th fluxes measured in sediment traps based on a steady-state ²³⁴Th model. This suggests that the sediment traps were not subject to large trapping efficiency problems (collection efficiency ranges from 70% to 100% for four traps). The export flux of particulate organic carbon (POC) can be calculated from the model-derived export flux of ²³⁴Th and the POC/²³⁴Th ratio. POC/²³⁴Th ratios measured in suspended and trapped particles were very different (52.0±9.9 and 5.3±2.2 μmol dpm⁻¹, respectively). The agreement between calculated and measured POC fluxes when the POC/²³⁴Th ratio of trapped particles was used confirms that the POC/²³⁴Th ratio in trap particles is representative of sinking particles. Large discrepancies were observed between calculated and measured POC fluxes when the POC/²³⁴Th ratio of suspended particles was used. In the Barents Sea, vertical POC fluxes are higher than POC fluxes estimated in the central Arctic Ocean and the Beaufort Sea and lower than those calculated in the Northeast Water Polynya and the Chukchi Sea. We suggest that the latter fluxes may have been strongly overestimated, because they were based on high POC/²³⁴Th ratios measured on suspended particles. It seems that POC fluxes cannot be reliably derived from thorium budgets without measuring the POC/²³⁴Th ratio of sediment trap material or of large filtered particles.     

Biomarker records from core GH02-1030 off Tokachi in the northwestern Pacific over the last 23,000 years: Environmental changes during the last deglaciation

We investigated marine and terrestrial environmental changes at the northern Japan margin in the northwestern Pacific during the last 23,000 years by analyzing biomarkers (alkenones, long-chain n-alkanes, long-chain n-fatty acids, and lignin-derived materials) in Core GH02-1030. The U ₃₇^K′-derived temperature in the last glacial maximum (LGM) centered at 21 ka was ∼10°C, which was 2°C lower than the core-top temperature (∼12°C). This small temperature drop does not agree with pollen evidence of a large air temperature drop (more than 4°C) in the Tokachi area. This disagreement might be attributed to a bias of U ₃₇^K′-derived temperature within 2.5°C by a seasonal shift in alkenone production. The U ₃₇^K′-derived temperature was significantly low during the last deglaciation. Because this cooling was significant in the Kuroshio-Oyashio transition zone, the temperature drops are attributable to the southward displacement of the Kuroshio-Oyashio boundary. Abundant lignin-derived materials, long-chain n-alkanes and long-chain n-fatty acids indicate a higher contribution of terrigenous organic matter from 17 to 12 ka. This phenomenon might have resulted from an enhanced coastal erosion of terrestrial soils due to marine transgression and/or an efficient inflow of higher plant debris to river waters from 17 to 12 ka.