Seasonality of particle-associated trace element fluxes in the deep northeast Atlantic Ocean

In the framework of the German contribution to the Joint Global Ocean Flux Study (JGOFS), deep-water fluxes of particle-associated trace elements were measured in the northeast Atlantic Ocean. The sinking particles were collected almost continuously from 1992 to 1996 at three time-series stations, L1 (33°N/22°W), L2 (47°N/20°W), and L3 (54°N/21°W), using sediment traps. The focus of the present study is the temporal variability of the particle-associated elemental fluxes of Al, Ca, Cd, Co, Cu, Fe, Mn, Ni, P, Pb, Ti, V, and Zn at a depth of 2000 m.A clear seasonality of the fluxes that persisted for several years was documented for the southernmost station (L1) at stable oligotrophic conditions in the area of the North Atlantic Subtropical Gyre East (NASTE). At L2 and L3, an episodic nature of the elemental fluxes was determined. Mesoscale eddies are known to frequently cause temporal and spatial variability in the flux of biogenic components in that area. These events modified the simple seasonal pattern controlled by the annual cycle at L2, in the North Atlantic Drift Region (NADR), and at L3, which was influenced by the Atlantic Arctic province (ARCT). All stations were characterized by an additional episodic lithogenic atmospheric supply reaching the deep sea.The integrated annual fluxes during the multi-year study revealed similar flux magnitudes for lithogenic elements (Al, Co, Fe, Ti, and V) at L2 and L3 and roughly twofold fluxes at L1. Biogenic elements (Cd, P, and Zn) showed the opposite trend, i.e., two to fourfold higher values at L2 and L3 than at L1. For Mn, Ni, and Cu, the spatial differences were smaller, perhaps because of the intermediate behavior, between lithogenic and biogenic, of these elements. Similarly, among the three study sites, there were no noticeable differences in the total annual flux of Pb.The respective lithogenic fractions of the deep-sea fluxes of Cd, Co, Cu, Mn, Ni, V, and Zn were subtracted based on the amount of Al, with the average composition of the continental crust as reference. This procedure allowed estimation of the labile trace element fraction (TE_exc) of the particles, i.e., TE taken up or scavenged during particle production and sedimentation. The ratios of TE_exc/P clearly demonstrated an enrichment of TE over labile P from biogenic surface material to the deep sea for Zn (factor 4–6), Mn (12–27), Ni (3–5), and Cu (9–25); an intermediate status for Co (0.5–2.2); and depletion for Cd vs. P (0.2–0.4). Surprisingly, the recycling behavior of excess Co was found to be similar to that of P. Hence, Co_exc behaved like a biogenic element; this is in contrast to total Co, which is dominated by the refractory lithogenic fraction.Moreover, it is argued that these excess elemental fluxes caused a loss of the dissolved elements in upper waters, since their transport reaches the deep-sea waters at 2000 m, a depth far below of deep-winter mixing and upwelling. The annual amount of excess TE exported from surface waters was estimated to be 1.3×10⁹ mol Zn y^?1, 4.4×10⁹ mol Mn y^?1, 4.9×10⁸ mol Ni y^?1, 2.2×10⁷ mol Cd y^?1, 7.4×10⁸ mol Cu y^?1, and 2.7×10⁷ mol Co y^?1 for the whole North Atlantic Ocean. Important primary sources that could replenish these losses are the aeolian and fluvial supply processes.     

Bioaccumulation and trophic transfer of mercury in striped bass (Morone saxatilis) and tautog (Tautoga onitis) from the Narragansett Bay (Rhode Island,USA)

We examined the bioaccumulation and trophic transfer of mercury in two marine finfish species, striped bass (Morone saxatilis) and tautog (Tautoga onitis), collected from the Narragansett Bay (Rhode Island, USA). For each of these target fish, white muscle tissue was analyzed for total mercury (Hg) and results were evaluated relative to fish age, body size, and Hg content of preferred prey. Dietary and stable isotope analysis was also used to elucidate the effect of trophic processes on Hg concentrations in fish. The Hg content of muscle tissue was positively correlated with fish age and length for both species, although striped bass accumulated Hg faster than tautog. Accelerated Hg bioaccumulation in striped bass is consistent with its high trophic level (trophic level = 4.07) and Hg-enriched prey (forage fish and macrocrustaceans; mean Hg content = 0.03 mg Hg kg wet wt^?1). In contrast, tautog maintain a lower trophic status (trophic level = 3.51) and consume prey with lower Hg levels (mussels and crabs; mean Hg content = 0.02 mg Hg kg wet wt^?1). Despite differences in Hg bioaccumulation between target fish, the mean Hg concentration of tautog exceeded levels in striped bass (0.24 and 0.16 mg Hg kg wet wt^?1, respectively) due to a disparity in age-at-catch between sampled groups (mean age of tautog and bass = 11.3 and 4.3 yr, respectively). Taking into account legal minimum catch lengths further revealed that 75.0% of legal-size striped bass (>70.2 cm TL; n = 4) and 44.8% of tautog (>40.6 cm TL; n = 29) had Hg levels beyond the US EPA regulatory threshold of 0.3 mg Hg kg wet wt^?1. Moreover, Hg-length relationships suggest that each target fish meets this threshold near their minimum legal catch length. Our findings reiterate the value of species ecology to improve predictions of fish Hg and permit better management of human contamination by this important dietary source.     

