Sources of δ15N variability in sinking particulate nitrogen in the Cariaco Basin,Venezuela

Ten years of monthly observations of the δ¹⁵N of sinking particulate nitrogen (δ¹⁵N–PN (in ‰ versus atmospheric N₂)=[(¹⁵N/¹⁴N)_sample/(¹⁵N/¹⁴N)_standard)−1]1000) in the Cariaco Basin, Venezuela, confirm that the basin's bottom sediments store information about nitrogen dynamics related to seasonal and interannual variability in regional surface ocean processes. During the upwelling period of the southern Caribbean Sea (February–April), the δ¹⁵N–PN is similar to that of the thermocline nitrate (∼3.5‰). This nitrate is imported into the Cariaco Basin with Subtropical Underwater (SUW), which wells up near the coast. Thus, particles generated by phytoplankton photosynthesis during this productive period bear a sub-tropical North Atlantic isotopic imprint of N₂ fixation (low compared to the global average of nitrate δ¹⁵N≈5‰). During the non-upwelling period when surface waters are stratified (September–November), the δ¹⁵N–PN is also 3.5–4.0‰, and reflects a mixture of local N₂ fixation within the mixed layer, inputs of terrigenous organic matter and SUW nitrate consumption by phytoplankton below the mixed layer, which most likely exerts the strongest control on the δ¹⁵N–PN signal during this time. In the transition periods of May–July and December–January, the δ¹⁵N–PN increases to 4.5–6.5‰. This coincides with maxima of continental material fluxes (terrestrial PON δ¹⁵N is >6‰) into the Cariaco Basin. The δ¹⁵N signal in the sediments of the Cariaco Basin thus provides information about the relative strength of the local coastal upwelling, the relative input of continental material via river runoff, and local N₂ fixation. The findings contribute to interpretations of the basin's paleoclimatic nitrogen cycle variations based on observations of the sedimentary δ¹⁵N record at this location.     

The supply and preservation of ancient and modern components of organic carbon in the Canadian Beaufort Shelf of the Arctic Ocean

The provenance of organic matter in sediments from the Mackenzie River and Beaufort Shelf was investigated using the stable carbon and radiocarbon isotopic compositions of bulk organic matter and the stable carbon isotopic compositions of individual organic compounds, including lignin-derived phenols and lipid-derived fatty acids. Most river suspended sediments and shelf surface sediments contained organic carbon characterized by highly depleted Δ¹⁴C values that were consistent with average radiocarbon ages exceeding 7000 years. The stable carbon isotopic signatures of lignin phenols were uniformly depleted (−25≥δ¹³C≥−32‰), indicating the predominant contributions of C₃ vascular plant sources. The isotopic compositions of C₁₄ and C₁₆ fatty acids exhibited important contrasts between the river (−36‰ to −40‰) and shelf (−25‰ to −29‰) sediments that were consistent with contributions from freshwater algae and/or vascular plants in the former and marine phytoplankton in the latter. Using ¹⁴C isotopic mass balance, the abundances of modern and ancient organic matter were quantitatively constrained. The fate of organic matter in the Beaufort Shelf was explored by normalizing these abundances to the specific surface area of sediments. Ancient organic carbon, which may include old pre-aged soil material as well as fossil bitumen or kerogen, accounted for the majority (∼70%) of the particulate organic matter exported by the Mackenzie River and deposited in surface sediments of the Beaufort Shelf. Modern organic carbon accounted for ∼30% in both river and shelf sediments, with significant contributions from vascular plant-derived materials in both river and shelf samples and from marine algae in the shelf sediments. Respiration (and/or leaching) of particle-bound marine organic matter dominates the carbon metabolism in the Mackenzie Delta/Beaufort Shelf region. However, land-derived pools, including modern carbon derived from vascular plants as well as ancient carbon also appeared to undergo a degree of post-depositional degradation prior to burial in the shelf. These novel source apportionments are reflected in an updated carbon budget for the study area.     

