Sulfur stable isotopes indicate the source of sinking materials in a coastal bay: Otsuchi Bay,Sanriku, Japan

Through 2004 and 2005, δ ³⁴S of sinking material from Otsuchi Bay was measured at the center and rocky shore of the bay. At the center of the bay δ ³⁴S was high (18∼21‰) in the material collected from April to November. However, δ ³⁴S was low (9∼14‰) in the material collected from December to March. The increase in δ ³⁴S in April was attributed to an increase in phytoplankton biomass because marine phytoplanktonic δ ³⁴S is high. When δ ³⁴S of sinking material was low, input of riverine material or bottom sediment resuspension were considered as the probable causes, because their δ ³⁴S is low. Marine sulfur was always high (more than 70%) at both stations. The difference between the δ ³⁴S of sinking material collected from the different sampling stations indicates that marine macroalgae contribute to sinking material near the shore when phytoplankton is scarce. In conclusion, the relative influence of different material sources to sinking materials could be successfully estimated using δ ³⁴S.     

Geochemistry of pore waters from the Xisha Trough, northern South China Sea and their implications for gas hydrates

This paper reports all available geochemical data on sediments and pore waters from the Xisha Trough on the northern continental margin of the South China Sea. The methane concentrations in marine sediments display a downhole increasing trend and their carbon isotopic compositions (δ ¹³C = −25 to −51‰) indicate a thermogenic origin. Pore water Cl⁻ concentrations show a range from 537 to 730 mM, and the high Cl⁻ samples also have higher concentrations of Br⁻, Na⁺, K⁺, and Mg²⁺, implying mixing between normal seawater and brine in the basin. The SO₄ ²⁻ concentrations of pore waters vary from 19.9 to 36.8 mM, and show a downhole decreasing trend. Calculated SMI (sulfate-methane interfaces) depths and sulfate gradients are between 21 and 47 mbsf, and between −0.7 and −1.7 mM/m, respectively, which are similar to values in gas hydrate locations worldwide and suggest a high methane flux in the basin. Overall, the geochemical data, together with geological and geophysical evidence, such as the high sedimentation rates, high organic carbon contents, thick sediment piles, salt and mud diapirs, active faulting, abundant thermogenic gases, and occurrence of huge bottom simulating reflector (BSR), are suggestive of a favorable condition for occurrence of gas hydrates in this region.     

Molecular and isotopic signatures in sediments and gas hydrate of the central/southwestern Ulleung Basin: high alkalinity escape fuelled by biogenically sourced methane

Natural marine gas hydrate was discovered in Korean territorial waters during a 2007 KIGAM cruise to the central/southwestern Ulleung Basin, East Sea. The first data on the geochemical characterization of hydrate-bound water and gas are presented here for cold seep site 07GHP-10 in the central basin sector, together with analogous data for four sites (07GHP-01, 07GHP-02, 07GHP-03, and 07GHP-14) where no hydrates were detected in other cores from the central/southwestern sectors. Hydrate-bound water displayed very low concentrations of major ions (Cl⁻, SO₄²⁻, Na⁺, Mg²⁺, K⁺, and Ca²⁺), and more positive δD (15.5‰) and δ¹⁸O (2.3‰) signatures compared to seawater. Cl^– freshening and more positive isotopic values were also observed in the pore water at gas hydrate site 07GHP-10. The inferred sulfate–methane interface (SMI) was very shallow (<5 mbsf) at least at four sites, suggesting the widespread occurrence of anaerobic oxidation of methane (AOM) at shallow sediment depths, and possibly high methane flux. Around the SMI, pore water alkalinity was very high (>40 mM), but the carbon isotopic ratios of dissolved inorganic carbon (δ¹³C_DIC) did not show minimum values typical of AOM. Moreover, macroscopic authigenic carbonates were not observed at any of the core sites. This can plausibly be explained by carbon with high δ¹³C values diffusing upward from below the SMI, increasing alkalinity via deep methanogenesis and eventually escaping as alkalinity into the water column, with minor precipitation as solid phase. This contrasts, but is not inconsistent with recent reports of methane-fuelled carbonate formation at other sites in the southwestern basin sector. Methane was the main hydrocarbon component (>99.85%) of headspace, void, and hydrate-bound gases, C₁/C₂₊ ratios were at least 1,000, and δ¹³C_CH4 and δD_CH4 values were in the typical range of methane generated by microbial reduction of CO₂. This is supported by the δ¹³C_C2H6 signatures of void and hydrate-bound gases, and helps clarify some contradictory interpretations existing for the Ulleung Basin as a whole. In combination, these findings suggest that deep biogenic gas and pore waters migrate upward through pathways such as hydrofractures, and measurably influence the shallow carbon cycle. As a result, cation-adjusted alkalinity/removed sulfate diagrams cannot always serve to estimate the degree of alkalinity produced by sulfate reduction and AOM in high methane flux areas.     