Particulate trace element fluxes in the deep northeast Atlantic Ocean

Particulate fluxes of trace elements (Al, Cd, Co, Cu, Fe, Mn, Ni, P, Ti, V and Zn) in the northeast Atlantic Ocean (three positions at latitudes from 33°N to 54°N along ∼20°W) were measured using time-series sediment traps between March 1992 and September 1994. Significant variabilities of fluxes with season and depth (1000 m to maximum of 4000 m) were observed only for ‘biogenic elements’, such as Cd, Ni, Zn or P. On the other hand, we found a distinct large-scale increase of fluxes into the deep-sea traps to the south for Al, Co, Fe, Mn and V. We attribute this latitudinal gradient to the increasing influence of the Saharan dust plume. The biogenic flux decreased towards the south. This trend was clearly visible for Cd and P only. The fluxes of other ‘nutrient-like’ elements, such as Ni or Zn, exhibited a general decrease between 53°N and 33°N. We compared our sedimentation flux data with published data from the western North Atlantic basins. For this purpose we corrected the deep-sea fluxes of Cu, Mn, Ni and Zn for their lithogenic fractions on the basis of Al, with average crustal material and granitic rocks as references. The comparison indicates that these ‘excess’ fluxes are a factor of at least 2 higher in the western basins for the selected elements. Estimated fluxes are in good agreement with reported atmospheric deposition in the two areas. The noted imbalance between the non-lithogenic atmospheric input of Mn and the determined ‘excess flux’ in the deep northeast Atlantic indicates an additional input in the form of a lateral flux of dissolved Mn(II) species and scavenging onto sinking particles. With respect to the mechanism of sedimentation, a unique behaviour is noticed for the refractory elements Co, Fe, Mn, Ti and V, which were found to correlate with the vertical transport of Al (clay). The ‘excess’ fluxes of Cu, Ni and Zn are linearly related to C_org, whereas the overall relation of Cd to P fluxes exhibits a molar Cd/P ratio of 2.0×10^-4, which is close to the ratio in the dissolved fractions in the northeast Atlantic.     

Biogenic fluxes in the Cariaco Basin: a combined study of sinking particulates and underlying sediments

The fluxes of total mass, organic carbon (OC), biogenic opal, calcite (CaCO₃) and long-chain C₃₇ alkenones (ΣAlk₃₇) were measured at three water depths (275, 455 and 930 m) in the Cariaco Basin (Venezuela) over three separate annual upwelling cycles (1996–1999) as part of the CARIACO sediment trap time-series. The strength and timing of both the primary and secondary upwelling events in the Cariaco Basin varied significantly during the study period, directly affecting the rates of primary productivity (PP) and the vertical transport of biogenic materials. OC fluxes showed a weak positive correlation (r²=0.3) with PP rates throughout the 3 years of the study. The fluxes of opal, CaCO₃ and ΣAlk₃₇ were strongly correlated (0.6<r²<0.8) with those of OC. The major exception was the lower than expected ΣAlk₃₇ fluxes measured during periods of strong upwelling. All sediment trap fluxes were significantly attenuated with depth, consistent with marked losses during vertical transport. Annually, strong upwelling conditions, such as those observed during 1996–1997, led to elevated opal fluxes (e.g., 35 g m⁻² yr⁻¹ at 275 m) and diminished ΣAlk₃₇ fluxes (e.g., 5 mg m⁻² yr⁻¹ at 275 m). The opposite trends were evident during the year of weakest upwelling (1998–1999), indicating that diatom and haptophyte productivity in the Cariaco Basin are inversely correlated depending on upwelling conditions.The analyses of the Cariaco Basin sediments collected via a gravity core showed that the rates of OC and opal burial (10–12 g m⁻² yr⁻¹) over the past 5500 years were generally similar to the average annual water column fluxes measured in the deeper traps (10–14 g m⁻² yr⁻¹) over the 1996–1999 study period. CaCO₃ burial fluxes (30–40 g m⁻² yr⁻¹), on the other hand, were considerably higher than the fluxes measured in the deep traps (∼10 g m⁻² yr⁻¹) but comparable to those obtained from the shallowest trap (i.e. 38 g m⁻² yr⁻¹ at 275 m). In contrast, the burial rates of ΣAlk₃₇ (0.4–1 mg m⁻² yr⁻¹) in Cariaco sediments were significantly lower than the water column fluxes measured at all depths (4–6 mg m⁻² yr⁻¹), indicating the large attenuation in the flux of these compounds at the sediment–water interface. The major trend throughout the core was the general decrease in all biogenic fluxes with depth, most likely due to post-depositional in situ degradation. The major exception was the relatively low opal fluxes (∼5 g m⁻² yr⁻¹) and elevated ΣAlk₃₇ fluxes (∼2 mg m⁻² yr⁻¹) measured in the sedimentary interval corresponding to 1600–2000 yr BP. Such compositions are consistent with a period of low diatom and high haptophyte productivity, which based on the trends observed from the sediment traps, is indicative of low upwelling conditions relative to the modern day.     