Fluxes,source and transport of organic matter in the western Sea of Okhotsk: Stable carbon isotopic ratios of n-alkanes and total organic carbon

Settling particles and surface sediments collected from the western region of the Sea of Okhotsk were analyzed for total organic carbon (TOC), long-chain n-alkanes and their stable carbon isotope ratio (δ¹³C) to investigate sources and transport of total and terrestrial organic matter in the western region of the sea. The δ¹³C measurements of TOC in time-series sediment traps indicate lateral transport of resuspended organic matter from the northwestern continental shelf to the area off Sakhalin via the dense shelf water (DSW) flow at intermediate depth. The n-alkanes in the surface sediments showed strong odd carbon number predominance with relatively lighter δ¹³C values (from −33‰ to −30‰). They fall within the typical values of C3-angiosperms, which is the main vegetation in east Russia, including the Amur River basin. On the other hand, the molecular distributions and δ¹³C values of n-alkanes in the settling particles clearly showed two different sources: terrestrial plant and petroleum in the Sea of Okhotsk. We reconstructed seasonal change in the fluxes of terrestrial n-alkanes in settling particles using the mixing model proposed by Lichtfouse and Eglinton [1995. ¹³C and ¹⁴C evidence of a soil by fossil fuel and reconstruction of the composition of the pollutant. Organic Geochemistry 23, 969–973]. Results of the terrestrial n-alkane fluxes indicate that there are two transport pathways of terrestrial plant n-alkanes to sediments off Sakhalin, the Sea of Okhotsk. One is lateral transport of resuspended particles with lithogenic material from the northwestern continental shelf by the DSW flow. Another is the vertical transport of terrestrial plant n-alkanes, which is independent of transport of lithogenic material. The latter may include dry/wet deposition of aerosol particles derived from terrestrial higher plants possibly associated with forest fires in Siberia.     

胶州湾沉积物中有机质的来源与组成及其对百年尺度环境变化的指示

The Jiaozhou Bay is characterized by heavy eutrophication that is associated with intensive anthropogenic activities. Four core sediments from the Jiaozhou Bay are analyzed using bulk technologies, including sedimentary total organic carbon(TOC), total nitrogen(TN), the stable carbon(δ~(13)C) and nitrogen(δ~(15) N) isotopic composition to obtain the comprehensive understanding of the source and composition of sedimentary organic matter and further shed light on the environmental changes of the Jiaozhou Bay on a centennial time scale.Results suggest that the TOC and TN concentrations increase in the upper core, having indicated a probable eutrophication process since the 1920 s in the inner bay and the 2000 s in the bay mouth. The TOC and TN concentrations outside the bay have also changed since 1916 owing to the variation of terrigenous input.Considering TOC/TN ratio, δ~(13) C and δ~(15) N, it can be concluded there is a mixture of terrigenous and marine organic matter sources in the study area. A simple two end-member(terrigenous and marine) mixing model usingδ~(13) C indicats that 45%–79% of TOC in the Jiaozhou Bay is from the marine source. The environmental changes of the Jiaozhou Bay are recorded by geochemical proxies, which are influenced by the intensive anthropogenic activities(e.g., extensive use of fertilizers, and discharge of sewage) and climate changes(e.g., rainfall).     

Radiocarbon and stable carbon isotope compositions of organic compound classes in sediments from the NE Pacific and Southern Oceans

