Sources and biological fractionation of Silicon isotopes in the Eastern Equatorial Pacific

Silicon isotopes in dissolved silicic acid were measured in the upper four kilometers between 4°N and 3°S latitude at 110°W longitude in the eastern Equatorial Pacific. Silicon isotopes became progressively heavier with silicic acid depletion of surface water as expected from biological fractionation. The value of ε estimated by applying a steady-state isotope fractionation model to data from all stations between 4°N and 3°S was −0.77 ± 0.12‰ (std. err.). When the analysis was restricted to those stations whose temperature and salinity profiles indicated that they were directly influenced by upwelling of the Equatorial Undercurrent (EUC), the resulting value of ε was −1.08 ± 0.27‰ (std. err.) similar to the value established in culture studies (−1.1‰). When the non steady state Rayleigh model was applied to the same restricted data set the resulting value of ε was significantly more positive, −0.61 ± 0.16‰ (std. err.). To the extent that the equatorial system approximates a steady state these results support a value of −1.1‰ for the fractionation factor for isotopes of Si in the sea. Without the assumption of steady state the value of ε can only be constrained to be between −0.6 and −1.1‰. Silicic acid in Equatorial Pacific Deep Water below 2000 m had a near constant δ³⁰Si of +1.32 ± 0.05‰. That value is significantly more positive than obtained for North Pacific Deep Water at similar depths at stations to the northwest of our study area (0.9-1.0‰) and it is slightly less positive than new measures of the δ³⁰Si of silicic acid from the silicic acid plume centered over the Cascadia basin in the Northeast Pacific (Si(OH)₄ > 180  μM, δ³⁰Si = +1.46 ± 0.12‰ (SD, n = 4). We show that the data from the equator and Cascadia basin fit a general trend of increasing δ³⁰Si(OH)₄ with increasing silicic acid concentration in the deep sea, but that the isotope values from the Northeast Pacific are anomalously light. The observed level of variation in the silicon isotope composition of deep waters from this single ocean basin is considerably larger than that predicted by current models based on fractionation during opal formation with no isotope effect during dissolution. Confirmation of such high variability in deep water δ³⁰Si(OH)₄ within individual ocean basins will require reassessment of the mechanisms controlling the distribution of isotopes of silicon in the sea.     

Mechanisms controlling silicon isotope distribution in the Eastern Equatorial Pacific

The distribution of silicon isotopes along a meridional transect at 140°W longitude in the Eastern Equatorial Pacific was used to test the hypothesis that δ³⁰Si of silicic acid in surface waters should correlate with net silica production rates (gross silica production minus silica dissolution) rather than rates of gross silica production due to the opposing Si isotope fractionations associated with silica production and silica dissolution. Variations in δ³⁰Si appeared significantly correlated with net silica production rates in equatorial surface waters and not with gross production rates. Around the Equator, values of δ³⁰Si as low as deep water values occurred in the upper mesopelagic in a zone of net silica dissolution and high detrital biogenic silica content, where the release of low δ³⁰Si silicic acid from opal dissolution would be expected to decrease δ³⁰Si. The δ³⁰Si of the deep water at 140°W appears constant for depths >2000 m and is similar to the deep water at 110°W. This study brings to light the importance of considering Si fractionation during diatom silica dissolution, the biological fractionation during silica production and physical factors such as currents and mixing with adjacent water masses when interpreting silicon isotope distributions.     

A new index for variations in the position of the South Pacific convergence zone 1910/11–2011/2012

Quality controlled and recently homogenised mean sea level pressure records for the South Pacific are used to specify the location and variability of the South Pacific convergence zone (SPCZ) during the austral warm season (November–April). The SPCZ is the world’s largest rainfall band during the austral summer, when it dominates the climate of the South Pacific. A new index called the South Pacific convergence zone index (SPCZI) is derived, and is shown to be coherent with changes in low level wind convergence associated with the SPCZ. This index replaces the earlier SPCZ position index because it uses higher quality mean sea level pressure data than the superseded index and extends the time series further forward in time. The SPCZI allows interannual to decadal variability in the climate of the South Pacific to be tracked for more than a century from 1910/1911 to 2011/2012. During El Niño episodes the SPCZ is displaced by about 1°–3° east, and La Niña events 1°–3° west of the mean position on average. The index indicates a striking movement eastward for the period 1977/78–1998/99, compared with 1944/45–1976/77 in association with the Interdecadal Pacific oscillation (IPO). The eastward movement of the SPCZ in the late twentieth century is related to significant precipitation trends in the South Pacific region. Since 1998/99 the SPCZ has regressed westward with the negative phase change of the IPO. The long-term trend in the SPCZI is very small relative to the interannual to decadal variability and is not statistically significant, suggesting that there has been little overall change in the mean position of the SPCZ over the past century.     

