Evidence for cyanobacterial inputs and heterotrophic alteration of lipids in sinking particles in the Alboran Sea (SW Mediterranean)

The different sources of lipid compounds present in sinking particles collected in a sediment trap mooring deployed in the Alboran Sea (SW Mediterranean) were elucidated using the molecular marker concept. A significant contribution of cyanobacterial lipids was identified based on the occurrence of a series of 3- and 5-methylalkanes and dimethylalkanes. Further evidence of cyanobacterial inputs was obtained by principal component analysis of all data showing diploptene and n-alkanes in the range C₁₄–C₂₂ clustered together with those branched alkanes. The use of methyl and dimethyl alkanes to trace cyanobacterial sources in the water column is proposed with advantage to sterols which are usually masked by phytoplanktonic sterols. The sterol distribution indicates phytoplankton as a major source with a contribution from heterotrophic zooplanktonic. Both fossil and biogenic sources can be contributors to the large unresolved complex mixture (UCM) found in these samples.     

Compositions and transport of lipid biomarkers through the water column and surficial sediments of the equatorial Pacific Ocean

A systematic investigation of fluxes and compositions of lipids through the water column and into sediments was conducted along the U.S. JGOFS EgPac transect from l2°N to l5°S at 140°W. Fluxes of lipids out of the euphotic zone varied spatially and temporally, ranging from ≈0.20 – 0.6 mmol lipid-C m⁻² day⁻¹. Lipid fluxes were greatly attenuated with increasing water column depth, dropping to 0.002-0.06 mmol lipid-C m⁻² day⁻¹ in deep-water sediment traps. Sediment accumulation rates for lipids were ≈ 0.0002 – 0.00003 mmol lipid-C m⁻² day⁻¹. Lipids comprised ≈ 11–23% of C_org in net-plankton, 10–30% in particles exiting the euphotic zone, 2–4% particles in the deep EgPac, and 0.1-1 % in sediments. Lipids were, in general, selectively lost due to their greater reactivity relative to bulk organic matter toward biogeochemical degradation in the water column and sediment. Qualitative changes in lipid compositions through the water column and into sediments are consistent with the reactive nature of lipids. Fatty acids were the most labile compounds, with polyunsaturated fatty acids (PUFAs) being quickly lost from particles. Branchedchain C₁₅ and C₁₇ fatty acids increased in relative abundance as particulate matter sank and was incorporated into the sediment, indicating inputs of organic matter from bacteria. Long-chain C₃₉ alkenones of marine origin and long-chain C₂₀-C₃₀ fatty acids, alcohols and hydrocarbons derived from land plants were selectively preserved in sediments. Compositional changes over time and space demonstrate the dynamic range of reactivities among individual biomarker compounds, and hence of organic matter as a whole. A thorough understanding of biogeochemical reprocessing of organic matter in the oceanic water column and sediments is, thus, essential for using the sediment record for reconstructing past oceanic environments.     

Sources and transport of lipids on Amazon continental shelf

Dissolved material and recent sediment from the Amazon continental shelf have been analyzed for hydrocarbons to study the sources and potential fate of the transported organic matter. Dissolvedn-alkanes are present at low concentrations (ppb level) and are dominated by lipids from marine phytoplankton with carbon number maxima (C_max) at C₁₈/C₂₂ and an even-to-odd carbon predominance < C₃₀ (CPI_17–27 from 0.18 to 0.54). In the sediments, bimodal distributions ofn-alkane chain length suggest a mixed input of terrestrial (C_max at C₂₇/C₂₉/C₃₁ and CPI_25–33 from 0.75 to 1.82) and phytoplanktonic/microbial (C_max at C₂₀ and CPI_15–25 from 0.38 to 0.62) organic matter. Sesquiterpenes were the most significant cyclic compounds in all the dissolved samples analyzed reflecting a contribution from resinous trees to the terrestrial organic pool. On the other hand, enhanced concentrations of these compounds in the dissolved phase on the northwest portion of the Amazon shelf, contrasting with decreased concentrations in the sediment samples, suggest that dissolved lipids are released from solid phase in the intensely stirred seabed. Structured organic matter in the sediment has been characterized as being composed of, on average: 19% plant cuticles, 25% woody tissue, 13% pollens and spores, 24% amorphous material, 7% bituminite and 12% altered organic material.     