Radiocarbon (Δ¹⁴C) abundance and stable carbon isotope (δ¹³C) compositions were measured for total lipid, total hydrolyzable amino acids (THAA), total carbohydrates (TCHO), and acid-insoluble organic fractions separated from phytoplankton, zooplankton, and sediment cores collected from two abyssal sites, one in the northeast (NE) Pacific Ocean and one in the Southern Ocean. These results are compared with those obtained for a separate core from the NE Pacific and reported by Wang et al. [Geochim. Cosmochim. Acta 62 (1998) 1365.]. An uncharacterized acid-insoluble fraction dominated (43–57%) the sediment TOC pool at both sites. Sediment collected from the NE Pacific exhibited higher TOC, TN. and higher Δ¹⁴C values and contained both labile (THAA and TCHO) and refractory (lipid and acid-insoluble) fractions. In contrast, sediment from the Southern Ocean had much lower TOC and Δ¹⁴C values, which indicated that organic matter was extremely refractory. Sedimentation rates calculated from ¹⁴C ages of TOC for both sites indicate that the differences in the organic composition and Δ¹⁴C signatures of organic matter in the sediments likely resulted from the differences in production and deposition of organic matter to the sediment, and the diagenetic stages of sedimentary organic matter in the two oceans.Unlike Δ¹⁴C, stable carbon isotopic (δ¹³C) compositions of TOC in the sediments of the two oceans had similar values, which reflect not only the organic matter input from marine-derived sources but also the nature of degraded, predominately uncharacterized organic fraction in these sediments. The differences in δ¹³C values among the compound classes in sediments at both sites can be attributed to the carbon isotopic signatures in original sources during photosynthesis and associated environmental factors. Preferential degradation of organic matter and heterotrophic effects may also play important roles for the observed δ¹³C variations and these effects need to be further investigated.     

Stable isotope constraints on the nitrogen cycle of the Mediterranean Sea water column

We used the nitrogen isotope ratio of algae, suspended particles and nitrate in the water column to track spatial variations in the marine nitrogen cycle in the Mediterranean Sea. Surface PON (5–74 m) was more depleted in ¹⁵N in the eastern basin (−0.3±0.5‰) than in the western basin (+2.4±1.4‰), suggesting that nitrogen supplied by biological N₂ fixation may be an important source of new nitrogen in the eastern basin, where preformed nitrate from the Atlantic Ocean could have been depleted during its transit eastward. The δ¹⁵N of nitrate in the deep Mediterranean (∼3‰ in the western-most Mediterranean and decreasing toward the east) is significantly lower than nitrate at similar depths from the North Atlantic (4.8–5‰), also suggesting an important role for N₂ fixation. The eastward decrease in the δ¹⁵N of surface PON is greater than the eastward decrease in the δ¹⁵N of the subsurface nitrate, implying that the amount of N₂ fixation in the eastern Mediterranean is great enough to cause a major divergence in the δ¹⁵N of phytoplankton biomass from the δ¹⁵N of the nitrate upwelled from below. Variations in productivity associated with frontal processes, including shoaling of the nitracline, did not lead to detectable variations in the δ¹⁵N of PON. This indicates that no differential fertilization or productivity gradient occurred in the Almerian/Oran area. Our results are consistent with a lack of gradient in chlorophyll-a (chl-a) and nitrate concentration in the Alboran Sea. ¹⁵N enrichment in particles below 500 m depth was detected in the Alboran Sea with respect to surface PON, reaching an average value of +7.4±0.7‰. The δ¹⁵N in sinking particles caught at 100 m depth (4.9–5.6‰) was intermediate between suspended surface and suspended deep particles. We found a consistent difference in the isotopic composition of nitrogen in PON compared with that of chlorophyll (Δδ¹⁵N[PON-chlorin]=+6.4±1.4‰) in the surface, similar to the offset reported earlier in cultures for cellular N and chl-a. This indicates that δ¹⁵N of phytoplankton biomass was retained in surface PON, and that alteration of the isotopic signal of PON at depth was due to heterotrophic activity.     

Origins and maturity of organic matter in mid-Cretaceous black shales from ODP Site 1138 on the Kerguelen Plateau

We have conducted elemental, isotopic, and Rock-Eval analyses of Cenomanian–Santonian sediment samples from ODP Site 1138 in the southern Indian Ocean to assess the origin and thermal maturity of organic matter in mid-Cretaceous black shales found at this high-latitude location. Total organic carbon (TOC) concentrations range between 1 and 20 wt% in black to medium-gray sediments deposited around the Cenomanian–Turonian boundary. Results of Rock-Eval pyrolysis indicate that the organic matter is algal Type II material that has experienced modest alteration. Important contributions of nitrogen-fixing bacteria to the amplified production of organic matter implied by the high TOC concentrations is recorded in δ¹⁵N values between −5 and 1‰, and the existence of a near-surface intensified oxygen minimum zone that favored organic carbon preservation is implied by TOC/TN ratios between 20 and 40. In contrast to the marine nature of the organic matter in the Cenomanian–Turonian boundary section, deeper sediments at Site 1138 contain evidence of contributions land-derived organic matter that implies the former presence of forests on the Kerguelen Plateau until the earliest Cenomanian.     

