Particulate barium fluxes on the continental margin: a study from the Alboran Sea (Western Mediterranean)

Particulate biogenic barium (bio-Ba) fluxes obtained from three instrumented arrays moored in the Alboran Sea, the westernmost basin in the Mediterranean Sea, are presented in this study. The mooring lines were deployed over almost 1 year, from July 1997 to May 1998, and were equipped with sediment traps at 500–700 m depth, 1000–1200 m depth and 30 m above the seafloor (1000–2200 m). The results obtained support the growing body of evidence that the relationship between particulate bio-Ba and Corg throughout the water column in margin systems is clearly different from this relation in the open ocean. In the Alboran Sea, the annual averaged bio-Ba fluxes range from 0.39 to 1.07 μmol m⁻² day⁻¹, with mean concentrations of 1.31–1.69 μmol g⁻¹ and bio-Ba/Corg ratios lower than in the open ocean. The low bio-Ba values obtained also indicate that calculating bio-Ba is extremely sensitive to the detrital Ba/Al ratio of each sample. The lithogenic Ba fraction in the Alboran Sea continental margin area contributes between 24% and 85% of the total Ba. Increased bio-Ba export efficiency was observed after periods of high primary productivity and suggests that the processes limiting the bio-Ba formation in the study area relate to settling dynamics of organic matter aggregates. Furthermore, the ballasting effect of the abundant lithogenic and carbonate particles may limit decomposition of organic matter aggregates and enhance the transfer of particles rich in Corg and relatively poor in bio-Ba to the deep seafloor. Lateral input of freshly sedimented biogenic material, including particulate bio-Ba, has been observed on the lower continental slope in the western Alboran Sea. These observations emphasize that the use of the bio-Ba as a proxy of export productivity from the surface ocean must be used cautiously in highly dynamic environments such as those in the Alboran Sea.     

Time-series measurements of Th in water column and sediment trap samples from the northwestern Mediterranean Sea

Disequilibrium between ²³⁴Th and ²³⁸U in water column profiles has been used to estimate the settling flux of Th (and, by proxy, of particulate organic carbon); yet potentially major non-steady-state influences on ²³⁴Th profiles are often not able to be considered in estimations of flux. We have compared temporal series of ²³⁴Th distributions in the upper water column at both coastal and deep-water sites in the northwestern Mediterranean Sea to coeval sediment trap records at the same sites. We have used sediment trap records of ²³⁴Th fluxes to predict temporal changes in water column ²³⁴Th deficits and have compared the predicted deficits to those measured to determine whether the time-evolution of the two coincide. At the coastal site (327 m water depth), trends in the two estimates of water column ²³⁴Th deficits are in fairly close agreement over the 1-month deployment during the spring bloom in 1999. In contrast, the pattern of water column ²³⁴Th deficits is poorly predicted by sediment trap records at the deep-water site (DYFAMED, 2300 m water depth) in both 2003 and 2005. In particular, the transition from a mesotrophic to an oligotrophic system, clearly seen in trap fluxes, is not evident in water column ²³⁴Th profiles, which show high-frequency variability. Allowing trapping efficiencies to vary from 100% does not reconcile the differences between trap and water column deficit observations; we conclude that substantial lateral and vertical advective influences must be invoked to account for the differences.Advective influences are potentially greater on ²³⁴Th fluxes derived from water column deficits relative to those obtained from traps because the calculation of deficits in open-ocean settings is dominated by the magnitude of the “dissolved” ²³⁴Th fraction. For observed current velocities of 5–20 cm s⁻¹, in one radioactive mean-life of ²³⁴Th, the water column at the DYFAMED site can reflect ²³⁴Th scavenging produced tens to hundreds of kilometers away. In contrast, most of the ²³⁴Th flux collected in shallow sediment traps at the DFYFAMED site was in the fraction settling >200 m d⁻¹; in effect the sediment trap can integrate the ²³⁴Th flux over distances 40-fold less than water column ²³⁴Th distributions. In some sense, sediment trap and water column sampling for ²³⁴Th provide complementary pictures of ²³⁴Th export. However, because the two methods can be dominated by different processes and are subject to different biases, their comparison must be treated with caution.     