Uptake and metabolism of arsenate by anexic cultures of the microalgae Dunaliella tertiolecta and Phaeodactylum tricornutum

Axenic cultures of the microalgae species, Dunaliella tertiolecta and Phaeodactylum tricornutum were grown at arsenic (As) concentrations typically found in uncontaminated marine environments ( 2 µg L^− 1) under different phosphorus concentrations. D. tertiolecta accumulated higher arsenic concentrations (mean: 13.7 ± 0.7 µg g^− 1 dry mass) than P. tricornutum (mean: 1.9 ± 0.2 µg g−1 dry mass). Media phosphorus concentrations (0.6–3 mg/L) had little influence on microalgae growth rates or arsenic accumulation. Arsenic was present as lipid bound (29–38%; 4.2–9.5%), water-soluble (20–29%; 26–34%) and residue bound (41–45%; 57–69%) arsenic species in D. tertiolecta and P. tricornutum respectively. Hydrolysed lipids contained mostly glycerol arsenoribose (OH- ribose), dimethylarsinate (DMA) and inorganic arsenic (As(V)) moieties. Water-soluble species of microalgae were very different. D. tertiolecta contained inorganic arsenic (54–86%) with variable amounts of DMA (7.4–20%), arsenoriboses (5–25%) and traces of methylarsonate (MA) ( 1%). P. tricornutum contained mostly DMA (32–56%) and phosphate arsenoribose (PO₄-ribose, 23–49%) and small amounts of OH-ribose (3.8–6.5%) and As(V) (9–16%). Both microalgae contained an unknown cationic arsenic species. The residue fractions of both microalgae contained predominately inorganic arsenic (99–100%). These results show that at natural seawater arsenic concentrations, both algae take up substantial amounts of inorganic arsenic that is complexed with structural elements or sequestered in vacuoles as stable complexes. A significant portion is also incorporated into lipids. Arsenic is metabolised to simple methylated species and arsenoriboses.     

桑沟湾沉积碳库年汇入速率的长期变化及其区域性差异

对取自桑沟湾北西南三根柱样近200 a碳来源及埋藏通量的解析,分析了湾内不同站位各形态碳的差异性,进而对全湾碳埋藏进行了估算。湾内环流、贝藻养殖等造成湾内不同区域碳埋藏的差异;桑沟湾总碳（TC）平均量1.79%,有机碳（TOC）平均量0.54%,无机碳（TIC）平均量1.25%,TOC含量相对较小,为海陆混合来源,以陆源有机碳（C_t）为主,大规模人工养殖后,海源有机碳（C_a）有明显增加的趋势。桑沟湾碳埋藏通量平均为228.9 g/（m2·a）,以无机碳为主要埋藏形式（约占70%）,高的沉积速率及生物残骸沉降使桑沟湾养殖区碳的来源及埋藏区别于其他陆架海域。     

Distributions and sources of bulk organic matter and aliphatic hydrocarbons in surface sediments of the Bohai Sea, China

Surface sediment samples from a matrix of fifty-five sites covering virtually the entire Bohai Sea (Bohai), China were analyzed for total organic carbon (TOC), total nitrogen (TN), n-alkanes, unresolved complex mixture (UCM), biomarkers and stable carbon isotopic composition (δ¹³C), and principal component analysis was performed for source identification of organic matter (OM). The distribution of organic carbon correlated well with sediment grain size with the finest sediments having the highest concentration, suggesting the influence of hydrodynamics on the accumulation of sedimentary organic matter (SOM). The corrected TOC/ON (organic nitrogen) ratios and δ¹³C indicated mixed marine and terrestrial sources of SOM. Results suggested that δ¹³C could be used as a potential indicator to observe the dispersion of Huanghe-derived sediments in Bohai. Total n-alkane concentrations varied over 10-fold from 0.39 to 4.94 μg g^− 1 (dry weight) with the maximum terrigenous/aquatic alkane ratio observed at the Huanghe River Estuary (HRE) due to more higher plant OM from riverine inputs. C₁₂–C₂₂ n-alkanes with even-to-odd predominance were observed in several central-eastern Bohai sites. The HRE and its adjacent area is the main sink for the Huanghe river-derived OC. The ubiquitous presence of UCM, biomarkers (hopanes and steranes) and PCA results indicated the presence of petroleum contamination in Bohai, mainly from offshore oil exploration, discharge of pollutants from rivers, shipping activities and atmospheric deposition.     