生物硅的生成与溶解速率的研究-以胶州湾为例

营养盐的含量与元素间的比值直接控制着生态系统的生产力和浮游植物的种类组成.近岸海区硅藻可占初级生产的75%,但其生长速率受Si(OH)4含量的限制.胶州湾浮游植物的物种组成以硅藻为主.用29Si同位素示踪培养方法,采用四极杆质谱同位素稀释技术同时测定了胶州湾硅的生成速率与溶解速率.胶州湾生物硅(BSi)的含量为0.90～1.14 μmol/L,岩成硅(LSi)的含量为46.3～52.3 μmol/L.岩成硅是生物硅的约50倍.胶州湾BSi的含量处于世界近岸海区的低值范围,LSi的含量与LSi/BSi的比值均处于高值区.BSi的绝对生成速率为4～6 nmol/L*d,比生成速率为6～17/d.BSi的绝对溶解速率为<9 nmol/d,比溶解速率为<23/d.进一步开展胶州湾不同季节水体中BSi的生成速率与溶解速率的研究,是深入认识海湾浮游植物生长限制及其资源可持续利用的基础.     

Enumeration of the bacterial contamination of bivalves in monitoring the marine bacterial pollution

Marine organisms such as shellfish are capable of filtering large amounts of sea water and of retaining pathogenic bacteria. This property constitutes a way for evaluating the level of bacterial contamination in sea water. Despite some limitations, the use of shellfish as concentrating material appears to improve the bacterial enumeration results both in accuracy and consistency.     

Potentially mobile pools of phosphorus and silicon in sediment from the Bay of Brest: Interactions and implications for phosphorus dynamics

Competitive interactions between silicate and phosphate at ligand exchange sites in the sediment surface layer may increase the release of phosphorus (P) from the sediment into the water column. In this study, the role of silicon (Si) in the release of P from the sediment surface layer was studied in a marine estuarine environment, the Bay of Brest, with the aid of a sequential sediment fractionation procedure developed for P, and the addition of inorganic or diatom-bound Si to surface sediment samples in vitro. The potentially mobile pools of P in the surface sediment (loosely bound P + Fe/Al-bound-P) amounted to 5.0 μmol g⁻¹ dry sed., 42% of the total extractable and 33% of the total amount of P in the sediment, while the similarly extracted pools of Si were bigger (ca. 20 μmol g⁻¹ dry sed., 50% of the total extractable Si). Additions of inorganic Si increased the concentration of dissolved P in the sediment interstitial water in a bottle experiment, and the addition of both inorganic Si and cultivated diatoms to intact sediment cores increased the outward flux of dissolved P. Model calculations based on the regression equation from the bottle experiment and Si and P water column data showed that the sedimentation of spring diatoms could cause Si pulses to the sediment which would produce a P flux to the water column of ca. 44 μmol m⁻² d⁻¹. Field data from the bay show that in spring, decreases in P and Si and an increase in chl a due to diatom production are often followed by a small separate P peak which may be caused by Si-induced P fluxes from the sediment surface.     