Particulate organic carbon–Th relationships in particles separated by settling velocity in the northwest Mediterranean Sea

In order to better understand the relationship between the natural radionuclide ²³⁴Th and particulate organic carbon (POC), marine particles were collected in the northwestern Mediterranean Sea (spring/summer, 2003 and 2005) by sediment traps that separated them according to their in situ settling velocities. Particles also were collected in time-series sediment traps. Particles settling at rates of >100 m d⁻¹ carried 50% and 60% of the POC and ²³⁴Th fluxes, respectively, in both sampling years. The POC flux decreased with depth for all particle settling velocity intervals, with the greatest decrease (factor of 2.3) in the slowly settling intervals (0.68–49 m d⁻¹) over trap depths of 524–1918 m, likely due to dissolution and decomposition of material. In contrast the flux of ²³⁴Th associated with the slowly settling particles remained constant with depth, while ²³⁴Th fluxes on the rapidly settling particles increased. Taking into account decay of ²³⁴Th on the settling particles, the patterns of ²³⁴Th flux with depth suggest that either both slow and fast settling particles scavenge additional ²³⁴Th during their descent or there is significant exchange between the particle classes. The observed changes in POC and ²³⁴Th flux produce a general decrease in POC/²³⁴Th of the settling particles with depth. There is no consistent trend in POC/²³⁴Th with settling velocity, such as might be expected from surface area and volume considerations. Good correlations are observed between ²³⁴Th and POC, lithogenic material and CaCO₃ for all settling velocity intervals. Pseudo-K_ds calculated for ²³⁴Th in the shallow traps (2005) are ranked as lithogenic material opal <calcium carbonate <organic carbon. Organic carbon contributes 33% to the bulk K_d, and for lithogenic material, opal and CaCO₃, the fraction is 22% each. Decreases in POC/²³⁴Th with depth are accompanied by increases in the ratio of ²³⁴Th to lithogenic material and opal. No change in the relationship between ²³⁴Th and CaCO₃ was evident with depth. These patterns are consistent with loss of POC through decomposition, opal through dissolution and additional scavenging of ²³⁴Th onto lithogenic material as the particles sink.     

Particulate organic matter and ballast fluxes measured using time-series and settling velocity sediment traps in the northwestern Mediterranean Sea

Prompted by recent data analyses suggesting that the flux of particulate organic carbon sinking into deep waters is determined by fluxes of mineral ballasts, we undertook a study of the relationships among organic matter (OM), calcium carbonate, opal, lithogenic material, and excess aluminum fluxes as part of the MedFlux project. We measured fluxes of particulate components during Spring and Summer of 2003, and Spring of 2005, using a swimmer-excluding sediment trap design capable of measuring fluxes both in a time-series (TS) mode and in a configuration for obtaining particle settling velocity (SV) profiles. On the basis of these studies, we suggest that distinct OM–ballast associations observed in particles sinking at a depth of 200 m imply that the mechanistic basis of the organic matter–ballast association is set in the upper water column above the Twilight Zone, and that the importance of different ballast types follows the seasonal succession of phytoplankton. As in other studies, carbonate appears to enhance the flux of organic matter over opal. Particles must be at least half organic matter before their settling velocity is affected by ballast concentration. This lack of change in ballast composition with SV in particles with <40% OM content suggests that particle SV reaches a maximum because of the increasing importance of inertial drag. Relative amounts of OM and opal decrease with depth due to decomposition and dissolution; carbonates and lithogenic material contribute about the same amount to total mass, or increase slightly, throughout the water column. The high proportion of excess Al cannot be explained by its incorporation into diatom opal or reverse weathering, so Al is most likely adsorbed to particulate oxides. On shorter time scales, dust appears to increase particle flux through its role in aggregation rather than by nutrient inputs enhancing productivity. We suggest that the role of dust as a catalyst in particle formation may be a central mechanism in flux formation in this region, particularly when zooplankton fecal pellet production is low.     

Direct barite determination using SEM/EDS-ACC system: implication for constraining barium carriers and barite preservation in marine sediments

Barite (BaSO₄) in marine sediments is considered as a proxy of surface ocean productivity and is widely used for paleo-productivity reconstructions. However, direct barite determination is not achieved by currently used methods, which rely on the measurement of total barium by inductively coupled plasma–mass spectrometry (ICP-MS) and instrumental neutron activation analysis (INAA) and correction from the allogenic Ba contribution. We report here on a technique that directly counts individual barite crystals using a scanning electron microscope (SEM) coupled to an energy dispersive spectrometer (EDS) equipped with an automated particle counting and classification (ACC) system. We show that barite–Ba concentrations can be deduced from the abundance, shape and size distributions of barite crystals with current precision and sensitivity as high as ±5 wt.% (2σ confidence limit) and 10 ppm, respectively. This technique, coupled with ICP-MS and INAA techniques for total Ba measurements, was applied to sediment samples from the tropical North Atlantic and the Central North Pacific oceans. Results show that: (1) barite and detrital aluminosilicates are the two main carriers of Ba in the investigated sediments; (2) calculated Ba/Al ratios range from 0.005 to 0.008 with an average value around 0.0066, in close agreement with previously reported values; (3) barite might not be the major source for released barium out of sediments and we suggest instead adsorbed barium as a potential source.     