Hydrocarbons in the Bay of Bengal and Central Indian Basin bottom sediments: indicators of geochemical processes in the lithosphere

A study on the bulk distributions and molecular structures of n-alkanes and polycyclic aromatic hydrocarbons (PAH) in organic matter of the sediments from the Bay of Bengal and the Eastern and Central Indian Basins was undertaken. The former two regions represent areas characterised by “normal” sedimentation while the third one mainly represents a region of “active tectonism”. Content of the hydrocarbons in the sediments of “normal” sedimentation ranges between 4.6 and 10.5 μg/g and aromatic hydrocarbons ranges between 0 and 0.38 μg/g. n-Alkanes in the sediments of the northern deep part of the Bay of Bengal consist mostly of long-chain structures (total C₂₅–C₃₃ up to 70%) with a high carbon preference index (CPI=3.01–3.43), indicating a large contribution of organic matter from terrigenous sources. The sediments from the Eastern Indian Basin have n-alkane distributions in which the long-chain components did not exceed 52.5% and the CPI was 1.7–1.90, indicating that the hydrocarbons are mostly derived from marine sources. Sharp increases of hydrocarbons are found in the vicinity of the tectonically active region of the Central Indian Basin, particularly in the sediments collected from the fracture zone. The total concentration of hydrocarbons increase to 170 μg/g and the aromatic hydrocarbons fraction to 156.3 μg/g. The proportion of short-chain n-alkanes increases up to 70%, CPI decreases to 0.76–1.12, and high concentrations of n-C₁₆ (16–40%) occur, all of which are absent in the other samples. The molecular content of PAH includes the unsubstituted individual structures: biphenyl, fluorene, pyrene, perylene, benzo(ghi)perylene, and the groups of homologues of naphthalene, benzofluorene, phenanthrene and chrysene. The association of the PAH and composition of paraffin hydrocarbons in the surficial sediments of deformation zone indicate that these are the resultant products of hydrothermal processes. It is, therefore, suggested that the association and composition of the hydrocarbons in sediments can be utilised as a paleoceanographic parameter to decipher the history of tectonism of an area.     

Investigation of Cd, Cu, Ni and Th in the colloidal size range in the Gulf of Maine

Size-fractionated seawater samples were collected from the Gulf of Maine to determine the fraction (f_c/d) of total dissolved (< 1 μm) Cd, Cu, Ni and ²³⁴Th in the colloidal size range (1,000 nominal molecular weight, NMW, to 1 μm) using cross-flow filtration. Colloidal Cd, Cu and Ni represents < 1–7% of the total dissolved concentration in these shelf waters and increases with an increase in particle concentration. By comparison, results obtained for particle-reactive ²³⁴Th indicate that < 1–47% of total dissolved is associated with the colloidal size fraction. A revised relationship between the concentration of colloids (C_c) and suspended particles (C_p) is reported (log C_c = 0.66 log C_p −2.01 kg L⁻¹) and used to examine the dependence of f_c/d for these metals on the concentration of suspended particles for C_p = 0.01–100 mg L⁻¹. Results indicate that a significant fraction (˜ 10–30%) of Cd, Cu, Ni and ²³⁴Th in the traditionally defined ‘dissolved’ fraction may exist in the colloidal size range in regions characterized by high particle concentrations (C_p > 1–10 mg L⁻¹), such as in near-shore and estuarine waters.     

Potential source and diagenetic signatures of oceanic dissolved and particulate organic matter as distinguished by lipid biomarker distributions

