Deposition, mineralization, and storage of carbon and nitrogen in sediments of the far northern and northern Great Barrier Reef shelf

The flow of carbon and nitrogen in sediments of the far northern and northern sections of the Great Barrier Reef continental shelf was examined. Most of the organic carbon (81–94%) and total nitrogen (74–92%) depositing to the seabed was mineralized, with burial of carbon (6–19%) and nitrogen (8–20%) being proportionally less on this tropical shelf compared with other non-deltaic shelves. Differences in carbon and nitrogen mineralization among stations related best to water depth and proximity to river basins, with rates of mineralization based on net ∑CO₂ production ranging from 17 to 39 ( mean=23) mmol C m⁻² d⁻¹. The overall ratio of O₂:CO₂ flux was 1.3, close to the Redfield ratio, implying that most organic matter mineralized was algal. Sulfate reduction was estimated to account for ≈30% (range: 6–62%), and denitrification for ≈5% (range: 2–13%), of total C mineralization; there was no measurable CH₄ production. Discrepancies between ∑CO₂ production across the sediment–water interface and sediment incubations suggest that as much as 5 mmol m⁻² d⁻¹ (≈25% of ∑CO₂ flux) was involved in carbonate mineral formation. Most microbial activity was in the upper 20 cm of sediment. Rates of net NH₄⁺ production ranged from 1.6 to 2.7 mmol N m⁻² d⁻¹, with highly variable N₂ fixation rates contributing little to total N input. Ammonification and nitrification rates were sufficient to support rapid rates of denitrification (range: 0.1–12.4 mmol N m⁻² d⁻¹). On average, nearly 50% of total N input to the shelf sediment was denitrified. The average rates of sedimentation, mineralization, and burial of C and N were greater in the northern section of the shelf than in the far northern section, presumably due to higher rainfall and river discharge, as plankton production was similar between regions. The relative proportion of plankton primary production remineralized at the seafloor was in the range of 30–50% which is at the high end of the range found on other shelves. The highly reactive nature of these sediments is attributed to the deposition of high-quality organic material as well as to the shallowness of the shelf, warm temperatures year-round, and a variety of physical disturbances (cyclones, trawling) fostering physicochemical conditions favorable for maintaining rapid rates of microbial metabolism. The rapid and highly efficient recycling of nutrients on the inner and middle shelf may help to explain why the coral reefs on the outer shelf have remained unscathed from increased sediment delivery since European settlement.     

Spatial distribution of polyfluoroalkyl compounds in dab (Limanda limanda) bile fluids from Iceland and the North Sea

The spatial distribution of polyfluoroalkyl compounds (PFCs) was investigated in dab (Limanda limanda) bile fluids collected from Iceland and the North Sea. Concentrations of various PFCs, including perfluorinated sulfonates (C₄-C₆, C₈ PFSAs), perfluorinated carboxylic acids (C₉-C₁₄ PFCAs) and n-methyl perfluorooctane sulfonamidoethanol (MeFOSE), were quantified. Perfluorooctane sulfonate (PFOS) was the predominant compound with highest concentrations along the Danish and German coast (mean 9.36 ng/g wet weight (ww)). Significantly lower PFOS concentrations were found at the other sampling stations in the North Sea and Iceland (p < 0.01, t-test). Conversely, the spatial distribution of the PFCAs in Iceland and the North Sea was more uniform. The most abundant PFCA was perfluorononanoic acid (PFNA), while the mean concentration decreased with increasing chain length from 4.7 ng/g ww for PFNA to 0.04 ng/g ww for perfluorotetradecanoic acid (PFTeDA). Overall, the different spatial distribution of PFCs indicates different origin of sources and different transportation mechanism.     