Home range and diel behavior of the ballan wrasse,Labrus bergylta,determined by acoustic telemetry

Effective fisheries management needs to consider spatial behavior in addition to more traditional aspects of population dynamics. Acoustic telemetry has been extensively used to provide information on fish movements over different temporal and spatial scales. Here, we used a fixed-receiver array to examine the movement patterns of Labrus bergylta Ascanius 1767, a species highly targeted by the artisanal fleet of Galicia, NW Spain. Data from 25 individuals was assessed for a period of 71 days between September and November 2011 in the Galician Atlantic Islands Maritime-Terrestrial National Park. Fish were present within the monitored area more than 92% of the monitored time. The estimated size of individual home ranges, i.e. the area where fish spent most of their time, was small. The total minimum convex polygons area based on all the estimated positions was 0.133 ± 0.072 km², whereas the home range size estimated using a 95% kernel distribution of the estimated positions was 0.091 ± 0.031 km². The core area (50% kernel) was 0.019 ± 0.006 km². L. bergylta exhibited different patterns of movement in the day versus the night, with 92% of the fish detected more frequently and traveling longer distances during the daytime. In addition, 76% of the fish displayed a larger home range during the day versus during the night. The linearity index was less than 0.005 for all fish suggesting random movements but within a relatively small area, and the volume of intersection index between consecutive daily home ranges was 0.75 ± 0.13, suggesting high site fidelity. The small home range and the sedentary behavior of L. bergylta highlight the potential use of small MPAs as a management tool to ensure a sustainable fishery for this important species.     

Lipid biomarkers in suspended particles from a subtropical estuary: Assessment of seasonal changes in sources and transport of organic matter

Temporal and spatial variations in the composition of particulate organic matter (POM) from Florida Bay, USA were examined. The predominance of short-chain homologues for n-alkanes, n-alcohols and n-fatty acids as well as relatively high abundance of C₂₇ and C₂₈ sterols suggested that an autochthonous/marine source of OM was dominant bay-wide. Several biomarker proxies such as P_aq [(C₂₃ + C₂₅)/(C₂₃ + C₂₅ + C₂₉ + C₃₁) n-alkanes], short/long chain n-alkanes, (C₂₉ + C₃₁) n-alkanes and taraxerol indicated a spatial shift in OM sources, where terrestrial OM rapidly decreased while seagrass and microbial OM markedly increased along a northeastern to southwestern transect. Regarding seasonal variations, POM collected during the dry season was enriched in terrestrial constituents relative to the wet season, likely as a result of reduced primary productivity of planktonic species and seagrasses during the dry season. Principal component analysis (PCA) classified the sample set into sub-groups based on PC1 which seemed to be spatially controlled by OM origin (terrestrial-mangrove vs. marine-planktonic/seagrass). The PC2 seemed to be more seasonally controlled suggesting that hydrological fluctuations and seasonal primary productivity are the drivers controlling the POM composition in Florida Bay.     

Production and air–sea flux of halomethanes in the western subarctic Pacific in relation to phytoplankton pigment concentrations during the iron fertilization experiment (SEEDS II)

Iron could play a key role in controlling phytoplankton biomass and productivity in high-nutrient, low-chlorophyll regions. As a part of the iron fertilization experiment carried out in the western subarctic Pacific from July to August 2004 (Subarctic Pacific iron Experiment for Ecosystem Dynamics Study II—SEEDS II), we analysed the concentrations of trace gases in the seawater for 12 d following iron fertilization. The mean concentrations of chlorophyll a in the mixed layer (5–30 m depth) increased from 0.94 to 2.81 μg L^–1 for 8 d in the iron patch. The mean concentrations of methyl bromide (CH₃Br; 5–30 m depth) increased from 6.4 to 13.4 pmol L^–1 for 11 d; the in-patch concentration increased relative to the out-patch concentration. A linear correlation was observed between the concentrations of 19′-hexanoyloxyfucoxanthin, which is a biomarker of several prymnesiophytes, and CH₃Br in the seawater. After fertilization, the air–sea flux of CH₃Br inside the patch changed from influx to efflux from the ocean. There was no clear evidence for the increase in saturation anomaly of methyl chloride (CH₃Cl) due to iron fertilization. Furthermore, CH₃Cl fluxes did not show a tendency to increase after fertilization of the patch. In contrast to CH₃Br, no change was observed in the concentrations of bromoform (in-patch day 11 and out-patch day 11: 1.7 and 1.7 pmol L^–1), dibromomethane (2.1 and 2.2 pmol L^–1), and dibromochloromethane (1.0 and 1.2 pmol L^–1, respectively). The concentration of isoprene, which is known to have a relationship with chlorophyll a, did not change in this study. The responses of trace gases during SEEDS II differed from the previous findings (in situ iron enrichment experiment—EisenEx, Southern Ocean iron experiment—SOFeX, and Subarctic Ecosystem Response to Iron Enrichment Study—SERIES). Thus, in order to estimate the concomitant effect of iron fertilization on the climate, it is important to assess the induction of biological activity and the distributions/air–sea fluxes of trace gases by iron addition.     