Potential biogenic sources of ultrafiltered dissolved and suspended particulate organic matter (UDOM and POM, respectively) from the Sargasso Sea (SS) and North Central Pacific (NCP) Ocean were investigated using lipid biomarker compounds. Organic carbon (OC) concentrations were ~ 20–40 times greater in UDOM than POM and decreased with depth. However, total OC-normalized lipid concentrations were 2–3 orders of magnitude higher in POM than in UDOM. Particulate total lipids decreased 3–10-fold with depth, compared to 10–20% for dissolved total lipids. Total fatty acids (FA), the most abundant lipids, showed similar patterns as total lipids, comprising ~ 62–88% of the total lipids analyzed in UDOM and ~ 57–84% in POM.FA were dominated by straight-chain saturated compounds followed by monounsaturated, polyunsaturated, and branched FA. Polyunsaturated FA were enriched in POM vs. UDOM and in surface vs. deep waters for both UDOM and POM, likely reflecting the algal origins and greater reactivity of surface-derived materials. In both UDOM and POM, sterols of planktonic origin dominated, including cholest-5-en-3β-ol (C₂₇Δ⁵), 24-methylcholesta-5,24(28)E-dien-3β-ol (C₂₈Δ^5,24(28)) and 24-ethylcholest-5-3β-ol (C₂₉Δ⁵), with varying contributions from cholesta-5,22E-3β-ol (C₂₇Δ^5,22), 24-methylcholesta-5,22E-3β-ol (C₂₈Δ^5,22) and 24-ethylcholesta-5,22E-3β-ol (C₂₉Δ^5,22).Factor analysis of lipid biomarkers showed major differences between the UDOM and POM pools and for each pool as a function of depth, but not between the SS and NCP. While UDOM and POM biomarkers were both dominated by autochthonous sources, differences between the two pools suggest potential effects from some combination of source and diagenetic factors. The lipid biomarker data are further evaluated relative to previous studies of radiocarbon (¹⁴C) and elemental (C:N:P) characteristics of UDOM and POM in the SS and NCP.     

The downward flux of biogenic material in the NE subarctic Pacific: importance of algal sinking and mesozooplankton herbivory

In the present study we examine factors that affect the downward flux of biogenic carbon in the NE subarctic Pacific, one of the important high-nutrient-low-chlorophyll (HNLC) regions in the open ocean. We focus on the role of mesozooplankton, since their seasonal peaks in biomass and growth are in phase with the seasonal variations in the downward POC fluxes, whereas phytoplankton biomass is more-or-less uniform year-round. The relative importance of mesozooplankton and algal sinking was examined using the pigment composition of material accumulated in short-term free-drifting sediment traps positioned just below the upper stratified surface layer (ca. 100–200 m). This was compared with the phytoplankton composition in the surface waters, and with the grazing activity (gut pigments and fecal pellet production rates) of the most abundant large copepods. We also examined whether the relationships between the downward flux of carbon and pelagic processes were similar in the coastal, continental margin and offshore HNLC regions of the NE subarctic Pacific, the latter represented by Ocean Station Papa (OSP).Our results show that grazing had a variable impact on the downward flux of biogenic carbon. Carbon-transformed pheopigments (particularly pyropheophorbide a, frequently associated with copepod grazing) represented up to 13% of the total downward POC flux inshore (in May 1996) and 8–9% at OSP in May and February 1996, respectively. This flux of pheopigments was accompanied by a large potential input of fecal pellets from large copepods (as estimated from defecation rates of freshly collected animals) only in May 1996 at OSP, suggesting that pheopigments came from other sources (other herbivores, senescing algae) in February. The larger flux of pheopigments in May was probably related to the abundance of mesozooplankton at that time of the year. During summer (August 1996), both the flux of pheopigments and the potential input of fecal pellets from large copepods were negligible at OSP, consistent with more intense pelagic recycling reported in other studies. Inshore, the flux of carbon-transformed pheopigments was slightly higher than at OSP, and its contribution to the downward POC flux in May 1996 was twice that in August 1996. In contrast, the potential input of feces carbon was higher in August than in May 1996, again suggesting other sources for pheopigments found in the traps. The contribution of sinking phytoplankton to the downward biogenic flux was negligible in summer, when prymnesiophytes (indicated by the presence of 19′-hexanoyloxyfucoxanthin) and pelagophytes (19′-butanoyloxyfucoxanthin-containing) dominated in surface offshore waters. The contribution of sinking algae was maximal (9%) in winter (February 1996) at OSP, when fucoxanthin (mainly a diatom marker) dominated the carotenoid composition in the traps and when the abundance of diatoms in surface waters showed its seasonal maximum for this station. Inshore, the low contribution of diatoms (fucoxanthin) to the sinking fluxes may have resulted from inadequate sampling (i.e. the spring bloom may have been missed).Overall, we conclude that: (a) large copepods significantly influenced the downward POC flux only during spring at OSP; (b) unidentified herbivores (e.g. salps, pteropods) producing pigmented, fast-sinking fecal material likely had an important impact during winter; (c) algal sinking made a small contribution to the downward POC flux (maximum in winter); and (d) neither algal sinking nor mesozooplankton grazing had a significant influence on the downward flux of biogenic material in summer at OSP.     