Monitoring the freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAH) and alkylphenols (AP) around a Norwegian oil platform by holistic passive sampling

In order to assess the environmental impact of aquatic discharges from the offshore oil industry, polar organic chemical integrative samplers (POCIS) and semipermeable membrane devices (SPMDs) were deployed around an oil platform and at reference locations in the North Sea. Exposure to polycyclic aromatic hydrocarbons (PAH) and alkylated phenols (AP) was determined from passive sampler accumulations using an empirical uptake model, the dissipation of performance reference compounds and adjusted laboratory derived sampling rates. Exposure was relatively similar within 1–2 km of the discharge point, with levels dominated by short chained C1–C3 AP isomers (19–51 ng L⁻¹) and alkylated naphthalenes, phenanthrenes and dibenzothiophenes (NPD, 29–45 ng L⁻¹). Exposure stations showed significant differences to reference sites for NPD, but not always for more hydrophobic PAH. These concentrations are several orders of magnitude lower than those reported to give both acute and sub-lethal effects, although their long term consequences are unknown.     

Sources of polyfluoroalkyl compounds in the North Sea, Baltic Sea and Norwegian Sea: Evidence from their spatial distribution in surface water

The spatial distribution of 15 polyfluoroalkyl compounds (PFCs) in surface water was investigated in the North Sea, Baltic Sea and Norwegian Sea. In addition, an interlaboratory comparison of the sampling techniques and analysis was conducted. Highest concentration in the North Sea was found near the coast, whereas the ∑PFC concentration decreased rapidly from 18.4 to 0.07 ng l⁻¹ towards the open North Sea. The river Elbe could identify as a local input source for PFCs into the North Sea, whereas perfluorobutanoic acid (PFBA) was transported into the sampling area with the easterly current. In contrast to the North Sea, the distribution of PFCs in the Baltic Sea was relatively homogenous, where diffuse sources dominated. In general, the composition profile was influenced from local sources caused by human activities, whereas atmospheric depositions of here analysed PFCs were negligible, but it could have possibly an influence on low contaminated sites like the open North Sea or Norwegian Sea.     

Consequences of coastal upwelling events on physical and chemical patterns in the central Gulf of Finland (Baltic Sea)

The consequences of a coastal upwelling event on physical and chemical patterns were studied in the central Gulf of Finland. Weekly mapping of hydrographical and -chemical fields were carried out across the Gulf between Tallinn and Helsinki in July–August 2006. In each survey, vertical profiles of temperature and salinity were recorded at 27 stations and water samples for chemical analyses (PO₄³⁻, NO₂⁻+NO₃⁻) were collected at 14 stations along the transect. An ordinary distribution of hydrophysical and -chemical variables with the seasonal thermocline at the depths of 10–20 m was observed in the beginning of the measurements in July. Nutrient concentrations in the upper mixed layer were below the detection limit and nutriclines were located just below or in the lower part of the thermocline. In the first half of August, a very intense upwelling event occurred near the southern coast of the Gulf when waters with low temperature and high salinity from the intermediate layer surfaced. High nutrient concentrations were measured in the upwelled water – 0.4 μmol l⁻¹ of phosphates and 0.6 μmol l⁻¹ of nitrates+nitrites. We estimated the amount of nutrients transported into the surface layer as 238–290 tons of phosphorus (P)-PO₄³⁻ and 175–255 tons of N-NO_x for a 12 m thick, 20 km wide and 100 km long coastal stretch. Taking into account a characteristic along-shore extension of the upwelling of 200 km, the phosphate-phosphorus amount is approximately equal to the average total monthly riverine load of phosphorus to the Gulf of Finland. It is shown that TS-characteristics of water masses and vertical distribution of nutrients along the study transect experienced drastic changes caused by the upwelling event in the entire studied water column. TS-analysis of profiles obtained before and during the upwelling event suggests that while welled up, the cold intermediate layer water was mixed with the water from the upper mixed layer with a share of 85% and 15%. We suggest that the coastal upwelling events contribute remarkably to the vertical mixing of waters in the Gulf of Finland. Intrusions of nutrient-rich waters along the inclined isopycnal surfaces in the vicinity of upwelling front were revealed. The upwelling event widened the separation of phosphocline and nitracline which in turn prevented surfacing of nitrate+nitrite-nitrogen during the next upwelling event observed a week after the upwelling relaxation. A suggestion is made that such widening of nutricline separation caused by similar upwelling events in early summer could create favourable conditions for late summer cyanobacterial blooms.     