Post-release survival and feeding in reared turbot

As part of the Danish restocking program, an experiment was carried out with four groups of turbot Psetta maxima released on two different occasions at the same location in Århus Bay, Denmark. One objective was to analyse the duration of post-release mortality and the magnitude of this mortality. In 2003 a group called Large turbot (17.1 cm total length (L_T)) and a group called Intermediate (L_T = 11.8 cm) were released, and in 2004 two similar-sized groups called Naive and Conditioned (L_T = 9.8 cm) were released. The Conditioned differed from the Naive turbot by being transferred to enclosures at the release location six days prior to the actual release. This experiment was performed to investigate whether such a conditioning period had a positive effect on the survival and hence the success of the stocking. All the groups released were monitored daily until day 8, using a juvenile flatfish-trawl to recapture the fish. The catches were analyzed on the basis of a normal distribution approximation method, founded in diffusion theory, from which daily abundance of the released fish and hence post-release mortality could be estimated. The group of Large turbot suffered negligible post-release mortality, but for the Conditioned, Naive and Intermediate groups the loss varied between 34 and 66% d^− 1. The mortality for the Conditioned group was found to be half that of the Naive turbot released simultaneously. The period of high post-release mortality was estimated to be restricted to three days after release. The only active predators observed in the area were birds. Besides estimating mortality the diffusion model provides an estimate on the catchability of the released turbot when fished with a juvenile flatfish-trawl. Catchabilities varied between 38 and 52% for all releases except for the 17 cm sized turbot released, where catchability was only 12%. The feeding performance of the released fish was also analysed and compared with that of wild fish caught at the same location. These results showed that the proportion of stomachs containing food increased not only with time after release, but also with the size of the turbot. However, whether or not fish was included in the diet was not related to size but to time after release and to whether they had been conditioned or not.     

Tracing seafloor methane emissions with benthic foraminifera: Results from the Ana submarine landslide (Eivissa Channel,Western Mediterranean Sea)

The hypothesis that benthic foraminifera are useful proxies of local methane emissions from the seafloor has been verified on sediment core KS16 from the headwall of the Ana submarine landslide in the Eivissa Channel, Western Mediterranean Sea. The core MS312 from a nearby location with no known methane emissions is utilised as control. The core was analysed for biostratigraphy, benthic foraminiferal assemblages, Hyalinea balthica and Uvigerina peregrina carbon and oxygen stable isotope composition, and sedimentary structures. The upper part of the core records post-landslide deglacial and Holocene normal marine hemipelagic sediments with highly abundant benthic foraminifera species that are typical of outer neritic to upper bathyal environment. In this interval, the δ¹³C composition of benthic foraminifera indicates normal marine environment analogous to those found in the control core. Below the sedimentary hiatus caused by the emplacement of the slide, the foraminiferal assemblages are characterised by lower density and higher Shannon Index. Markedly negative δ¹³C shifts in benthic foraminifera are attributed to the release of methane through the seabed. The mean values of the ¹³C anomaly in U. peregrina are ? 0.951 ± 0.208 in the pre-landslide sediments, and ? 0.269 ± 0.152 in post-slide reworked sediments deposited immediately above the hiatus. The δ¹³C anomaly in Hyalinea balthica is ? 2.497 ± 0.080 and ? 2.153 ± 0.087, respectively. To discard the diagenetic effects on the δ¹³C anomaly, which could have been induced by Ca–Mg replacement and authigenic carbonate overgrowth on foraminifera tests, a benthic foraminifera subsample has been treated following an oxidative and reductive cleaning protocol. The cleaning has resulted, only in some cases, in a slight reduction of the anomaly by 0.95% for δ¹³C and < 0.80% for δ¹⁸O. Therefore, the first conclusion is that the diagenetic alteration is minor and it does not alter significantly the overall carbon isotopic anomaly in the core. Consequently, the pre-landslide sediments have been subject to pervasive methane emissions during a time interval of several thousand years. Methane emissions continued during and immediately after the occurrence of Ana Slide at about 61.5 ka. Subsequently, methane emissions decreased and definitely ceased during the last deglaciation and the Holocene.     