Degradation and dissolution of zooplanktonic organic matter and lipids in early diagenesis

A degradation experiment with zooplankton was carried out to investigate the diagenesis of zooplanktonic organic matter, lipids, and lipid classes. In addition, reactivities and the quantitative relation between bulk organic carbon and waxes (which are the biomarkers of zooplankton) were compared during the experiment to evaluate the possibility of estimating the contributions of zooplanktonic organic matter in organic carbon pools, such as settling particles and surface sediments, from the wax concentration. Lipids were found to be more labile than the bulk organic carbon. Major parts of the organic carbon and lipids which remained on day 120 were found in the particulate fraction, and the accumulations of stable organic carbon and lipids in the dissolved fraction were limited. Although the lipids were more labile than the bulk organic carbon in the early phase of the experiment, the degradation rate of lipids obviously decreased in the subsequent degradation period, demonstrating the presence of stable lipids in zooplankton. Whereas triglycerides readily decreased, phospholipids persisted, making a major contribution to particulate lipids throughout the experiment. Waxes and other structural lipids such as glycolipids were also stably preserved in particulate lipids, suggesting that stable lipids in particulate matter are composed of structural lipids and waxes during early diagenesis. The degradation rate of waxes showed values comparable to that of bulk organic carbon after 11 days of degradation, resulting in constant ratios of waxes/bulk organic carbon (0.8 ± 0.2%, n = 7) during the later incubation period (after 11 days). This result suggests that the ratio could prove useful in evaluating the zooplanktonic organic carbon in organic carbon pools such as surface sediments and settling particulates.     

Standing stocks and production rates of phytoplankton and planktonic copepods in the Inland Sea of Japan

Standing stocks and production rates of phytoplankton and planktonic copepods were investigated at 15 stations in the Inland Sea of Japan during four cruises in October–November 1979, January, April and June 1980. The overall mean of phytoplankton biomass was relatively constant during the study period, ranging from 2.3 mg chl.a m^–3 in April to 3.6 mg chl.a m^–3 in October–November. Primary production was low in January (mean: 90 mg C m^–2 d^–1), but higher than 375 mg C m^–2 d^–1 on the other occasions. Integrated annual primary production was 122 g C m^–2 yr^–1. In terms of carbon weight,Paracalanus parvus was the most important copepod species. The variation of the mean copepod biomass (range: 7.6 mg C m^–3 in April to 20.2 mg C m^–3 in June) was smaller than that of copepod production, which was estimated by the Ikeda-Motoda's physiological method. Copepod producion was low in cold seasons (0.6 and 0.9 mg C m^–3 d^–1 in January and April, respectively), and increased, following the elevation of primary production, to 4.9 mg C m^–3 d^–1 in June. Annual copepod production was 33.7 g C m^–2 yr^–1, of which herbivore (secondary) production was 26.4 g C m^–2 yr^–1 (21.7% of primary production). The ratios of pelagic planktivorous fish catch and total fish catch to the primary production were 0.82 and 1.8%, respectively, indicating very high efficiency in exploiting fishery resources in the Inland Sea of Japan.     

A depocenter of organic matter at 7800 m depth in the SE Pacific Ocean

The Atacama trench, the deepest ecosystem of the southern Pacific Ocean (ca. 8000 m depth) was investigated during the Atacama Trench International Expedition. Sediments, collected at three bathyal stations (1040–1355 m depth) and at a hadal site (7800 m) were analyzed for organic matter quantity and biochemical composition (in terms of phytopigments, proteins, carbohydrates and lipids), bacterial abundance, biomass and carbon production and extracellular enzymatic activities. Functional chlorophyll-a (18.0±0.10 mg m⁻²), phytodetritus (322.2 mg m⁻²) and labile organic carbon (16.9±4.3 g C m⁻²) deposited on surface sediments at hadal depth (7800 m) reached concentrations similar to those encountered in highly productive shallow coastal areas. High values of bacterial C production and aminopeptidase activity were also measured (at in situ temperature and 1 atm). The chemical analyses of the Atacama hadal sediments indicate that this trench behaves as a deep oceanic trap for organic material. We hypothesize that, despite the extreme physical conditions, benthic microbial processes might be accelerated as a result of the organic enrichment.     