Ecosystem water use efficiency in an irrigated cropland in the North China Plain

The eddy covariance technique and the cuvette method were used to investigate water use efficiency in an irrigated winter wheat (Triticum asetivum L.)/summer maize (Zea mays L.) rotation system in the North China Plain. The results show that ecosystem water use efficiency (WUE_e) changed diurnally and seasonally. Daily maximal WUE_e appeared in the morning. WUE_e generally peaked in late April in wheat field and in late July/early August in maize field. From 2003 to 2006, seasonal mean WUE_e was 6.7–7.4 mg CO₂ g⁻¹ H₂O for wheat and 8.4–12.1 mg CO₂ g⁻¹ H₂O for maize. WUE_e was much lower than canopy water use efficiency (WUE_c) under small leaf area index (LAI) but very close to WUE_c under large LAI. With the increase in LAI, WUE_e enlarged rapidly under low LAI but slowly when LAI was higher than one. WUE_e was greater on the cloudy days than on the sunny days. Under the same solar radiation, WUE_e was higher in the morning than in the afternoon. The ratio of internal to ambient CO₂ partial pressure (C_i/C_a) decreased significantly with the increase in photosynthetically active radiation (PAR) when PAR was lower than the critical values (around 500 and 1000 μmol m⁻² s⁻¹ for wheat and maize, respectively). Beyond critical PAR, C_i/C_a was approximately constant at 0.69 for wheat and 0.42 for maize. Therefore, when LAI and solar radiation was large enough, WUE_e has negative correlation with vapor pressure deficit in both of irrigated wheat and maize fields.     

Total body burden and tissue distribution of polyfluorinated compounds in harbor seals (Phoca vitulina) from the German Bight

Total body burden and tissue distribution of polyfluorinated compounds (PFCs) were investigated in harbor seals (Phoca vitulina) from the German Bight in 2007. A total number of 18 individual PFCs from the following groups could be quantified in the different tissues: perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs) and their precursors perfluorinated sulfinates (PFSiAs), perfluorinated sulfonamides, and sulfonamido ethanols. Perfluorooctanesulfonate (PFOS) was the predominant compound in all measured seal tissues (up to 1665 ng g⁻¹ wet weight in liver tissue). The dominant PFCAs were perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA), but their concentrations were much lower compared to PFOS. The mean whole body burden in harbor seals of all detected PFCs was estimated to be 2665 ± 1207 μg absolute. The major amount of the total PFCs burden in the bodies was in blood (38%) and liver (36%), followed by muscle (13%), lung (8%), kidney (2%), blubber (2%), heart (1%), brain (1%), thymus (<0.01%) and thyroid (<0.01%). These data suggest large differences in body burden and accumulation pattern of PFCs in marine mammals.     

Mercury contamination history of an estuarine floodplain reconstructed from a Pb-dated sediment core (Berg River, South Africa)

Mercury deposition histories have been scarcely documented in the southern hemisphere. A sediment core was collected from the ecologically important estuarine floodplain of the Berg River (South Africa). We establish the concentration of Hg in this ²¹⁰Pb-dated sediment core at <50 ng g⁻¹ Hg_T throughout the core, but with 1.3 ng g⁻¹ methylmercury in surface sediments. The ²¹⁰Pb dating of the core provides a first record of mercury deposition to the site and reveals the onset of enhanced mercury deposition in 1970. The ratio of methylmercury to total mercury is relatively high in these sediments when compared to other wetlands.     