The role of crabs (Macrophthalmus japonicus) burrows on organic carbon cycle in estuarine tidal flat,Japan

The objective of this study is to elucidate the burrow structure and to clarify the role of burrows in material cycle in the tidal flat. In our work, we focused on the dominant species in muddy tidal flat, crab Macrophthalmus japonicus.Burrow structure of Macrophthalmus japonicus was investigated on a Katsuura river tidal flat in Tokushima prefecture, Japan, using in situ resin casting. Sampling was conducted in August 2006, and a total of 48 burrow casts were obtained. Burrows consisted mainly of J-shaped structures (98%) while the rest belonged to U-shaped structures (2%). The maximum measured burrow volume was 120 cm³ and wall surface area was 224 cm², while maximum burrow length and depth were 23.2 cm and 16.5 cm, respectively. Burrow volume and surface area were strongly correlated with carapace width of M. japonicus. Investigation of the individual number of M. japonicus in 13 quadrats (50 × 50 × 20 cm) was conducted using 2 mm sieve. The number of M. japonicus was 15–31 ind./m². Using cohort analysis we estimated that surface area of burrows was 0.07–0.15 m²/m².CO₂ emission rate was measured at the surface sediment during the period from June to December 2008. Results varied from 13.8 ± 2.2 to 49.4 ± 3.2 mg CO₂/m²/h, and organic carbon decomposition was 3.8 ± 0.6–13.5 ± 0.9 mg C/m²/h. This leads the increase of organic carbon decomposition by 1.1 times, because of the expansion of the tidal flat surface area by burrowing activity. Organic carbon decomposition in burrow walls therefore contributed to organic matter decomposition in the tidal flat. These results indicated that in situ activities of Macrophthalmus japonicus significantly influence the material cycle and it is important to consider the existence of burrow in order to understand the fluxes of materials and to evaluate the purification function of the tidal flat.     

Does Encope emarginata (Echinodermata: Echinoidea) affect spatial variation patterns of estuarine subtidal meiofauna and microphytobenthos?

Foraging macrofauna, such as the sand dollar Encope emarginata, can modify sediment properties and affect spatial distribution patterns of microphytobenthos and meiobenthos at different spatial scales. We adopted a spatial hierarchical approach composed of five spatial levels (km, 100 s m, 10 s m, 1 s m and cm) to describe variation patterns of microphytobenthos, meiobenthos and sediment variables in shallow subtidal regions in the subtropical Paranaguá Bay (Southern Brazil) with live E. emarginata (LE), dead E. emarginata (only skeletons — (DE), and no E. emarginata (WE). The overall structure of microphytobenthos and meiofauna was always less variable at WE and much of variation at the scale of 100 s m was related to variability within LE and DE, due to foraging activities or to the presence of shell hashes. Likewise, increased variability in chlorophyll-a and phaeopigment contents was observed among locations within LE, although textural parameters of sediment varied mainly at smaller scales. Variations within LE were related to changes on the amount and quality of food as a function of sediment heterogeneity induced by the foraging behavior of sand dollars. We provide strong evidence that top-down effects related to the occurrence of E. emarginata act in synergy with bottom-up structuring related to hydrodynamic processes in determining overall benthic spatial variability. Conversely, species richness is mainly influenced by environmental heterogeneity at small spatial scales (centimeters to meters), which creates a mosaic of microhabitats.     

Late Holocene paleoceanography and climate variability over the Mackenzie Slope (Beaufort Sea,Canadian Arctic)

Late Holocene paleoceanography and climate variability of the Southeastern Beaufort Sea (Canadian Arctic) have been investigated on the basis of sedimentary cores collected over the Mackenzie Slope. Piston, trigger and box cores were sampled at station 803 in 2004 aboard the CCGS Amundsen at 218 m water depth. The chronology of the piston core is constrained by 4 AMS-¹⁴C dates, as the sedimentation rate in the box core is assessed from ²¹⁰Pb data. We obtain a continuous composite sequence covering the last 4600 years, with a sedimentation rate of ~ 140 cm.kyr^? 1. Transfer functions (modern analogue technique) based on dinoflagellate cyst (dinocyst) assemblages were used to reconstruct the evolution of sea-surface conditions over the time period covered by the cores.Palynological data reveal that dinocyst assemblages are dominated by Operculodinium centrocarpum sensu lato (mean of 43.3%) throughout the core, with the accompanying taxa Brigantedinium spp. (19.6%), Islandinium minutum (15.6%) and cysts of Pentapharsodinium dalei (13.7%). Four zones have been established on the basis of dinocyst relative abundances. Dinocyst assemblage zone 1 (D1), from 4600 to 2700 cal years BP, is dominated by O. centrocarpum (mean of 49.0%). In zone D2 (2700–1500 cal years BP), the relative abundances of O. centrocarpum decrease (34.4%) in favour of the opportunistic, heterotrophic taxa Brigantedinium spp. (28.8%) and cysts of Polykrikos sp. var. arctic/quadratus (2.8%). Dinocyst zone D3 (1500–30 cal years BP or 450–1920 AD) is characterised by the high relative abundance of the peridinioid taxa I. minutum (19.9%). The last zone (D4), spanning from 1920 to 2004 AD, is again dominated by O. centrocarpum (44.5%), and shows low relative abundances of Brigantedinium spp. and cf. Echinidinium karaense.Quantitative reconstructions of past sea-surface parameters (August sea-surface temperature: SST, August sea-surface salinity: SSS, and duration of sea-ice cover) indicate relatively stable conditions over the last 4.6 kyr, with episodic cooling events (SST of ~ 1.5 °C below the modern value of 6 °C) that took place between 700 and 1820 AD. We associate the last and the longest of these cooling events (1560–1820 AD) with the Little Ice Age. Reconstructed SSS shows decadal oscillations since 1920 AD that we tentatively associate with the accumulation of freshwater by the Beaufort Gyre and the subsequent Great Salinity Anomalies. Our data suggest that similar salinity anomalies could have occurred ca. 1860 and 1790 AD.Stable isotopic data show a slight increase in δ¹³C values (from ~?27.1‰ at the base to ~?25.8‰ at the top) over the last 4.6 kyr that we associate with the gradual increase in atmospheric CO₂ concentration as recorded by Antarctic ice cores. Variations in the δ¹⁵N profile suggest variations in Pacific water influence from 4600 to ~ 1300 cal years BP, associated with centennial scale shifts of the Arctic Oscillation phases.     