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.     

Stable Carbon and Nitrogen Isotopic Characterization of Organic Matter in a Mangrove Ecosystem on the Southwestern Coast of Thailand

Organic matter in a tropical mangrove ecosystem was characterized by stable carbon and nitrogen isotopic analyze, conducted on various organic samples, including land and mangrove plants, soils, particulate organic matter (POM), and sea and river sediments along the southwestern coast of Thailand. The δ¹³C values of land plants and POM in river water can be explained in terms of a greater influence of C₃ plants than C₄ plants in this area. The POM and sediments from the Trang River and Ko Talibong area showed systematically higher δ¹⁵N values than those from Ko Muk and other coastal areas. Organic matter in the Trang River might be influenced by nitrogen released from agricultural or human waste, which could affect the isotopic composition of POM and sediments in the Trang River estuary and along the coast near the river mouth. We used a stochastic method to estimate the contributions of four organic end-members, identifiable by their δ¹³C and δ¹⁵N values. The results implied that seagrasses were a major source of sedimentary organic matter, contributing 42 ± 5% in the Ko Muk area and 36 ± 5% in the Ko Talibong area. The contribution of coastal POM to sediments was estimated to be only 13% in Ko Muk and 19% in Ko Talibong. Mangrove plants contributed approximately 23% in both areas. It was concluded that seagrasses are an important source of sedimentary organic matter in this coastal region of southwestern Thailand. This revised version was published online in August 2006 with corrections to the Cover Date.     

<Superscript>234</Superscript>Th/<Superscript>238</Superscript>U disequilibrium and particulate organic carbon export in the northern South China Sea

We utilized ²³⁴Th, a naturally occurring radionuclide, to quantify the particulate organic carbon (POC) export rates in the northern South China Sea (SCS) based on data collected in July 2000 (summer), May 2001 (spring) and November 2002 (autumn). Th-234 deficit was enhanced with depth in the euphotic zone, reaching a subsurface maximum at the Chl-a maximum in most cases, as commonly observed in many oceanic regimes. Th-234 was in general in equilibrium with ²³⁸U at a depth of ∼100 m, the bottom of the euphotic zone. In this study the ²³⁴Th deficit appeared to be less significant in November than in July and May. A surface excess of ²³⁴Th relative to ²³⁸U was found in the summer over the shelf of the northern SCS, most likely due to the accumulation of suspended particles entrapped by a salinity front. Comparison of the ²³⁴Th fluxes from the upper 10 m water column between 2-D and traditional 1-D models revealed agreement within the errors of estimation, suggesting the applicability of the 1-D model to this particular shelf region. 1-D model-based ²³⁴Th fluxes were converted to POC export rates using the ratios of bottle POC to ²³⁴Th. The values ranged from 5.3 to 26.6 mmol C m⁻²d⁻¹ and were slightly higher than those in the southern SCS and other oligotrophic areas. POC export overall showed larger values in spring and summer than in autumn, the seasonality of which was, however, not significant. The highest POC export rate (26.6 mmol C m⁻²d⁻¹) appeared at the shelf break in spring (May), when Chl-a increased and the community structure changed from pico-phytoplankton (<2 μm) dominated to nano-phytoplankton (2–20 μm) and micro-phytoplankton (20–200 μm) dominated.     

O<Subscript>2</Subscript> consumption rate and its isotopic fractionation factor in the deep water of the Philippine Sea

Concentration and stable isotopic compositions (δ ¹⁸O) of dissolved O₂ were measured in seawater samples collected from the Philippine Sea in June 2006. The in-situ O₂ consumption rate and the isotopic fractionation factor (α _r ) during dissolved O₂ consumption were obtained from field observations by applying a vertical one-dimensional advection diffusion model to the deep water mass of about 1000–4000 m. The average O₂ consumption rate and α _r were, respectively, 0.11 ± 0.07 μmol kg⁻¹yr⁻¹ and 0.990 ± 0.001. These estimated values agree well with values from earlier estimations of Pacific deep water. The in-situ O₂ consumption rates are two or more times higher north of 20°N, although the value of α _r was not significantly different between the north and south. Its levels varied rapidly in the water mass of less about 2000 m depth. These results suggest that organic matter from the continent imparts a meaningful contribution to the upper water in the northern part of the area; it might produce the strong O₂ minimum that is evident in the water mass from about 1000–2000 m in the northern part of the Philippine Sea.     