Thermal equation of state of magnesite to 32 GPa and 2073 K

Pressure–volume–temperature relations have been measured to 32 GPa and 2073 K for natural magnesite (Mg_0.975Fe_0.015Mn_0.006Ca_0.004CO₃) using synchrotron X-ray diffraction with a multianvil apparatus at the SPring-8 facility. A least-squares fit of the room-temperature compression data to a third-order Birch–Murnaghan equation of state (EOS) yielded K₀ = 97.1 ± 0.5 GPa and K′ = 5.44 ± 0.07, with fixed V₀ = 279.55 ± 0.02 Å³. Further analysis of the high-temperature compression data yielded the temperature derivative of the bulk modulus (∂K_T/∂T)_P = −0.013 ± 0.001 GPa/K and zero-pressure thermal expansion α = a₀ + a₁T with a₀ = 4.03 (7) × 10⁻⁵ K⁻¹ and a₁ = 0.49 (10) × 10⁻⁸ K⁻². The Anderson–Grüneisen parameter is estimated to be δ_T = 3.3. The analysis of axial compressibility and thermal expansivity indicates that the c-axis is over three times more compressible (K_Tc = 47 ± 1 GPa) than the a-axis (K_Tc = 157 ± 1 GPa), whereas the thermal expansion of the c-axis (a₀ = 6.8 (2) × 10⁻⁵ K⁻¹ and a₁ = 2.2 (4) × 10⁻⁸ K⁻²) is greater than that of the a-axis (a₀ = 2.7 (4) × 10⁻⁵ K⁻¹ and a₁ = −0.2 (2) × 10⁻⁸ K⁻²). The present thermal EOS enables us to accurately calculate the density of magnesite to the deep mantle conditions. Decarbonation of a subducting oceanic crust containing 2 wt.% magnesite would result in a 0.6% density reduction at 30 GPa and 1273 K. Using the new EOS parameters we performed thermodynamic calculations for magnesite decarbonation reactions at pressures to 20 GPa. We also estimated stability of magnesite-bearing assemblages in the lower mantle.     

Organic biomarkers for tracing carbon cycling in the Gulf of Papua (Papua New Guinea)

Sediment traps were deployed in the Gulf of Papua in June–July 1997, to determine fluxes of organic matter and inorganic elements from the photic zone to deeper waters at the base of the continental slope and in the northern Coral Sea. Three stations, ranging from 900 to 1500 m depth, had “shallow” traps at 300 m below the water surface and “deep” traps set 100 m above the bottom. Infiltrex II water samplers collected particulate and dissolved organic matter from the Fly, Purari and Kikori rivers, and near-surface water from the shelf of the Gulf of Papua. Samples were analysed for molecular organic biomarkers to estimate the sources of organic carbon and its cycling processes.Dry weight fluxes from the shallow traps ranged from 115 to 181 mg m⁻² day⁻¹ and particulate organic carbon (POC) fluxes ranged from 1.2 to 1.9 mM OC m⁻² d⁻¹ with molar organic carbon to particulate nitrogen ratios (C/N) ranging from 6.0 to 6.5. Fluxes in deep traps were likely influenced by both early diagenesis and entrapment of resuspended shelf sediments. Dry weight fluxes in deep traps ranged from 106 to 574 mg m⁻² day⁻¹ and POC fluxes ranged from 0.6 to 1.5 mM OC m⁻² d⁻¹, with C/N ratios ranging from 8.5 to 10.8. ¹³C/¹²C ratios were −20.2‰ to −21.7‰ in all trap samples, indicating that most of the settling POC was “marine-derived”. Shallow traps had δ¹⁵N values of 6.3‰ to 7.2‰ while the values in deep traps were 4.9–5.0‰, indicating the N-rich near-surface OC was less degraded than that in the deep traps. The biogenic lipids consisted of hydrocarbon, sterol and fatty acid biomarkers indicative of marine zooplankton, phytoplankton and bacteria. Sterol markers for diatoms and dinoflagellates were abundant in the water samples. Highly branched isoprenoid alkenes, usually attributable to diatoms, were also detected in both water and shallow traps. Traces of C₂₆–C₃₄ n-alcohols indicative of land–plant biomarkers, were found in river water samples and in the shallow sediment traps. A large unresolved complex mixture (UCM) of hydrocarbons, and a uniform distribution of n-alkanes, indicative of petroleum hydrocarbons, were also detected in the traps. Hopane and sterane biomarkers detected in the trap oil were characteristic of a marine carbonate source, and the aromatic hydrocarbon composition distinguished at least two different oil signatures.We concluded that mass and POC fluxes were similar to those reported for other continental shelves and marginal oceans in tropical and subtropical regions. There was a dramatic decrease in POC as particles sank, due to zooplankton repackaging and photochemical and bacterial decomposition. Carbon isotopic and biomarker patterns showed most of the POC in the sediment traps was marine-sourced with only traces of terrestrial input. There was a significant flux of petroleum, which may signal the existence of natural petroleum seeps in this region.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