Vertical export flux of metals in the Mediterranean Sea

We examined metal (Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb) and particulate organic carbon (OC) concentrations of the marine vertical export flux at the DYFAMED time-series station in the Northwestern Mediterranean Sea. We present here the first data set of natural and anthropogenic metals from sediment trap moorings deployed at 1000 m-depth between 2003 and 2007 at the DYFAMED site. A highly significant correlation was observed between most metal concentrations, whatever the nature and emission source of the metal. Cu, Zn and Cd exhibit different behaviors, presumably due to their high solubility and complexation with organic ligands. The observed difference of atmospheric and marine fluxes in terms of temporal variability and elemental concentration suggests that dense water convection and primary production and not atmospheric deposition control the marine vertical export flux. This argument is strengthened by the fact that significant Saharan dust events did not result in concomitant marine vertical export fluxes nor did they generate significant changes in metal concentrations of trapped particles.     

General patterns of circulation, sediment fluxes and ecology of the Palamós (La Fonera) submarine canyon, northwestern Mediterranean

Currents, particle fluxes and ecology were studied in the Palamós submarine canyon (also known as the Fonera canyon), located in the northwestern Mediterranean. Seven mooring arrays equipped with current meters and sediment traps were deployed along the main canyon axis, on the canyon walls and on the adjacent slope. Additionally, local and regional hydrographic cruises were carried out. Current data showed that mean near surface and mid-depth currents were oriented along the mean flow direction (NE–SW), although at 400 and 1200 m depth within the canyon current reversals were significant, indicating a more closed circulation inside the canyon. Mean near-bottom currents were constrained by the local bathymetry, especially at the canyon head. The most significant frequency at all levels was the inertial frequency. A second frequency of about three days, attributed to a topographic wave, was observed at all depths, suggesting that this wave was probably not trapped near the bottom. The current field observed during the most complete survey revealed a meandering pattern with cyclonic vorticity just upstream from and within the canyon. The associated vertical velocity ranged between 10 and 20 m/day and was constrained to the upper 300 m. This latter feature, together with other computations, suggests that during this survey the meander was not induced by the canyon but by some kind of instability of the mean flow.In the canyon, suspended sediment concentration, downward particle fluxes, chlorophyll and particulate C and N were significantly higher up-canyon from about 1200 m depth than offshore, defining, along with the different hydrodynamics, two canyon domains: one from the canyon head to about 1200 m depth more affected by the canyon confinement and the other deeper than 1200 m depth more controlled by the mean flow and the shelf-slope front. The higher near-bottom downward total mass fluxes were recorded in the canyon axis at 1200 m depth along with sharp turbidity increases and are related to sediment gravity flows. During the deployment period, the increase in downward particle fluxes occurred by mid-November, when a severe storm took place. On the canyon walls at 1200 m depth, suspended sediment concentrations, downward particle fluxes, chlorophyll and particulate C and N were higher on the southern wall than on the northern wall inversely to the current’s energy. This could be caused by an upward water supply on the southern canyon wall and/or the mean flow interacting with the canyon bathymetry. In the swimmers collected by the sediment traps, the dominant species was an elasipod holothurian, which has not been recorded in other canyons or elsewhere in the Mediterranean, indicating particular speciation.     

High-frequency fluxes of labile compounds in the central Ligurian Sea,northwestern Mediterranean