Burial fluxes and source apportionment of carbon in culture areas of Sanggou Bay over the past 200 years

In this study,we assessed the burial fluxes and source appointment of different forms of carbon in core sediments collected from culture areas in the Sanggou Bay,and preliminarily analyzed the reasons for the greater proportion of inorganic carbon burial fluxes(BFTIC).The average content of total carbon(TC) in the Sanggou Bay was 2.14%.Total organic carbon(TOC) accounted for a small proportion in TC,more than 65% of which derived from terrigenous organic carbon(Ct),and while the proportion of marine-derived organic carbon(Ca) increased significantly since the beginning of large-scale aquaculture.Total inorganic carbon(TIC) accounted for 60%–75%of TC,an average of which was 60%,with a maximum up to 90% during flourishing periods(1880–1948) of small natural shellfish derived from seashells inorganic carbon(Shell-IC).The TC burial fluxes ranged from 31 g/(m2·a)to 895 g/(m2·a) with an average of 227 g/(m2·a),which was dominated by TIC(about 70%).Shell-IC was the main source of TIC and even TC.As the main food of natural shellfish,biogenic silica(BSi) negatively correlated with BFTIC through affecting shellfish breeding.BFTIC of Sta.S1,influenced greatly by the Yellow Sea Coastal Current,had a certain response to Pacific Decadal Oscillation(PDO) in some specific periods.     

Vertical transport of particulate organic matter in the deep Bering Sea and gulf of Alaska

Sediment trap arrays were deployed at two deep ocean stations, one in the Bering Sea and the other in the Gulf of Alaska, in the summer of 1975. The sediment trap was constructed of a pair of polyethylene cylinders (0.185 m² opening) with funnel-shaped bases. The trap is equipped with a lid which is closed before recovery by a tripping messenger system triggered by an electric time release. 37–68% of the total organic carbon fluxes (37–38% in the Bering Sea; 48–68% in the Gulf of Alaska) were represented by large particles (67µm<) such as fecal matter and fecal pellets which contributed minor fractions to the total particulate organic matter concentration in sea water. The total fluxes were 11.1 and 14.2 mg C m^–2d^–1 at 1,510 and 2,610 m respectively at the station (3,800 m) in the Bering Sea, and were 7.60, 4.66 and 3.27 mg C m^–2d^–1 at 900, 1,500 and 1,875 m respectively at the station (4,150 m) in the Gulf of Alaska. The former values are several times greater than the latter, suggesting that there is a regional variation in the vertical carbon flux in deep layers. The fluxes were approximately equivalent to 1 to 3% of primary productivity in the overlying surface layers. These observations suggest that deep-water ecosystems may be influenced by relatively rapid sinking of large particles such as fecal matter and fecal pellets from near surface production.     

Biogeochemistry of sterols in plankton, settling particles and recent sediments in a cold ocean ecosystem (Trinity Bay, Newfoundland)

In the context of a multidisciplinary study to determine current and past ecosystem health and the relative contributions of sources of organic matter (marine vs. terrestrial and natural vs. anthropogenic input), sterols were determined in plankton, settling particles and sediments from Trinity Bay, Newfoundland, a sub-polar Atlantic Ocean ecosystem. The centric diatoms Chaetoceros spp., Thalassiosira spp. and Leptocylindrus danicus were all prominent in the plankton samples, and centric diatoms predominated in the settling particles. Plankton samples contained 0.4±0.4 mg/g dw (1995) or 1.4±1.3 mg/g dw (1996) total sterols, with cholesta-5,24-dien-3β-ol (mean 26% of total sterols), cholest-5-en-3β-ol (24%) and cholesta-5,22(E)-dien-3β-ol (13%) chief among these, denoting diatom and zooplankton sources. In settling particles, the prominence of cholesta-5,24-dien-3β-ol (24%), cholest-5-en-3β-ol (24%), cholesta-5,22(E)-dien-3β-ol (13%) and 24-methylcholesta-5,22(E)-dien-3β-ol (9%) again suggested mainly marine sources. The sterol composition of plankton and settling particles from different sampling periods showed a high degree of consistency. Higher plant C₂₉ sterols (notably 24-ethylcholest-5-en-3β-ol, 9–26%) were prominent in sediments from both inshore and offshore sites. No decreasing trend in total or individual sterols was observed down the 30-cm sediment cores, suggesting good overall preservation. No 5β-stanols such as 5β-cholestan-3β-ol (coprostanol) were detected in offshore sediments, plankton or settling particles, with only low levels (5β-cholestan-3β-ol max. 4.4%, 5β-cholestan-3α-ol max. 5.1%) in certain inshore sediments. This suggests that raw sewage discharges in rural Newfoundland are being efficiently degraded or dispersed, or that inputs are highly localized. Source apportionation of organic matter in the sediment samples based on sterol composition was attempted. This highlighted the large terrestrial contribution to the sterols in marine sediments (up to 58% of sterols inshore, 24% offshore) and suggests either degradation or effective recycling of marine sterols.     