Fractionation of silicon isotopes during biogenic silica dissolution

Silicon isotopes have been investigated for their potential to reveal both past and present patterns of silicic acid utilization, primarily by diatoms, in surface waters of the ocean. Interpretation of this proxy has thus far relied on characteristic trends in the isotope composition of the dissolved and particulate silicon pools in the upper ocean, as driven by biological fractionation during the production of biogenic silica (bSiO₂, or opal) by diatoms. However, other factors which may influence the silicon isotope composition of diatom opal, particularly post-formational aging and maturation processes, remain largely uninvestigated. Here, we report a consistent fractionation of silicon isotopes during the physicochemical dissolution of diatom bSiO₂ suspended in seawater under closed conditions. This fractionation acts counter to that occurring during bSiO₂ production and at about half its absolute magnitude, with dissolution discriminating against the release of the heavier isotopes of silicon at an enrichment factor ε_DSi–BSi of −0.55‰, corresponding to a fractionation factor α_30/28 of 0.99945. The enrichment factor did not vary with source material, indicating the lack of a significant species effect, or with temperature from 3 to 20 °C. Thus, the dissolution of bSiO₂ produces dissolved silicon with a δ³⁰Si value that is 0.55‰ more negative than its parent bSiO₂, an effect that must be accounted for when interpreting oceanic δ³⁰Si distributions. The δ³⁰Si values of both the dissolved and particulate silicon pools increased linearly as dissolution progressed, implying a measurable (±0.1‰) change in the relative δ³⁰Si of opal samples whenever the difference in preservation efficiency between them is >20%. This effect could account for 10–30% of the difference in diatom δ³⁰Si values observed between glacial and interglacial conditions. It is unlikely, however, that the inferred maximum possible change in δb³⁰SiO₂ of +0.55‰ would be manifested in situ, as a high mean percentage of dissolution would include complete loss of the more soluble members of the diatom assemblage.     

The impact of groundwater discharges on mercury partitioning, speciation and bioavailability to mussels in a coastal zone

The Mussel Watch program conducted along the French coasts for the last 20 years indicates that the highest mercury concentrations in the soft tissue of the blue mussel (Mytilus edulis) occur in animals from the eastern part of Seine Bay on the south coast of the English Channel, the “Pays de Caux”. This region is characterized by the presence of intertidal and submarine groundwater discharges, and no particular mercury effluent has been reported in its vicinity. Two groundwater emergence systems in the karstic coastal zone of the Pays de Caux (Etretat and Yport with slow and fast water percolation pathways respectively) were seasonally sampled to study mercury distribution, partitioning and speciation in water. Samples were also collected in the freshwater–seawater mixing zones in order to compare mercury concentrations and speciation between these “subterranean” or “groundwater” estuaries and the adjacent macrotidal Seine estuary, characterized by a high turbidity zone (HTZ). The mercury concentrations in the soft tissue of mussels from the same areas were monitored at the same time.The means of the “dissolved” (< 0.45 μm) mercury concentrations (HgT_D) in the groundwater springs were 0.99 ± 0.15 ng l^− 1 (n = 18) and 0.44 ± 0.17 ng l^− 1 (n = 17) at Etretat and Yport respectively. High HgT_D concentrations were associated with strong runoff over short water pathways during storm periods, while low concentrations were associated with long groundwater pathways. Mean particulate mercury concentrations were 0.22 ± 0.05 ng mg^− 1 (n = 16) and 0.16 ± 0.10 ng mg^− 1 (n = 17) at Etretat and Yport respectively, and decreased with increasing particle concentration probably as a result of dilution by particles from soil erosion. Groundwater mercury speciation was characterized by high reactive-to-total mercury ratios in the dissolved phase (HgR_D/HgT_D: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l^− 1). The HgT_D distributions in the Yport and Etretat mixing zones were similar (overall mean concentration of 0.73 ± 0.21 ng l^− 1, n = 43), but higher than those measured in the adjacent industrialized Seine estuary (mean: 0.31 ± 0.11 ng l^− 1, n = 67). In the coastal waters along the Pays de Caux dissolved monomethylmercury (MMHg_D) concentrations varied from 9.5 to 13.5 pg l^− 1 (2 to 8% of the HgT_D). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l⁻¹; 6–12% of the HgT_D). These groundwater karstic estuaries seem to be mostly characterized by the higher HgT_D and HgR_D concentrations than in the adjacent HTZ Seine estuary. While the HTZ of the Seine estuary acts as a dissolved mercury removal system, the low turbid mixing zone of the Pays de Caux receives the dissolved mercury inputs from the groundwater seepage with an apparent Hg transfer from the particulate phase to the “dissolved” phase (< 0.45 μm). In parallel, the soft tissue of mussels collected near the groundwater discharges, at Etretat and Yport, exhibited significantly higher values than those found in the mussel from the mouth of the Seine estuary. We observe that this difference mimics the differences found in the mercury distribution in the water, and argue that the dissolved phase of the groundwater estuaries and coastal particles are significant sources of bioavailable mercury for mussels.     

Orogen-parallel brittle extension as a major tectonic imprint in the Neogene evolution of the south-western Alpine arc

International Journal of Earth Sciences - We present a new analysis of the late Alpine brittle deformation in the southern branch of the western Alpine arc, focusing on the stack of internal...