Original oxygen isotopic composition of planktic foraminifers preserved in diagenetically altered Pleistocene shallow-marine carbonates

The original stable isotopic composition of low-Mg calcitic planktic foraminifer tests is preserved in Pleistocene shallow-marine carbonates (in the Ryukyu Group; Okinawa, Japan) that have been altered by meteoric diagenesis. Whole-rock analyses indicate depleted isotopic values for both δ¹³C (−1.9 to −5.4‰) and δ¹⁸O (−2.9 to −5.2‰), as well as carbonate mineralogy exclusively composed of low-Mg calcite. However, analysis of carefully-extracted planktic foraminifer tests (Globigerinoides sacculifer) that were separated from these whole-rock samples yield heavier δ¹³C values (−0.4 to 1.9‰) and δ¹⁸O values (−3.2 to −1.0‰). The foraminiferal values themselves and comparison of values of various components suggest that the low-Mg calcite tests preserve the original stable isotopic values. Subsequently, the downcore δ¹⁸O change of planktic foraminifers recorded in the Ryukyu Group results from middle Pleistocene glacial–interglacial change. By comparison, isotopic measurements based on whole-rock samples can be obtained diagenetic environmental signals, but misleading with regard to paleoclimatic inferences.     

The nitrogen isotope biogeochemistry of sinking particles from the margin of the Eastern North Pacific

The nitrogen isotopic composition of time-series sediment trap samples, dissolved NO^-₃, and surficial sediments was determined in three regions along the margin of the eastern North Pacific: Monterey Bay, San Pedro Basin, and the Gulf of California (Carmen and Guaymas Basins). Complex physical regimes are present in all three areas, and each is influenced seasonally by coastal upwelling. Nevertheless, sediment trap material evidently records the isotopic composition of new nitrogen sources, since average δ¹⁵N is generally indistinguishable from δ¹⁵N values for subsurface NO^-₃. Surficial sediments are also very similar to the average δ¹⁵N value of the sediment traps, being within 1‰. This difference in δ¹⁵N between trap material and sediment is much less than the previously observed 4‰ difference for the deep sea. Better organic matter preservation at our margin sites is a likely explanation, which may be due to either low bottom O₂ concentrations or higher organic matter input to the sediments. All sites have δ¹⁵N for sub-euphotic zone NO^-₃ (8–10‰) substantially elevated from the oceanic average (4.5–5‰). This isotopic enrichment is a result of denitrification in suboxic subsurface waters (Gulf of California) or northward transport of denitrification influenced water (Monterey Bay and San Pedro Basin). Our results therefore suggest that downcore δ¹⁵N data, depending on site location, would record the intensity of denitrification and the transport of its isotopic signature along the California margin. Temporal variations in δ¹⁵N for the sediment traps do appear to respond to upwelling or convective injections of NO^-₃ to surface waters as a result of isotopic fractionation during phytoplankton uptake. Overall, though, the coupling between NO^-₃ injection, δ¹⁵N, and flux is looser than previously observed for the open-ocean, most likely the result of the smaller time/space scales of the events. In the Gulf of California, wintertime convective mixing/upwelling does produce distinct δ¹⁵N minima co-occurring with particle flux maxima. Interannual variations are apparent in this region when these winter-time δ¹⁵N minima fail to occur during El Niño conditions. There appears to be a positive relationship between the Southern Oscillation Index (SOI) anomaly and annual average δ¹⁵N. One explanation calls for hydrographic changes altering the δ¹⁵N of subeuphotic zone NO^-₃.     