海底地下水排放对典型红树林蓝碳收支的影响

海底地下水排放(Submarine Groundwater Discharge,SGD)是陆海相互作用的重要表现形式之一,其携带的物质对近岸海域生源要素的收支有重要影响。本文利用222Rn示踪技术估算了我国典型红树林海湾—广西珍珠湾在2019年枯季(1月)SGD携带的碳通量。调查发现,地下水中222Rn活度、溶解无机碳(DIC)和溶解有机碳(DOC)的平均浓度均高于河水和湾内表层海水。利用222Rn质量平衡模型估算得到珍珠湾SGD速率为(0.36±0.36) m/d,SGD输入到珍珠湾的DIC和DOC通量分别为(2.41±2.63)×107 mol/d和(1.96±2.20)×106 mol/d。珍珠湾溶解碳的源汇收支表明,SGD携带的DIC和DOC分别占珍珠湾总DIC和总DOC来源的91%和89%。因此,SGD携带的DIC和DOC是珍珠湾DIC和DOC的主要来源,是海岸带蓝碳收支和生物地球化学循环过程中的重要组成。     

考洲洋牡蛎养殖海域海-气界面CO2交换通量的时空变化

根据2018年7月、11月和2019年1月、4月对广东考洲洋牡蛎养殖海域进行4个季节调查获得的p H、溶解无机碳(DIC)、水温、盐度、溶解氧(DO)及叶绿素a(Chla)等数据,估算该区域表层海水溶解无机碳体系各分量的浓度、初级生产力(PP)、表层海水CO₂分压[p(CO₂)]和海-气界面CO₂交换通量(FCO₂),分析牡蛎养殖活动对养殖区碳循环的影响。结果表明:牡蛎养殖区表层海水中Chl a、DIC、HCO₃^–和PP显著低于非养殖区;养殖淡季表层海水中pH、DO、DIC、HCO₃^–、和CO₃^2–显著大于养殖旺季,养殖旺季的p(CO₂)和FCO₂显著大于养殖淡季。牡蛎养殖区表层海水夏季、秋季、冬季和春季的海-气界面CO₂交换通量FCO₂平均值分别是(42.04±9.56)、(276...     

Variability of organic δC and C/N in the Mersey Estuary, U.K. and its implications for sea-level reconstruction studies

Microfossil analysis (e.g. diatoms, foraminifera and pollen) represents the cornerstone of Holocene relative sea-level (RSL) reconstruction because their distribution in the contemporary inter-tidal zone is principally controlled by ground elevation within the tidal frame. A combination of poor microfossil preservation and a limited range in the sediment record may severely restrict the accuracy of resulting RSL reconstructions. Organic δ¹³C and C/N analysis of inter-tidal sediments have shown some potential as coastal palaeoenvironmental proxies. Here we assess their viability for reconstructing RSL change by examining patterns of organic δ¹³C and C/N values in a modern estuarine environment. δ¹³C and C/N analysis of bulk organic inter-tidal sediments and vegetation, as well as suspended and bedload organic sediments of the Mersey Estuary, U.K., demonstrate that the two main sources of organic carbon to surface saltmarsh sediments (terrestrial vegetation and tidal-derived particulate organic matter) have distinctive δ¹³C and C/N signatures. The resulting relationship between ground elevation within the tidal frame and surface sediment δ¹³C and C/N is unaffected by decompositional changes. The potential of this technique for RSL reconstruction is demonstrated by the analysis of part of an early Holocene sediment core from the Mersey Estuary. Organic δ¹³C and C/N analysis is less time consuming than microfossil analysis and is likely to provide continuous records of RSL change.     