Sinking particles were collected every 4 h with drifting sediment traps deployed at 200 m depth in May 1995 in a 1-D vertical system during the DYNAPROC observations in the northwestern Mediterranean sea. POC, proteins, glucosamine and lipid classes were used as indicators of the intensity and quality of the particle flux. The roles of day/night cycle and wind on the particle flux were examined. The transient regime of production from late spring bloom to pre-oligotrophy determined the flux intensity and quality. POC fluxes decreased from, on average, 34 to 11 mg m⁻² d⁻¹, representing 6–14% of the primary production under late spring bloom conditions to 1–2% under pre-oligotrophic conditions. Total protein and chloroplast lipid fluxes correlated with POC and reflected the input of algal biomass into the traps. As the season proceeded, changes in the biochemical composition of the exported material were observed. The C/N ratio rose from 7.8 to 12. Increases of serine (10–28% of total proteins), total lipids (7–9 to 14–28% of POC) and reserve lipids (1–5 to 5–22% of total lipids) were noticeable, whereas total protein content in POC decreased (20–27 to 18–7%). N-acetyl glucosamine, a tracer of fecal pellet flux, showed that zooplankton grazing was a major vector of downward export during the decaying bloom. Against this background pattern, episodic events specifically increased the flux, modifying the quality and the settling velocity of particles. Day/night signals in biotracers (POC, N-acetyl glucosamine, protein and chloroplast lipids) showed that zooplankton migrations were responsible for sedimentation of fresh material through fast sinking particles (V=170–180 m d⁻¹) at night. Periodic signatures of re-processed material (high lipolysis and bacterial biomass indices) suggested that other zooplankton fecal pellets or small aggregates, probably of lower settling velocities (V<170 m d⁻¹), contributed to the flux during calm periods. At the beginning of the experiment, during the development of a prymnesiophyte bloom in the upper layers, the sterol signal with no periodicity enabled us to estimate high particle settling velocities (⩾600 m d⁻¹) likely related to large aggregate formation. A wind event increased biotracer fluxes (POC, protein, chloroplast lipids). The rapid transmission of surface signals through extremely fast sinking particles could be a general feature of particle fluxes in marine areas unaffected by horizontal advection.     

厦门湾水体中颗粒有机碳的垂向输出通量:~(234)Th/~(238)U不平衡的应用

对厦门湾塔角附近海域某站位叶绿素 a、POC、初级生产力、234Th/238U不平衡进行的周日变化研究表明,POC含量介于14.4～34.6 mmol/m3之间,其中碎屑有机碳与活体有机碳所占份额分别为74％～92％和8％～26％.POC垂直分布呈现由表及底降低的趋势,且白昼期间POC含量高于晚间,说明研究海域POC含量与生物过程具有密切联系.初级生产力水平在1d之中变化达5倍,垂直分布亦随深度增加而降低,与叶绿素a的变化相对应.短时间（2h）培养获得的初级生产力水平明显高于长时间培养（24 h）的结果,证实部分新固定的碳被优先呼吸排出.结合234Th/238U不平衡法获得的颗粒态234Th输出通量及输出界面颗粒物中的POC/PTh比值,可计算出真光层 POC的垂向输出通量为16.0mmol/（m2·d）,其中碎屑有机碳与活体有机碳贡献的数量分别为13.3和2.7mmol/（m2·d）.POC输出通量与初级生产力的比值（ThE比值）平均为0.31,真光层POC停留时间平均为11d.上述结果与Aksnes和Wassmann[1]的模型计算结果相吻合,但与其他大多数模型的结果仍存在一定的差异.     

234 Th示踪法测定北太平洋西北海域冬季真光层中颗粒态有机碳输出通量

讨论了1997年冬季在北太平洋西北海域7个站位的表层至200m水深水柱中溶解及颗粒态234Th,颗粒态有机碳(POC)、氮(PON)及叶绿素a浓度的垂直分布剖面.溶解态、颗粒态及总的234Th的放射性在真光层中显著低于母体238U的放射性,总的234Th放射性在水深大于100m时趋于平衡.利用234Th-238U在海洋表层海水中的放射性不平衡推导出了北太平洋西北海域冬季真光层海水中234Th的平均停留时间和输出通量以及颗粒态有机碳和有机氮的输出通量.在亚北极环流区溶解态234Th的停留时间为40~50d,而在黑潮-亲潮共同影响区为20d左右.颗粒态有机碳和有机氮从真光层的输出通量范围分别为3.8~8.2和0.50~0.98mmol/(m2·d),西部海区高于东部海区,南部海区高于北部海区.在黑潮-亲潮共同影响区较高的颗粒态有机碳输出通量表明光照量及陆源营养盐物质的提供是两个决定生产力的主要因素.叶绿素a的水深分布和POC/PON的值同Redfield的比值的一致性表明这个海区的冬季颗粒物主要由浮游植物构成.北太平洋西北海域在冬季的颗粒有机碳输出通量可高于世界大洋一些海区春、夏季的颗粒有机碳输出通量.     