Transformation of suspended particulate matter into sediment in the Kara Sea in September of 2011

The biogeochemical processes participating in the transformation of the particulate matter into sediment along the Yenisei River-St. Anna Trough (Kara Sea) meridional profile were studied using hydrochemical, geochemical, microbiological, radioisotope, and isotope methods. The water-sediment contact zone consists of three subzones: the suprabottom water, the fluffy layer, and the surface sediment. The total number, biomass, and integral activity of the microorganisms (dark ¹⁴CO₂ assimilation) in the fluffy layer are usually higher than in the suprabottom water and sediment. The fluffy layer shows a decrease in the oxygen content and the growth of the dissolved biogenic elements. It was provided by the particulate organic matter supporting the vital activity of the heterotrophs from the overlying water column and by the flux of reduced compounds (NH₄, H₂S, CH₄, Fe²⁺, Mn²⁺, and others) from the underlying sediments. The C_org isotopic composition of the fluffy layer and the sediments is 2–4 ‰ heavier than that of the particulate matter and sediment due to the presence of the isotopically heavy biomass of microorganisms. A change in the isotopic composition of the C_org in the fluffy layer and surface sediment as compared to the C_org of the particulate matter is a widespread phenomenon in the Arctic shelf seas and proves the leading role of microorganisms in the transformation of the particulate matter into sediment.     

Distribution and burial of organic carbon in sediments from the Indian Ocean upwelling region off Java and Sumatra,Indonesia

Sediments were sampled and oxygen profiles of the water column were determined in the Indian Ocean off west and south Indonesia in order to obtain information on the production, transformation, and accumulation of organic matter (OM). The stable carbon isotope composition (δ¹³C_org) in combination with C/N ratios depicts the almost exclusively marine origin of sedimentary organic matter in the entire study area. Maximum concentrations of organic carbon (C_org) and nitrogen (N) of 3.0% and 0.31%, respectively, were observed in the northern Mentawai Basin and in the Savu and Lombok basins. Minimum δ¹⁵N values of 3.7‰ were measured in the northern Mentawai Basin, whereas they varied around 5.4‰ at stations outside this region. Minimum bottom water oxygen concentrations of 1.1 mL L^?1, corresponding to an oxygen saturation of 16.1%, indicate reduced ventilation of bottom water in the northern Mentawai Basin. This low bottom water oxygen reduces organic matter decomposition, which is demonstrated by the almost unaltered isotopic composition of nitrogen during early diagenesis. Maximum C_org accumulation rates (CARs) were measured in the Lombok (10.4 g C m^?2 yr^?1) and northern Mentawai basins (5.2 g C m^?2 yr^?1). Upwelling-induced high productivity is responsible for the high CAR off East Java, Lombok, and Savu Basins, while a better OM preservation caused by reduced ventilation contributes to the high CAR observed in the northern Mentawai Basin. The interplay between primary production, remineralisation, and organic carbon burial determines the regional heterogeneity. CAR in the Indian Ocean upwelling region off Indonesia is lower than in the Peru and Chile upwellings, but in the same order of magnitude as in the Arabian Sea, the Benguela, and Gulf of California upwellings, and corresponds to 0.1–7.1% of the global ocean carbon burial. This demonstrates the relevance of the Indian Ocean margin off Indonesia for the global OM burial.     

Elemental and biochemical composition of organic matter in the waters of the Russian sector of the Arctic Basin under the present conditions

The considered area of the Russian sector of the Arctic Basin was characterized in August–September of 2008 by the wide horizontal and vertical variability of the concentrations of dissolved and particulate organic matter (OM), as well as of its elemental and biochemical composition. The concentration ranges amounted to 51.6–434 and 2.2–18.6 μM, respectively, for the dissolved and particulate C_org; up to 1.9–30.2 μM for N_org; and up to 0.08–1.53 μM for P_org. The maximum values were characteristic for the Russian Arctic shelf. The analysis of the authors’ and published data showed that a pronounced accumulation of OM, mainly in the dissolved form, took place in the Arctic Basin within the past 12 years. The concentrations of dissolved OM were higher in the western sector of the Russian Arctic than those in the eastern sector. The main biochemical components in all the waters constituting the Arctic Ocean are carbohydrates and lipids for dissolved OM and proteins and carbohydrates for particulate matter.     