A carbon,nitrogen, and sulfur elemental and isotopic study in dated sediment cores from the Louisiana Shelf

Three sediment cores were collected off the Mississippi River delta on the Louisiana Shelf at sites that are variably influenced by recurring, summer-time water-column hypoxia and fluvial loadings. The cores, with established chronology, were analyzed for their respective carbon, nitrogen, and sulfur elemental and isotopic composition to examine variable organic matter inputs, and to assess the sediment record for possible evidence of hypoxic events. Sediment from site MRJ03-3, which is located close to the Mississippi Canyon and generally not influenced by summer-time hypoxia, is typical of marine sediment in that it contains mostly marine algae and fine-grained material from the erosion of terrestrial C4 plants. Sediment from site MRJ03-2, located closer to the mouth of the Mississippi River and at the periphery of the hypoxic zone (annual recurrence of summer-time hypoxia >50%), is similar in composition to core MRJ03-3, but exhibits more isotopic and elemental variability down-core, suggesting that this site is more directly influenced by river discharge. Site MRJ03-5 is located in an area of recurring hypoxia (annual recurrence >75%), and is isotopically and elementally distinct from the other two cores. The carbon and nitrogen isotopic composition of this core prior to 1960 is similar to average particulate organic matter from the lower Mississippi River, and approaches the composition of C3 plants. This site likely receives a greater input of local terrestrial organic matter to the sediment. After 1960 and to the present, a gradual shift to higher values of δ¹³C and δ¹⁵N and lower C:N ratios suggests that algal input to these shelf sediments increased as a result of increased productivity and hypoxia. The values of C:S and δ³⁴S reflect site-specific processes that may be influenced by the higher likelihood of recurring seasonal hypoxia. In particular, the temporal variations in the C:S and δ³⁴S down-core are likely caused by changes in the rate of sulfate reduction, and hence the degree of hypoxia in the overlying water column. Based principally on the down-core C:N and C:S ratios and δ¹³C and δ³⁴S profiles, sites MRJ03-3 and MRJ03-2 generally reflect more marine organic matter inputs, while site MRJ03-5 appears to be more influenced by terrestrial deposition.     

Spatial variability in the primary productivity in the East China Sea and its adjacent waters

Primary productivity in the East China Sea and its adjacent area was measured by the¹³C tracer method during winter, summer and fall in 1993 and 1994. The depth-integrated primary productivity in the Kuroshio Current ranged from 220 to 350 mgC m⁻²d⁻¹, and showed little seasonal variability. High primary productivity (above 570 mgC m⁻²d⁻¹) was measured at the center of the continental shelf throughout the observation period. The productivity at the station nearest to the Changjiang estuary exhibited a distinctive seasonal change from 68 to 1,500 mgC m⁻²d⁻¹. Depth-integrated primary productivity was 2.7 times higher in the shelf area than the rates at the Kuroshio Current. High chlorophyll-a specific productivity (mgC mgChl.-a⁻²d⁻¹) throughout the euphotic zone was mainly found in the shelf area rather than off-shelf area, probably due to higher nutrient availability and higher activity of phytoplankton at the subsurface layer in the shelf area.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Helium and oxygen isotope analyses of hydrothermal fluids from the East Pacific Rise between 17°S and 19°S

 Hydrothermal vent fields south of the Garret Fracture zone were sampled for the isotope composition of helium and oxygen ([¹⁸O]H₂O/[¹⁶OH₂O). The helium isotopes end-member (³He / ⁴He=8.3×R _a and [⁴He]≈1.2–2.4×10^-5 cm³ STP g^-1) is quite similar to other known hydrothermal sites pointing to the homogeneous helium composition of the upper mantle. The δ¹⁸O end-member value (δ¹⁸O≈0.5–0.6‰) confirms previous suggestions from other sites and from isotope modeling, that hydrothermal fluids are slightly enriched in ¹⁸O relative to the ocean as a result of water–rock interactions at high temperature. Received: 11 December 1995/Revision received: 20 December 1996     

Determination of phospholipid fatty acid structures and stable carbon isotope compositions of deep-sea sediments of the Northwest Pacific, ODP site 1179