Bacterioplankton and phytoplankton biomass and production during summer stratification in the northwestern Mediterranean Sea

We examined bacterioplankton biomass and heterotrophic production (BHP) during summer stratification in the northwestern Mediterranean in four successive stratification seasons (June–July of 1993–1996). Values of phytoplankton biomass and primary production were determined simultaneously so that the data sets for autotrophic and heterotrophic microbial plankton could be compared. Three standard stations were set along a transect from Barcelona to the channel between Mallorca and Menorca, representing coastally influenced shelf waters, frontal waters over the slope front, and open sea waters. Conversion factors from ³H-leucine incorporation to BHP were empirically determined and varied between 0.29 and 3.25 kg C mol^-1. Bacterial biomass values were among the lowest found in any marine environment. BHP values (between 0.02 and 2.5 μg C L^-1 d^-1) were larger than those of low nutrient low chlorophyll areas such as the Sargasso Sea and lower than those from high nutrient low chlorophyll areas such as the equatorial Pacific. Growth rates of bacterioplankton were highest at the slope front (0.20 d^-1) and lowest at the open sea station (0.04 d^-1). Phytoplankton growth rates were similar at the three stations (∼0.50 d^-1). Integrated values of bacterioplankton biomass, BHP and bacterial growth rates did not show significant differences among years, but differences between the three stations were clearly significant. Phytoplankton biomass, primary production, and phytoplankton growth rates did not show significant differences either with year or with station. As a consequence the bacterioplankton to phytoplankton biomass (BB/BPHY) and production (BHP/PP) ratios varied from the coastal to the open sea stations. The BB/BPHY ratio was 0.98 at the coast and ∼0.70 at the other two stations. These ratios are similar to those found in other oligotrophic marine environments. The BHP/PP ratio was 0.83 at the coast, 0.36 at the slope and 0.09 at the open sea station. The last value is also similar to values found in other oligotrophic marine environments. Vertical distribution of these ratios was also examined.The comparison of microbial parameters at the three stations indicates a different kind of relationship between bacterioplankton and phytoplankton in oligotrophic open sea waters and in coastal, nutrient-richer waters. According to such parameters and to the values of the BB/BPHY and BHP/PP ratios, open waters in the northwestern Mediterranean (despite their relatively short distance from the shore) were intermediate between the extremely oligotrophic waters of the eastern Mediterranean or the Sargasso Sea and the more productive waters of the equatorial Pacific.     

A time-series study of particulate matter export in the North Pacific Subtropical Gyre based on Th : U disequilibrium

Depth profiles of total ²³⁴Th (dissolved+particulate) were collected at Station ALOHA (22°45N, 158°00W) in the North Pacific Subtropical Gyre during 9 cruises from April 1999 to March 2000. Samples were collected and processed by a new 2 L technique that enables more detailed depth resolution then previous ²³⁴Th studies. Significant zones of particle export (²³⁴Th deficiency) and particle remineralization (²³⁴Th excess) were measured both temporally and with depth. ²³⁴Th derived particulate carbon (PC) and nitrogen (PN) fluxes were determined with steady-state and non-steady-state models and PC/²³⁴Th and PN/²³⁴Th ratios measured with both in situ pumps and free-drifting particle interceptor traps deployed at 150 m. ²³⁴Th based export estimates of 4.0±2.3 mmol C m⁻² d⁻¹ and 0.53±0.19 mmol N m⁻² d⁻¹, were approximately 60% higher than those measured in PIT style sediment traps from the same time period, 2.4±0.2 mmol C m⁻² d⁻¹ and 0.32±0.08 mmol N m⁻² d⁻¹. Most of this difference is attributable to two large export events that occurred during October and December 1999, when traps undercollected for ²³⁴Th by a factor of 2 to 4. ²³⁴Th export (ThE) ratios based on ²³⁴Th derived PC flux/¹⁴C based primary production ranged from 4% to 22% (average=8.8%). Our results confirm the recent estimates of C export by Emerson et al. (Nature 389 (1997) 951) and Sonnerup et al. (Deep-Sea Research I 46 (1999) 777) and indicate that C export from the oligotrophic ocean must be considered when discussing C sequestration in global climate change.     