Transport and fate of Danube Delta terrestrial organic matter in the Northwest Black Sea mixing zone

Within the framework of the European project EROS 21, a biogeochemical study of particles transported from the Danube Delta to the Northwestern Black Sea whose carbon cycle is dominated by riverine inputs was carried out in spring off the Sulina branch of the Danube Delta. The distribution of particulate organic carbon (POC), chlorophyll a (Chl a), C/N, and δ¹³C evidenced an omnipresent contribution of terrestrial organic matter throughout the study area together with a dilution of these inputs by freshwater and marine organisms. Four lipid series, n-alkanoic acids, n-alkanes, n-alkanols, and sterols were analyzed by gas chromatography and gas chromatography/mass spectrometry. Several signature compounds were selected to delineate dispersion of terrestrial organic carbon: (1) long-chain n-alkanoic acids in the range C₂₄–C₃₄, long-chain n-alkanes in the range C₂₅–C₃₅, long-chain n-alkanols in the range C₂₂–C₃₀, 24-ethylcholesta-5,22-dien-3β-ol (29Δ^5,22) and 24-ethylcholesterol (29Δ⁵) for vascular plant-derived material and (2) coprostanol (27Δ^0,5β) for faecal contamination associated with sewage effluents. A marked decrease was observed between the concentrations of different vascular plant markers characterizing the two end members: riverine at salinity 0.3 and marine at salinity 15.5. The decrease observed for marine/riverine end members (expressed as a function of organic carbon) varied in a large range, from 4% for n-alkanes to 18.6%, 20.4% and 24% for n-fatty acids, n-alkanols and sterols, respectively. These values reflect a combination of various processes: size-selective particle sedimentation, resuspension of different particle pools of different sizes and ages, and/or selective biological utilization. The multi-marker approach also suggested the liberation in the mixing zone of terrestrial moieties, tightly trapped in macromolecular structures of the riverine material. The greatest decrease for marine/riverine end members was observed for coprostanol (0.9%), underlining the efficiency of the mixing zone as a sink for sewage-derived carbon.     

Effect of iron enrichment on the dynamics of transparent exopolymer particles in the western subarctic Pacific

Dynamics of transparent exopolymer particles (TEP) was studied during the first in situ iron-enrichment experiment conducted in the western subarctic Pacific in July–August 2001, with the goal of evaluating the contribution of TEP to vertical flux as a result of increased primary production following iron enrichment in open ocean ecosystems. Subsequent to the enhancement of phytoplankton production, we observed increase in TEP concentration in the surface layer and sedimentation of organic matter beneath it. Vertical profiles of TEP, chlorophyll a (Chl a) and particulate organic carbon (POC) were obtained from six depths between 5 and 70 m, from a station each located inside and outside the enriched patch. TEP and total mass flux were estimated from the floating sediment traps deployed at 200 m depth. Chl a and TEP concentrations outside the patch varied from 0.2 to 1.9 μg L⁻¹ and 40–60 μg XG equiv. L⁻¹, respectively. Inside the patch, Chl a increased drastically from day 7 reaching the peak of 19.2 μg L⁻¹ on day 13, which coincided with the TEP peak of 189 μg XG equiv. L⁻¹. TEP flux in the sediment trap increased from 41 to 88 mg XG equiv. m⁻² d⁻¹, with 8–14% contribution of TEP to total mass flux. This forms the basic data set on ambient concentrations of TEP in the western subarctic Pacific, and evaluation of the effect of iron enrichment on TEP.     