Sediment samples ranging from 0.05 to 278 m below sea floor (mbsf) at a Northwest Pacific deep-water (5564 mbsl) site (ODP Leg 191, Site 1179) were analyzed for phospholipid fatty acids (PLFAs). Total PLFA concentrations decreased by a factor of three over the first meter of sediment and then decreased at a slower rate to approximately 30 mbsf. The sharp decrease over the first meter corresponds to the depth of nitrate and Mn(IV) reduction as indicated by pore water chemistry. PLFA-based cell numbers at site 1179 had a similar depth profile as that for Acridine orange direct cell counts previously made on ODP site 1149 sediments which have a similar water depth and lithology. The mole percentage of straight chain saturated PLFAs increases with depth, with a large shift between the 0.95 and 3.95 mbsf samples. PLFA stable carbon isotope ratios were determined for sediments from 0.05 to 4.53 mbsf and showed a general trend toward more depleted δ¹³C values with depth. Both of these observations may indicate a shift in the bacterial community with depth across the different redox zones inferred from pore water chemistry data. The PLFA 10me16:0, which has been attributed to the bacterial genera Desulfobacter in many marine sediments, showed the greatest isotopic depletion, decreasing from − 20 to − 35‰ over the first meter of sediment. Pore water chemistry suggested that sulfate reduction was absent or minimal over this same sediment interval. However, 10me16:0 has been shown to be produced by recently discovered anaerobic ammonium oxidizing (anammox) bacteria which are known chemoautotrophs. The increasing depletion in δ¹³C of 10me16:0 with the unusually lower concentration of ammonium and linear decrease of nitrate concentration is consistent with a scenario of anammox bacteria mediating the oxidation of ammonium via nitrite, an intermediate of nitrate reduction.     

Helium Isotopes in Pacific Waters from Adjacent Region of Honshu, Japan

We have measured helium isotopic ratios of thirty-seven Pacific water samples from various depths collected in adjacent regions of Honshu, Japan. The ³He/⁴He ratios vary significantly from 0.989 R _atm to 1.208 R _atm where R _atm is the atmospheric ratio of 1.39 × 10⁻⁶. The mid-depth (750–1500 m) profile of ³He/⁴He ratios at ST-1 located Northwestern Pacific Ocean east of Japan (Off Joban; 37°00′ N, 142°40′ E) is significantly different from that at ST-2 of the Northern Philippine Sea south of Japan (Nankai Trough; 33°07′ N, 139°59′ E), suggesting that these waters were separated by a topographic barrier, the Izu-Ogasawara Ridge. Taking ³He/⁴He data of the Geosecs expeditions in the western North Pacific, an extensive plume of 15% excess ³He relative to the air may be traced at ST-1 over 12,000 kilometers to the northwest of the East Pacific Rise where the mantle helium may originate. The 20% excess found at ST-2 may be attributable to the additional source of the subduction-type mantle helium in the Okinawa Trough. A 15% excess of ³He has also been discovered at a depth of about 1000∼1500 m at ST-3 adjacent to Miyakejima Island (33°57′ N, 139°22′ E) and ST-4 of Sagami Bay (35°00′ N, 139°22′ E). It is confirmed that mid-depth all over the western North Pacific water is affected by the mantle helium with a high ³He/⁴He ratio. This revised version was published online in July 2006 with corrections to the Cover Date.     

Assessment of nitrogen loading from the Kiso-Sansen Rivers into Ise Bay using stable isotopes

Concentrations of particulate organic nitrogen (PN), dissolved inorganic nitrogen (DIN), and their nitrogen isotope ratios (δ ¹⁵N) in the Kiso-Sansen Rivers were determined from monthly observations over the course of a year to assess variations in the form and sources of riverine nitrogen discharged into Ise Bay. The δ ¹⁵N values of NO₃ ⁻ observed in the Kiso-Sansen Rivers showed a logarithmic decreasing trend from 8 to 0‰, which varied with the river discharge, indicating mixing between point sources with high δ ¹⁵N and non-point sources with low δ ¹⁵N. The influence of isotope fractionation of in situ biogeochemical processes (mainly DIN assimilation by phytoplankton) on δ ¹⁵N of NO₃ ⁻ was negligible, because sufficient concentrations of NH₄ ⁺ for phytoplankton demand would inhibit the assimilation of NO₃ ⁻. A simple relationship between river discharge and δ ¹⁵N of NO₃ ⁻ showed that the fraction of total NO₃ ⁻ flux arising from point sources increased from 4.0–6.3% (1.1–1.8 tN day⁻¹) during higher discharge (>600 m³ s⁻¹) to 30.2–48.3% (2.6–4.1 tN day⁻¹) during lower discharge (<300 m³ s⁻¹). Riverine NO₃ ⁻ discharge from the Kiso-Sansen Rivers can explain 75% of the variations in surface NO₃ ⁻ at the head of Ise Bay over the year.     