The origin and biogeochemistry of organic matter in surface sediments of Lake Shihwa and Lake Hwaong

To understand the origin and biogeochemistry of the organic matter in surface sediments of Lake Shihwa and Lake Hwaong, organic nitrogen, inorganic nitrogen, labile organic carbon, and residual organic carbon contents as well as stable isotope ratios for carbon and nitrogen were determined by KOBr-KOH treatment. Ratios of organic carbon to organic nitrogen (C_org/N_org) (mean = 24) were much higher than ratios of organic carbon to total nitrogen (C_org/N_tot) (mean=12), indicating the presence of significant amounts of inorganic nitrogen in the surface sediments of both lakes. Stable isotope ratios for organic nitrogen were, on average, 5.2‰ heavier than ratios of inorganic nitrogen in Lake Shihwa, but those same ratios were comparable in Lake Hwaong. This might be due to differences in the origin or the degree of degradation of sedimentary organic matter between the two lakes. In addition, stable isotope ratios for labile organic carbon were, on average, 1.4‰ heavier than those for residual organic carbon, reflecting the preferential oxidation of¹³C-enriched organic matter. The present study demonstrates that KOBr-KOH treatment of sedimentary organic matter can provide valuable information for understanding the origin and degradation state of organic matter in marine and brackish sediments. This also suggests that the ratio of C_org/N_org and stable isotope ratios for organic nitrogen can be used as indexes of the degree of degradation of organic matter.     

Nitrogen isotope patterns in the oxygen-deficient waters of the Eastern Tropical North Pacific Ocean

We analyzed the stable nitrogen isotope composition of an extensive set of samples of particulate matter (PM) and seawater nitrate collected during October/November 1997 along the Mexican coastline from 24° to 11.5°N. At the northern and southern end of our study area, the δ¹⁵N of PM ranged between 5 and 7‰ in the upper 200 m of the water column with higher values at intermediate depths. These data are very similar to those reported from other parts of the open ocean. In the oxygen minimum zone (OMZ), we found significantly higher δ¹⁵N values for suspended particles. Furthermore, the δ¹⁵N of nitrate (NO₃) was elevated within the OMZ and we found a strong relationship between the oxygen concentration, nitrate deficit and the ¹⁵N content of the nitrate. The core of the OMZ between 22°N, 105°W and 15°N, 110°W coincided with higher nitrate deficits and δ¹⁵N values relative to the stations near the boundaries. The δ¹⁵N of nitrate was highest, with values up to 18.7‰, where oxygen concentrations were below 1–2 μmol/l. This pattern is consistent with an overall nitrogen isotopic enrichment factor of 22.5‰ for denitrification in the core of the OMZ using the Rayleigh equation (closed-system approach). Results from a diffusion model (open-system approach), however, gave a fractionation factor of 30±7.5‰, implying that the Rayleigh formula only gives a lower estimate of the fractionation factor ε. The vertical flux of particles collected in short-term deployments (ca. 35 h) of a drifting sediment trap was not significantly correlated with the water column nitrate deficit. The isotopic signature of the nitrate within the gradient is very similar to the δ¹⁵N value of sedimenting particles, suggesting that there might be a strong link between the production and sedimentation of particles. Upward flux of nitrate across the thermocline can account for less than half of the particle flux leaving the mixed layer. Mixing and transport of nitrate across the lower boundary of the OMZ can lead to significant enrichment in the ¹⁵N content of deep waters, and our isotopic data imply that at least 14% of the nitrate in the waters below the OMZ originates from this source.     