厦门湾水体中颗粒有机碳的垂向输出通量:234Th/238U不平衡的应用

对厦门湾塔角附近海域某站位叶绿素 a、POC、初级生产力、234Th/238U不平衡进行的周日变化研究表明,POC含量介于14.4～34.6 mmol/m3之间,其中碎屑有机碳与活体有机碳所占份额分别为74%～92%和8%～26%.POC垂直分布呈现由表及底降低的趋势,且白昼期间POC含量高于晚间,说明研究海域POC含量与生物过程具有密切联系.初级生产力水平在1d之中变化达5倍,垂直分布亦随深度增加而降低,与叶绿素a的变化相对应.短时间(2h)培养获得的初级生产力水平明显高于长时间培养(24 h)的结果,证实部分新固定的碳被优先呼吸排出.结合234Th/238U不平衡法获得的颗粒态234Th输出通量及输出界面颗粒物中的POC/P_Th比值,可计算出真光层 POC的垂向输出通量为16.0mmol/(m2·d),其中碎屑有机碳与活体有机碳贡献的数量分别为13.3和2.7mmol/(m2·d).POC输出通量与初级生产力的比值(ThE比值)平均为0.31,真光层POC停留时间平均为11d.上述结果与Aksnes和Wassmann[1]的模型计算结果相吻合,但与其他大多数模型的结果仍存在一定的差异.     

Particle fluxes in San Pedro Basin, California: A four-year record of sedimentation and physical forcing

Moored sediment traps were deployed from January 2004 through December 2007 at depths of 550 and 800 m in San Pedro Basin (SPB), CA (33°33.0′N, 118°26.5′W). Additionally, floating sediment traps were deployed at 100 and 200 m for periods of 12-24 h during spring 2005, fall 2007, and spring 2008. Average annual fluxes of mass, particulate organic carbon (POC), ??¹³C_org, particulate organic nitrogen (PON), ??¹⁵N-PON, biogenic silica (bSiO₂), calcium carbonate (CaCO₃), and detrital material (non-biogenic) were coupled with climate records and used to examine sedimentation patterns, vertical flux variability, and organic matter sources to this coastal region. Annual average flux values were determined by binning data by month and averaging the monthly averages. The average annual fluxes to 550 m were 516±42 mg/m² d for mass (sdom of the monthly averages, n=117), 3.18±0.26 mmol C/m² d for POC (n=111), 0.70±0.05 mmol/m² d for CaCO₃ (n=110), 1.31±0.21 mmol/m² d for bSiO₂ (n=115), and 0.35±0.03 mmol/m² d for PON (n=111). Fluxes to 800 and to 550 m were similar, within 10%. Annual average values of ??¹³C_org at 550 m were −21.8±0.2‰ (n=108), and ??¹⁵N averages were 8.9±0.2‰ (n=95). The timing of both high and low flux particle collection was synchronous between the two traps. Given the frequency of trap cup rotation (4-11 days), this argues for particle settling rates ≥83 m/d for both high and low flux periods. The moored traps were deployed over one of the wettest (2004-2005, 74.6 cm rainfall) and driest (2006-2007, 6.6 cm) rain years on record. There was poor correlation (Pearson's correlation coefficient, 95% confidence interval) of detrital mass flux with: C_org/N ratio (r=0.10, p=0.16); ??¹⁵N (r=−0.19, p=0.02); and rainfall (r=0.5, p=0.43), suggesting that runoff does not immediately cause increases in particle fluxes 15 km offshore. ??¹³C_org values suggest that most POC falling to the basin floor is marine derived. Coherence between satellite-derived chlorophyll a records from the trap location (±9 km² resolution) and SST data indicates that productivity and export occurs within a few days of upwelling and both of these parameters are reasonable predictors of POC export, with a time lag of a few days to 2 weeks (with no time lag—SeaWiFS chlorophyll a and POC flux, r=0.25, p=0.0014; chlorophyll a and bSiO₂ flux, r=0.28, p=0.0002).     

Particulate organic carbon export fluxes and size-fractionated POC/234Th ratios in the Ligurian,Tyrrhenian and Aegean Seas