Authigenic carbonates from methane seeps of the northern Congo fan: Microbial formation mechanism

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The δ¹³C values of the Hydrate Hole carbonates range from ?62.5‰ to ?46.3‰ PDB, while the δ¹³C values of the Diapir Field carbonate are somewhat higher, ranging from ?40.7‰ to ?30.7‰ PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of ¹⁸O (δ¹⁸O values as high as 5.2‰ PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO₃-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in δ¹³C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.     

Persian Gulf response to a wintertime shamal wind event

The results from a～1 km resolution HYbrid Coordinate Ocean Model (HYCOM), forced by 1/2° Navy Operational Global Atmospheric Prediction System (NOGAPS) atmospheric data, were used in order to study the dynamic response of the Persian Gulf to wintertime shamal forcing. Shamal winds are strong northwesterly winds that occur in the Persian Gulf area behind southeast moving cold fronts. The period from 20 November to 5 December 2004 included a well defined shamal event that lasted 4–5 days. In addition to strong winds (16 m s^?1) the winter shamal also brought cold dry air (T_a=20 °C, q_a=10 g kg^?1) which led to a net heat loss in excess of 1000 W m^?2 by increasing the latent heat flux. This resulted in SST cooling of up to 10 °C most notably in the northern and shallower shelf regions. A sensitivity experiment with a constant specific humidity of q_a=15 g kg^?1 confirmed that about 38% of net heat loss was due to the air–sea humidity differences. The time integral of SST cooling closely followed the air–sea heat loss, indicating an approximate one-dimensional vertical heat balance. It was found that the shamal induced convective vertical mixing provided a direct mechanism for the erosion of stratification and deepening of the mixed layer by 30 m. The strong wind not only strengthened the circulation in the entire Persian Gulf but also established a northwestward flowing Iranian Coastal Current (ICC, 25–30 cm s^?1) from the Strait of Hormuz to about 52°E, where it veered offshore. The strongest negative sea level of 25–40 cm was generated in the northernmost portion of the Gulf while the wind setup against the coast of the United Arab Emirates established a positive sea level of 15–30 cm. The transport through the Strait of Hormuz at 56.2°E indicated an enhanced outflow of 0.25 Sv (Sv≡10⁶ m³ s^?1) during 24 November followed by an equivalent inflow on the next day.     

Behaviors of dissolved and particulate Co,Ni, Cu,Zn, Cd and Pb during a mesoscale Fe-enrichment experiment (SEEDS II) in the western North Pacific

During mesoscale Fe enrichment (SEEDS II) in the western North Pacific ocean, we investigated dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb in seawater from both field observation and shipboard bottle incubation of a natural phytoplankton assemblage with Fe addition. Before the Fe enrichment, strong correlations between dissolved trace metals (Ni, Zn and Cd) and PO₄³⁻, and between particulate trace metals (Ni, Zn and Cd) and chlorophyll-a were obtained, suggesting that biogeochemical cycles mainly control the distributions of Ni, Zn and Cd in the study area. Average concentrations of dissolved Co, Ni, Cu, Zn, Cd and Pb in the surface mixed layer (0–20 m) were 70 pM, 4.9, 2.1, 1.6, 0.48 nM and 52 pM, respectively, and those for the particulate species were 1.7 pM, 0.052, 0.094, 0.46, 0.037 nM and 5.2 pM, respectively. After Fe enrichment, chlorophyll-a increased 3 fold (up to 3 μg L⁻¹) during developing phases of the bloom (<12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch hinted at an increase in the concentrations, but there were no analytically significant differences between concentrations inside and outside the patch. The bottle incubation with Fe addition (1 nM) showed an increase in chlorophyll-a (8.9 μg L⁻¹) and raised the particulate fraction up to 3–45% for all the metals, accompanying changes in Si/P, Zn/P and Cd/P. These results suggest that Fe addition lead to changes in biogeochemical cycling of trace metals. The comparison between the mesoscale Fe enrichment and the bottle incubation experiment suggests that although Fe was a limiting factor for the growth of phytoplankton, the enhanced biomass of mesozooplankton also limited the growth of phytoplankton and the transformation of trace metal speciation during the mesoscale Fe enrichment. Sediment trap data and the elemental ratios taken up by phytoplankton suggest that export loss was another reason that no detectable change in the concentrations of particulate trace metals was observed during the mesoscale Fe enrichment.     