Seasonal and decadal shifts in particulate organic matter processing and sedimentation in the Bering Strait Shelf region

We present data on the quality and quantity of particulate organic material deposited to the benthos in the Chukchi Sea. This analysis is undertaken by using ⁷Be, a short-lived radiotracer, which is associated with particle deposition, the stable carbon isotopic composition of organic material and its C/N ratio in the water column and within the sediments, and the inventories of chlorophyll a present in surface sediments. Using previously published data, we show that sedimentation processes in the regional Bering Strait ecosystem may have shifted in the past decade. Surface sediments collected in 2004 adjacent to the Russian coastline in the Chukchi Sea are less refractory in terms of carbon isotope ratios and C/N ratios than was observed for surface sediments at similar locations in 1995 and 1988. Based upon sediment ⁷Be and chlorophyll a inventories, short-term sedimentation on the shelf occurs immediately north of Bering Strait, and within and downstream of Barrow and Herald Canyons. Seasonal differences (i.e., ice-covered versus open-water conditions) in the quality of particulate organic carbon reaching the benthos appear to be small in the most productive waters, such as Barrow Canyon. However, in less productive waters, C/N ratios and δ¹³C values show seasonal variations. Once on the bottom, δ¹³C values in the organic fractions of the sediments are less negative than observed in settling material in the water column, which is commonly thought to result from biological processing within the sediments.     

Nitrogen isotopic composition of sinking particles from the southern Bay of Bengal: Evidence for variable nitrogen sources

An 8-year record of N fluxes and δ¹⁵N of sinking particles from the deep southern Bay of Bengal, northern Indian Ocean, is presented. Fluxes and δ¹⁵N vary between ∼0.1 and 3 mg m⁻² day⁻¹ and ∼2‰ and 8‰, respectively. The seasonal variation is determined mainly by oceanographic processes coupled to the Indian monsoon system. The annual pattern of δ¹⁵N is characterized by minima during spring intermonsoon (∼March–May), when nutrient inputs to the euphotic zone should be low because of stratification, and lighter nitrate/particulate matter is expected to be advected from the central Bay. Highest δ¹⁵N are associated with peak fluxes during southwest monsoon (∼June–September), when the southern Bay comes under the influence of the SW monsoon current, which appears to advect particulate matter with distinctly higher δ¹⁵N. The impact of this process, however, varies interannually under the influence of factors such as ENSO and the Indian Dipole Mode. Weakened advection leads to relatively low N fluxes and reduced δ¹⁵N. The data highlight the necessity of multi-annual studies to comprehend the natural variability of a system.     

Fatty acid composition of surface sediments in the subtropical Pearl River estuary and adjacent shelf,Southern China

Surface sediments (10 cm) of the subtropical Pearl River estuary and adjacent shelf, Southern China were collected. Fatty acids and compound-specific carbon isotopic analyses were determined to infer their sources and biogeochemical cycle of this lipid in the subtropical Pearl River estuary and adjacent northern South China Sea (SCS). The total concentrations of fatty acids ranged from ∼1.28 to ∼42.25 μg g⁻¹ dry weight. The levels of polyunsaturated fatty acids (PUFA) were low (0.2–4.8% of total fatty acids), suggesting that fatty acids derived from algae were effectively recycled during the whole settling and depositing process. Bacterial fatty acids were significantly high and terrigenous fatty acids were low in the sediments. Principal component analysis (PCA) of the data also indicates that a clear separation of the biogeochemical sources can be seen. The δ¹³C values of bacterial fatty acids, i.e., i/aiC₁₅ (−22.9‰ to −29.4‰) suggest that bacteria within the sediments mainly utilize a labile pool of organic matter derived from algae for their growth in the subtropical Pearl River estuary system.     

酸化过程对不同碳酸钙含量的海洋沉积物中总氮及其同位素分析的影响

为节约成本和样品,一些学者同时分析海洋沉积物中的碳、氮及其同位素（TOC、TN、δ¹³C和δ¹⁵N）。分析沉积物中的δ¹³C,需要对样品进行酸化去除无机碳,但是这一酸化过程会使TN和δ¹⁵N的分析结果产生偏差,且偏差范围与沉积物中无机碳含量（CaCO₃）有关。本研究选取了低CaCO₃含量（1-16%）和高CaCO₃含量（20-40%）的海洋沉积物样品,比较了酸化过程对TN和δ¹⁵N的影响。研究结果表明,酸化过程对海洋沉积物中TN和δ¹⁵N的分析结果产生了显著影响。对于低CaCO₃含量的样品,酸化导致样品中TN流失了约0-40%,δ¹⁵N偏移了约0-2‰;而对于高CaCO₃含量的样品,酸化导致样品中TN流失了约10-60%,δ¹⁵N偏移了约1-14‰。表明酸化对TN和δ¹⁵N的影响已经超过了仪器的误差范围0.002%（TN）和0.08‰（δ¹⁵N）,将影响TN和δ¹⁵N的环境指示意义。因此,即使海洋沉积物样品中CaCO₃含量很低,也必须用原样分析TN和δ¹⁵N以避免酸化过程的影响。     