Measurements of ²³⁴Th/²³⁸U disequilibria and particle size-fractionated (1, 10, 20, 53, 70, 100 μm) organic C and ²³⁴Th were made to constrain estimates of the export flux of particulate organic C (POC) from the surface waters of the Ligurian, Tyrrhenian and Aegean Seas in March–June 2004. POC exported from the surface waters (75–100 m depth) averaged 9.2 mmol m⁻² d⁻¹ in the Ligurian and Tyrrhenian Seas (2.3±0.5–14.9±3.0 mmol m⁻² d⁻¹) and 0.9 mmol m⁻² d⁻¹ in the Aegean Sea. These results are comparable to previous measurements of ²³⁴Th-derived and sediment-trap POC fluxes from the upper 200 m in the Mediterranean Sea. Depth variations in the POC/²³⁴Th ratio suggest two possible controls. First, decreasing POC/²³⁴Th ratios with depth were attributed to preferential remineralization of organic C. Second, the occurrence of maxima or minima in the POC/²³⁴Th ratio near the DCM suggests influence by phytoplankton dynamics. To assess the accuracy of these data, the empirical ²³⁴Th-method was evaluated by quantifying the extent to which the ²³⁴Th-based estimate of POC flux, P_POC, deviates from the true flux, F_POC, defined as the p-ratio (p-ratio=P_POC/F_POC=S_Th/S_POC, where S=particle sinking rate). Estimates of the p-ratio made using Stokes’ Law and the particle size distributions of organic C and ²³⁴Th yield values ranging from 0.93–1.45. The proximity of the p-ratio to unity implies that differences in the sinking rates of POC- and ²³⁴Th-carrying particles did not bias ²³⁴Th-normalized POC fluxes by more than a factor of two.     

POC export from ocean surface waters by means of Th/U and Po/Pb disequilibria: A review of the use of two radiotracer pairs

²³⁴Th (T_1/2=24.1 d) and ²¹⁰Po (T_1/2=138.4 d) are particle reactive radioisotopes that are used as tracers for particle cycling in the upper ocean. Particulate organic carbon (POC) export has frequently been estimated using ²³⁴Th/²³⁸U disequilibrium. Recent evidence suggests that ²¹⁰Po/²¹⁰Pb disequilibrium may be used as an additional tool to examine particle export, given the direct biological uptake of ²¹⁰Po into cellular material. Differences in these two radioisotope pairs with regard to their half-lives, particle reactivity and scavenging affinity in seawater should provide complementary information to be obtained on the processes occurring in the water column. Here, we review eight different studies that have simultaneously used both approaches to estimate POC export fluxes from the surface ocean. Our aim is to provide a complete “dataset” of all the existing POC flux data derived from the coupled use of both ²³⁴Th and ²¹⁰Po and to evaluate the advantages and limitations of each tracer pair. Our analysis suggests that the simultaneous use of both radiotracers provides more useful comparative data than can be derived from the use of a single tracer alone. The difference in half-lives of ²³⁴Th and ²¹⁰Po enables the study of export production rates over different time scales. In addition, their different biogeochemical behaviour and preferred affinity for specific types of particles leads to the conclusion that ²³⁴Th is a better tracer of total mass flux, whereas ²¹⁰Po tracks POC export more specifically. The synthesis presented here is also intended to provide a basis for planning future sampling strategies and promoting further work in this field to help reveal the more specific application of each tracer under specific water column biogeochemistries.     

Sampling the vertical particle flux in the upper water column using a large diameter free-drifting NetTrap adapted to an Indented Rotating Sphere sediment trap

Further development of the large, surface-tethered sediment trap (NetTrap) employed as part of the MedFlux program is described whereby the large collection capacity of the NetTrap is combined with an Indented Rotating Sphere/Sample Carousel (IRSC) sediment trap (IRSC–NT). This trap is capable of collecting particle flux either in a time series or settling velocity mode; settling velocity mode allows the collection of particles that fall within discrete settling velocity intervals. During short field deployments in the Mediterranean Sea the IRSC–NT configured in the settling velocity mode successfully collected unpoisoned samples for chemical and microbiological experiments. In addition to the development of the IRSC–NT, particle-settling behavior above and below the swimmer-excluding IRS valve was tested during on-deck experiments using a specially constructed water-tight trap. Chemical analyses of settling materials (published elsewhere) suggested that separation of particles by settling velocity was achieved. However, due to the motion of the ship, it was not possible to directly measure particle-settling velocities within the trap. Particle release from the IRS did not bias the apparent settling velocity spectrum. Rotation of the IRS did not engender turbulence at the surface of the sphere or within the skewed funnel below. Tests of different ball designs over the course of the MedFlux program showed that a “ridge and saddle” pattern was optimal for efficiently transferring particles under the IRS seal while still reducing swimmer entrance to the collection funnel. The large size of the IRSC–NT did not prevent it from drifting effectively with the current. Several modifications of the present design are proposed that should improve the accuracy of the settling velocity measurements.     