Life history of the bathyal octopus Pteroctopus tetracirrhus (Mollusca,Cephalopoda) in the Mediterranean Sea

The life cycle of the deep-sea octopus Pteroctopus tetracirrhus was studied from monthly samples obtained throughout the year in different areas of the western Mediterranean (mainly around the Balearic Islands and along the coast of the Iberian Peninsula). A total of 373 individuals (205 females, 168 males) were analyzed; females ranged from 4.5 to 14.0 cm mantle length (ML) and males from 4.5 to 11.5 cm ML. There were few small-sized octopuses (<7 cm ML) in the samples, which might indicate that these individuals inhabit rocky grounds that are not accessible to trawlers or waters deeper than the maximum depth sampled (800 m). The species occurred more frequently around the Balearic Islands than along the Iberian Peninsula as they appeared in 20% and 7%, respectively, of the hauls in these areas. The octopus inhabits the lower continental shelf and upper slope in both areas, primarily between 200 and 500 m depth. Modal lengths were followed from autumn, when recruits were caught by trawlers, to summer, when reproduction took place. Females grew from 8 to 10 cm ML from winter to spring, but this modal size did not increase further in summer; males grew from 7 to 9 cm ML from winter to spring. The total disappearance of large individuals after summer suggests a life cycle lasting a single year. The evolution of the monthly mean sizes showed that the growth was best described by log-linear functions in both sexes. The length at first maturity was clearly higher in females (12 cm ML) than in males (8 cm ML). A total of 30 different prey items, belonging to four major taxonomic groups (crustaceans, osteichthyes, cephalopods and gastropods), were identified in the stomach contents. The diet of the octopus was based on crustaceans and teleosts, which accounted for 75% and 23% of the prey items, respectively. Cephalopods and gastropods were accessory prey as they only represented 1.6% and 0.7%, respectively, of the total. The octopus showed a marked preference for the benthic fish Symphurus nigrescens and the endobenthic crustacean Alpheus glaber. The bathymetric distribution of P. tetracirrhus coincides with those of these two main prey, which suggests that the distribution of the octopus might be strongly linked to its trophic resources.     

YREE sorption on hydrous ferric oxide in 0.5 M NaCl solutions: A model extension

Distribution coefficients, _iK_Fe, were measured for sorption of yttrium and the rare earth elements (YREEs) on hydrous ferric oxide (HFO) in 0.5 M NaCl solutions over the pH range 3.9–8.4 (T = 25 °C). An existing, non-electrostatic model [Quinn, K.A., Byrne, R.H., Schijf, J., 2006. Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: influence of pH and ionic strength. Mar. Chem. 99, 128–150] was modified to account for sorption of YREE–chloride complexes, as well as YREE–hydroxide complexes at elevated pH. The extended model, which allows calculation of _iK_Fe as a function of [H⁺], contains two parameters, _SK₁ and _SK₂, to describe the equilibrium between positive, neutral, and negative forms of the hydroxyl functional groups on the HFO surface. In addition, it contains several composite, conditional stability constants, A_n, that represent YREE bonding to the neutral groups with release of n protons and/or to the negatively charged groups with release of n ? 1 protons.In 0.5 M NaCl solutions, YREE sorption on HFO is weaker and less pH dependent, yielding only 0.7–0.9 protons per YREE cation on average, vs. about 1.5 at low ionic strength. This is due to enhanced deprotonation of the HFO surface (_SK₁ ~ 0, p_SK₂ = 6.16), leading to an increase in the proportion of negatively charged groups, which release fewer protons per YREE cation sorbed. On a logarithmic scale, _iK_Fe is a nearly linear function of pH, except at pH > 8 where cumulative sorption of YREE–hydroxide complexes causes it to rise more rapidly, especially for the heavy REEs. Both our own data and prior results from the literature are well described by the extended model, using only three adjustable parameters, A₁–A₃. The constant A₃, representing YREE bonding to the negatively charged groups with release of two protons, shows an excellent linear free-energy relation when plotted against the first YREE hydrolysis constant, β₁*. There is no evidence for YREE bonding to the positively charged groups (i.e., A₀ = 0).     

Kinetic study reveals weak Fe-binding ligand,which affects the solubility of Fe in the Scheldt estuary