One-dimensional modelling of convective CO2 exchange in the Tropical Atlantic

Diurnal changes in seawater temperature affect the amount of air–sea gas exchange taking place through changes in solubility and buoyancy-driven nocturnal convection, which enhances the gas transfer velocity. We use a combination of in situ and satellite derived radiometric measurements and a modified version of the General Ocean Turbulence Model (GOTM), which includes the National Oceanic and Atmospheric Administration Coupled-Ocean Atmospheric Response Experiment (NOAA-COARE) air–sea gas transfer parameterization, to investigate heat and carbon dioxide exchange over the diurnal cycle in the Tropical Atlantic. A new term based on a water-side convective velocity scale (w_*w) is included, to improve parameterization of convectively driven gas transfer. Meteorological data from the PIRATA mooring located at 10°S10°W in the Tropical Atlantic are used, in conjunction with cloud cover estimates from Meteosat-7, to calculate fluxes of longwave, latent and sensible heat along with a heat budget and temperature profiles during February 2002. Twin model experiments, representing idealistic and realistic conditions, reveal that over daily time scales the additional contribution to gas exchange from convective overturning is important. Increases in transfer velocity of up to 20% are observed during times of strong insolation and low wind speeds (<6 m s⁻¹); the greatest enhancement from w_*w to the CO₂ flux occurs when diurnal warming is large. Hence, air–sea fluxes of CO₂ calculated using simple parameterizations underestimate the contribution from convective processes. The results support the need for parameterizations of gas transfer that are based on more than wind speed alone and include information about the heat budget.     

Surface phytoplankton pigment distributions in the Atlantic Ocean: an assessment of basin scale variability between 50°N and 50°S

We present an overview of the spatial distributions of phytoplankton pigments along transects between the UK and the Falkland Islands. These studies, undertaken as a component of the UK Atlantic Meridional Transect (AMT) programme, provided the first post-launch validation data for the NASA SeaWiFS satellite. Pigment data are used to characterise basin-scale variations in phytoplankton biomass and community composition over 100° of latitude, and to compliment the definition of hydrographic oceanic provinces. A summary of the key pigment characteristics of each province is presented.Concentrations of total chlorophyll a (totCHLa = chlorophyll a, CHLa + divinyl CHLa, dvCHLa) were greatest in high latitude temperate waters (>37°N and >35°S), and in the Canary Current Upwelling system. In these regions, the total carotenoid (totCAR) budget was dominated by photosynthetic carotenoids (PSCs). High accessory pigment diversity was observed of which fucoxanthin (FUC), 19'–hexanoyloxyfucoxanthin (HEX), and diadinoxanthin (DIAD) were most abundant, indicating proliferation of large eukaryotes and nanoflagellates. In contrast, tropical and sub-tropical waters exhibited concentrations of totCHLa below 500 ng l⁻¹, with the North Atlantic Sub-tropical East gyre (NASE, 26.7–35°N), South Equatorial Current (SeqC, 7–14.6°S) and South Atlantic tropical Gyre (SATG, 14.6–26°S) characterised by totCHLa of <100 ng⁻¹. These waters exhibited relatively limited pigment diversity, and the totCAR budget was dominated by photoprotecting pigments (PPCs) of which zeaxanthin (ZEA), a marker of prokaryotes (cyanobacteria and prochlorophytes), was most abundant. DvCHLa, a marker of prochlorophytes was detected in waters at temperatures >15°C, and between the extremes of 48°N and 42°S. DvCHLa accounted for up to two-thirds of totCHLa in oligotrophic provinces demonstrating the importance of prochlorophytes to oceanic biomass.Overall, HEX was the dominant PSC, contributing up to 75% of totCAR. HEX always represented >2% of totCAR and was the only truly ubiquitous carotenoid. Since HEX is a chemotaxonomic marker of prymnesiophytes, this observation reflects the truly cosmopolitan distribution of this algal class. ZEA was found to be the most abundant PPC contributing more than one third of the total carotenoid budget in each transect.Greatest seasonality was observed in highly productive waters at high latitudes and in shallow continental shelf waters and attributed to proliferation of large eukaryotes during spring. Concentrations of the prokaryote pigments (ZEA + dvCHLa) also exhibited some seasonality, with elevated concentrations throughout most of the transect during Northern Hemisphere spring.