Particulate carbohydrate fluxes in the Bransfield Strait and the Drake Passage

Carbohydrate fluxes were determined for five drifting sediment traps (max. 30 h) in the Bransfield Strait and one moored trap array (52 days) in the Drake Passage in December/January 1980. In a Phaeocystis-dominated zone in the Bransfield Strait the carbohydrate composition was comparable to that of water column suspended material with absolute fluxes of 9.0 and 56.7 mg carbohydrate carbon m⁻²d⁻¹. In Bransfield Strait waters dominated by bacillariophyceae, fluxes were 75.4, 92.6 and 276.8 mg carbohydrate carbon m⁻²d⁻¹ with a pronounced dominance of glucose. This is attributed to the presence of the reserve polysaccharide chrysolaminarin in diatom resting spores. Drake Passage fluxes were 1–2 orders of magnitude lower with a distinct degradation of glucose with depth.     

Dynamics of particle flux and carbon export in the northwestern Mediterranean Sea: A two decade time-series study at the DYFAMED site

The DYFAMED time-series station, located in the open Ligurian Sea, is one of the few pluriannual flux programs in the world and the longest in the Mediterranean Sea. The trap data series is one of only three multi-decadal data sets in existence, and it provides flux information for an environment that is distinct from the other long-term data sets. At DYFAMED, downward fluxes of particles, carbon and other major elements have been regularly measured with sediment traps since 1986 at fixed depths of 200 and 1000 m. An overview is presented of the main trends of particle and carbon fluxes observed during the period 1988–2005, period when the mooring was located on the northern side of the Ligurian Sea. In spite of considerable interannual variability, fluxes displayed a marked seasonal pattern with the highest fluxes occurring during winter and spring and lowest fluxes throughout the stratified season (summer–autumn). Organic carbon fluxes measured at both depths were highly variable over time, ranging from 0.3 to 59.9 (mean 6.8) mg C m⁻² d⁻¹ at 200 m, and from 0.2 to 37.1 (mean 4.3) mg C m⁻² d⁻¹ at 1000 m. Mass fluxes were maximal in winter, whereas carbon fluxes were maximal in late spring. Reasonably good agreement existed between particle fluxes at both depths over the years, indicating a relatively efficient and rapid transport of particles from the upper ocean to the deep sea. However, during certain periods mass flux increased with depth suggesting lateral inputs of particles that by-pass the upper trap. Since 1999, the system has apparently shifted towards an increasing occurrence of extreme flux events in response to more vigorous mixing of the water column during the winter months. Although annual mass fluxes have increased in the last years, mean POC fluxes have not substantially changed over time, due mainly to lower carbon contents of the sinking particles during maxima of mass flux.     

Particulate carbon and nitrogen fluxes and compositions in the central equatorial Pacific

Mass, carbon, and nitrogen fluxes and carbon and nitrogen compositions were determined for particulate samples from plankton net tows, shallow floating sediment traps, intermediate and deep moored sediment traps, and sediment cores collected along 140°W in the central equatorial Pacific Ocean during the US JGOFS EqPac program. Mass, particulate organic carbon (POC), and particulate inorganic carbon (PIC) fluxes measured by the floating sediment traps during the Survey I (El Niño) and Survey II (non-El Niño) cruises follow essentially the same pattern as primary production: high near the equator and decreasing poleward. POC fluxes caught in free-floating traps were compared with alternative estimates of export fluxes, including ²³⁴Th models, new production, and other sediment trap studies, resulting in widely differing estimates. Applying ²³⁴Th corrections to the trap-based fluxes yielded more consistent results relative to primary production and new production. Despite factors of five differences in measured fluxes between different trap types, POC : ²³⁴Th ratios of trap material were generally within a factor of two and provided a robust means of converting modeled ²³⁴Th export fluxes to POC export fluxes. All measured fluxes decrease with depth. Trap compositional data suggest that mineral “ballasting” may be a prerequisite for POC settling. POC remineralization is most pronounced in the epipelagic zone and at the sediment–water interface, with two orders of magnitude loss at each level. Despite seawater supersaturation with respect to calcium carbonate in the upper ocean, 80% of PIC is dissolved in the epipelagic zone. Given the time-scale differences of processes throughout the water column, the contrasting environments, and the fact that only 0.01% of primary production is buried, sedimentary organic carbon accumulation rates along the transect are remarkably well correlated to primary production in the overlying surface waters. POC to particulate total nitrogen (PTN) ratios for all samples are close to Redfield values, indicating that POC and PTN are non-selectively remineralized. This constancy is somewhat surprising given conventional wisdom and previous equatorial Pacific results suggesting that particulate nitrogen is lost preferentially to organic carbon.