The chemistry of dissolved Fe(III) was studied in the Scheldt estuary (The Netherlands). Two discrete size fractions of the dissolved bulk (< 0.2 μm and < 1 kDa) were considered at three salinities (S = 26, 10 and 0.3).Within the upper estuary, where fresh river water meets seawater, the dissolved Fe concentration decreases steeply with increasing salinity, for the fraction < 0.2 μm from 536 nM at S = 0.3 to 104 nM at S = 10 and for the fraction < 1 kDa from 102 nM to 36 nM Fe. Further downstream, in the middle and lower estuary, this decrease in the Fe concentration continues, but is far less pronounced. For all samples, the traditionally recognised dissolved strong organic Fe-binding ligand concentrations are lower than the dissolved Fe concentrations.Characteristics of dissolved Fe-binding ligands were determined by observing kinetic interactions with adsorptive cathodic stripping voltammetry. From these kinetic experiments we concluded that apart from the well-known strong Fe-binding organic ligands (L, logK′ = 19–22) also weak Fe-binding ligands (P) existed with an α value (binding potential = K′ · [P]) varying between 10^11.1 and 10^11.9. The presence of this relatively weak ligand explained the high concentrations of labile Fe present in both size fractions in the estuary. This weak ligand can retard or prevent a direct precipitation after an extra input of Fe.The dissociation rate constants of the weak ligand varied between 0.5 × 10^− 4 and 4.3 × 10^− 4 s^− 1. The rate constants of the strong organic ligand varied between k_d = 1.5 × 10^− 3–17 × 10^− 2 s^− 1 and k_f = 2.2 × 10⁸–2.7 × 10⁹ M^− 1 s^− 1. The dissociation rate constant of freshly amorphous Fe-hydroxide was found to be between 4.3 × 10^− 4 and 3.7 × 10^− 3 s^− 1, more labile or equal to the values found by Rose and Waite [Rose, A.L., Waite, T.D., 2003a. Kinetics of hydrolysis and precipitation of ferric iron in seawater. Environ. Sci. Technol., 37, 3897–3903.] for freshly precipitated Fe in seawater.Kinetic rate constants of Fe with the ligand TAC (2-(2-Thiazolylazo)-p-cresol) were also determined. The formation rate constant of Fe(TAC)₂ varied between 0.1 × 10⁸ and 3.6 × 10⁸ M^− 1 s^− 1, the dissociation rate constant between 0.2 × 10^− 5 and 17 × 10^− 5 s^− 1 for both S = 26 and S = 10. The conditional stability constant of Fe(TAC)₂ (β_Fe(TAC)2′) varied between 22 and 23.4 for S = 10 and S = 26 more or less equal to that known from the literature (logβ_Fe(TAC)2′ = 22.4; [Croot, P.L., Johansson, M., 2000. Determination of iron speciation by cathodic stripping voltammetry in seawater using the competing ligand 2-(2-Thiazolylazo)-p-cresol (TAC). Electroanalysis, 12, 565–576.]). However, at S = 0.3 the logβ_Fe(TAC)2′ was 25.3, three orders of magnitude higher. Apparently the application of TAC to samples of low salinity can only be done when the correct β_Fe(TAC)2′ is known.     

Air–sea CO2 fluxes in the north-eastern shelf of the Gulf of Cádiz (southwest Iberian Peninsula)

An intra-annual investigation of the fugacity of CO₂ (fCO₂) has been conducted in surface waters of the north-eastern shelf of the Gulf of Cádiz (SW Iberian Peninsula) in four cruises made in 2006 and 2007. Intra-annual variability of fCO₂ was assessed and is discussed in terms of mixing, temperature and biology. In the study area of the shelf, thermodynamic control over fCO₂ predominates from early May to late November, and this is opposite and similar in magnitude to the net biological effect. However, biological control over fCO₂ predominates during winter. The results suggest that surface waters in the coastal area are under-saturated with respect to atmospheric CO₂ during most of the year; therefore they represent a sink for atmospheric CO₂ between November and May (? 1.0 mmol m^? 2 day^? 1), but a weak source in June (1.3 mmol m^? 2 day^? 1). In contrast, the coastal ecosystems studied (the lower estuary of Guadalquivir Estuary and Bay of Cádiz) acted as a weak sink for atmospheric CO₂ during February (? 1.3 mmol m^? 2 day^? 1) and as a source between May and November (2.6 mmol m^? 2 day^? 1). The resulting mean annual CO₂ flux in the north-eastern shelf of the Gulf of Cádiz was ? 0.07 mol m^? 2 year^? 1 (? 0.2 mmol m^? 2 day^? 1), indicating that the area acts as a net sink on an annual basis.     

The feeding habits of slope dwelling macrourid fishes in the eastern North Pacific

The diet of slope dwelling macrourid fishes in the eastern North Pacific is poorly known. We collected several hundred stomach samples to investigate the feeding habits of Coryphaenoides acrolepis and Albatrossia pectoralis, the two dominant slope dwelling macrourids off the continental United States. Coryphaenoides acrolepis exhibited a pronounced ontogenetic shift in diet. Specimens <15 cm pre-anal fin length (PAF) consumed primarily polychaetes, amphipods, cumaceans and mysids, while larger individuals consumed increasingly larger, more pelagic prey such as fish, squid, and large crustaceans. Scavenging was also very important to specimens >15 cm with scavenged food constituting approximately 20% of the weight of total prey and occurring in approximately 20% of fish 21–29 cm. Albatrossia pectoralis consumed primarily midwater fish and squid, and we believe that it feeds in the water column. There were significant differences between the diets of A. pectoralis and C. acrolepis suggesting some degree of niche separation between macrourid species on the continental slope of the eastern North Pacific. Both species are at the top of the food web on the upper continental slope and, because of their abundance, may exert significant pressures on their prey populations.