Isotopic analyses of nitrate and nitrite from reference mixtures and application to Eastern Tropical North Pacific waters

Isotopic analyses of nitrate by the denitrifier method, and indeed by many other analytical methods, do not discriminate between nitrate and nitrite. For samples containing both chemical species, accurate isotopic analysis of nitrate requires either removal of nitrite or independent isotopic analysis of nitrite and subtraction of its contribution to the mixed isotopic signal. This study evaluates the application of a variety of available analytical approaches to the isotopic analysis of mixed nitrate and nitrite solutions, with the goal of producing accurate coupled isotopic analyses of both nitrate and nitrite. These methods are tested on mixtures of standard solutions of nitrate and nitrite, and then applied to the coupled δ¹⁵N and δ¹⁸O analyses of nitrate and nitrite in waters of the Eastern Tropical North Pacific (ETNP). Results from standard mixtures show that even for extreme values of nitrate and nitrite δ¹⁵N and δ¹⁸O, both nitrite removal by ascorbate and nitrite isotopic analysis and subtraction from the mixed isotopic signal yield nitrate δ¹⁵N and δ¹⁸O values that are close to the expected values. Application of these analyses to samples from the ETNP yielded δ¹⁵N_NO3 and δ¹⁸O_NO3 values as high as 21‰ vs. AIR and 19‰ vs. VSMOW, respectively. Conversely, very low δ¹⁵N values were observed in nitrite, with values ranging from − 7.2 to − 18.5‰ vs. AIR. Removal of nitrite from ETNP samples thus revealed differences of up to 5‰ between NO₃^- and NO₂^- + NO₃^- for both δ¹⁵N and δ¹⁸O. Moreover, the δ¹⁵N offset between co-occurring nitrate and nitrite is greater than expected from the action of denitrification alone and may provide a unique constraint on the processes involved in the cycling of nitrite in and around oxygen deficient zones. Finally, subtraction of the nitrite δ¹⁵N and δ¹⁸O from ETNP samples allows the extension of the Δ(15,18) tracer into suboxic regions containing nitrite. The magnitude and distribution of Δ(15,18) in these samples suggests an important role for nitrite reoxidation in nitrate isotope variations.     

Pelagic nitrogen dynamics in the Vietnamese upwelling area according to stable nitrogen and carbon isotope data

Upwelling and nitrogen (N) fixation provide new N for primary production off southern central Vietnam. Here we evaluate the roles of both N sources for zooplankton nutrition by comparing δ¹⁵N and δ¹³C values in nitrate, particulate organic matter (POM), and six net-plankton size fractions from monsoon and intermonsoon seasons. The δ¹³C values in POM and the net-plankton size fractions differed by 2–4‰ at any time. We assume that plankton from the POM filters was dominated by nano-and picoplankton as opposed to micro- and mesoplankton in the net-samples. The implications of this are discussed in terms of size differential pathways of C and N in the planktonic food web. We used δ¹⁵N to estimate the differences in N nutrition between the actual upwelling region and the oligotrophic area further offshore. The δ¹⁵N values of the net-plankton size fractions were depleted in δ¹⁵N by ca. 2‰ outside compared to inside the upwelling area during the monsoon season. We attribute these patterns to the additional utilization of N derived from N fixation. The concomitant findings of high N fixation rates reported earlier and low subthermocline nitrate (nitrate_sub) values of 2.9–3.6‰ support this conclusion. Net-plankton δ¹⁵N values increased with size, pointing to the dominance of higher trophic levels in the larger size fractions. According to a two source mixing model N fixation may have provided up to 13% of the N demand in higher trophic levels.