Time-series observation of dissolved inorganic carbon and nutrients in the northwestern North Pacific

Time-series measurements of dissolved inorganic carbon (DIC) and nutrient concentrations were conducted in the northwestern North Pacific from October 2002 to August 2004. Assuming that data obtained in different years represented time-series seasonal data for a single year, vertical distributions of DIC and nutrients showed large seasonal variabilities in the surface layer (∼100 m). Seasonal variabilities in normalized DIC (nDIC) and nitrate concentrations at the sea surface were estimated to be 81–113 μmol kg⁻¹ and 12.7–15.7 μmol kg⁻¹, respectively, in the Western Subarctic Gyre. The variability in nutrients between May and July was generally at least double that in other seasons. In the Western Subarctic Gyre, estimations based on statistical analyses revealed that seasonal new production was 39–61 gC m⁻² and tended to be higher in the southwestern regions or coastal regions. The seasonal new productions in the northwestern North Pacific were two or more times higher than in the North Pacific subtropical gyre and the northeastern North Pacific. It is likely that this difference is due to spatial variations in the concentrations of trace metals and the species of phytoplankton present. In addition, from estimations of surface pCO₂ it was verified that the Western Subarctic Gyre is a source of atmospheric CO₂ between February and May and a sink for CO₂ between July and October.     

Stable isotope and chemical composition of pearls: Biomineralization in cultured pearl oysters in ago bay, Japan

The δ¹⁸O, δ¹³C and trace element composition of pearls collected from Ago Bay, Japan, were investigated in order to evaluate biomineralization in the cultured pearl oyster (Pinctada fucata martensii). The oxygen isotopic data suggest that the pearls were produced around 23–24°C, mainly in June to early July, which is consistent with their occurrence in the field. Therefore the pearls were produced under or close to isotopic equilibrium conditions, although they showed high calcification rates (higher than 0.2–1.0 g cm^{− 2}yr⁻¹) under which, for example, coral skeletons (calcification rate ∼0.28 g cm^{− 2}yr⁻¹) often show non-equilibrium isotope partitioning. The δ¹³C values were ∼− 2.9‰ lower than those calculated for offshore waters under equilibrium conditions. This may be due to low-δ¹³C bottom waters resulting from the degradation of organic matter (OM) or to a contribution of low-δ ¹³C food. In the latter case, a simple mass balance calculation gives a respiration component of 14%. Twelve trace elements of bulk pearl samples were classified into four groups on the basis of their enrichment/depletion patterns relative to seawater and inter-element relationships: group 1, Co, Cr, Pb; group 2, Ba, Cs, U; group 3, Cu, Sn, V, and group 4, Mn, Rb, Mo. Comparison with coral skeletons suggests that Ba and Mn (groups 2 and 4) were definitely much enriched in proteinaceous OM relative to aragonite crystals in pearls and that V (group 3) in pearls showed only slight enrichment in the organicrich layer. By contrast, the other elements showed small differences between both layers (enrichment factor of <3), suggesting that these elements occur largely in aragonite crystals.     

Stable isotope analysis of some representative fish and invertebrates of the Newfoundland and Labrador continental shelf food web

We examined stable carbon and nitrogen isotopic signatures of 17 fish and 16 invertebrate taxa common to the Newfoundland and Labrador (NL) continental shelf food web. Particular sampling emphasis was placed on Atlantic cod (Gadus morhua) and related prey species (e.g. shrimp, Pandalus borealis, and capelin, Mallotus villosus). We found highly significant (p < 0.0001) differences between near-shore (bays) and offshore (shelf edge) δ¹⁵N signatures for cod, ‘other fish’ (pooled) and invertebrates (pooled). In contrast, there were only minor differences in δ¹³C signatures of ‘other fish’ (p < 0.05) and no difference for cod and invertebrates among the two habitats. We sampled at two times of the year (January and June) and found no systematic effect of season on both δ¹³C and δ¹⁵N in cod, ‘other fish’ and invertebrates. We calculated isotopic fractionation factors for cod from the entire shelf (mixed diet) and for cod with diets composed mainly of capelin or shrimp. These values ranged between 2.2‰ and 3.9‰ for δ¹⁵N and −0.4‰ and 0.8‰ for δ¹³C and, for δ¹⁵N, may reflect diet-related differences in bioenergetic status. We discuss potential mechanisms for near-shore versus offshore enrichment of δ¹⁵N signatures, and demonstrate the implications of this spatial variation on δ¹⁵N-derived trophic position estimates.