Imposex levels and concentrations of organotin compounds (TBT and its metabolites) in Nassarius nitidus from the Lagoon of Venice

Specimens of Nassarius nitidus were collected in seven stations of the Venice Lagoon to assess the levels of tributyltin (TBT) and its metabolites monobutyltin and dibutyltin in the tissues and monitor their effect on organisms, in particular the phenomenon of imposex (superimposition of male sexual characteristics on females). The following values of population indices were found: vas deferens sequence: 1.2 ± 0.7–4.0 ± 0.5; relative penis length: 6–47%. The least impacted station was situated in the northern part of the Lagoon, where females without imposex were found and Butyltin (BuTs) concentrations in the organisms (average sum of BuTs = 43 ± 14 ng Sn g⁻¹ w.) were significantly lower than in the other stations (range of average sum of BuTs: 101 ± 22–217 ± 27 ng Sn g⁻¹ d.w.). Population indices were found to be related to the TBT content in the tissues. In particular VDSI had a significant logarithmic correlation: r = 0.95, n = 8, p < 0.05.     

Simultaneous radio and optical observations of the mid-latitude atmospheric response to a major geomagnetic storm of 6–8 April 2000

Basic properties of the mid-latitude traveling ionospheric disturbances (TIDs) during the maximum phase of a major magnetic storm of 6–8 April 2000 are shown. Total electron content (TEC) variations were studied by using data from GPS receivers located in Russia and Central Asia. The nightglow response to this storm at mesopause and termospheric altitudes was also measured by optical instruments FENIX located at the observatory of the Institute of Solar-Terrestrial Physics (51.9°N,103.0°E), and MORTI located at the observatory of the Institute of Ionosphere (43.2°N, 77.0°E). Observations of the O (557.7 and 630.0 nm) emissions originating from atmospheric layers centered at altitudes of 90 and 250 km were carried out at Irkutsk and of the O₂(b¹∑_g⁺−X³∑_g⁻) (0-1) emission originating from an atmospheric layer centered at altitude of 94 km was carried out at Almaty. Our radio and optical measurement network observed a storm-induced solitary large-scale wave with duration of 1 h and a wave front width of no less than 5000 km, while it traveled equatorward with a velocity of 200 m/s from 62°N to 38°N geographic latitude. The TEC disturbance, basically displaying an electron content depression in the maximum of the F2 region, reveals a good correlation with growing nightglow emission, the temporal shift between the TEC and emission variation maxima being different for different altitudes. A comparison of the auroral oval parameters with dynamic spectra of TEC variations and optical 630 nm emissions in the frequency range 0.4–4 mHz (250–2500 s periods) showed that as the auroral oval expands into mid-latitudes, also does the region with a developed medium-sale and small-scale TEC structure.     

Transport of oceanic nitrate from the continental shelf to the coastal basin in relation to the path of the Kuroshio

Hydrographic and biogeochemical observations were conducted along the longitudinal section from Ise Bay to the continental margin (southern coast of Japan) to investigate changes according to the Kuroshio path variations during the summer. The strength of the uplift of the cold deep water was influenced by the surface intrusion of the Kuroshio water to the shelf region. When the intrusion of the Kuroshio surface water to the shelf region was weak in 2006, the cold and NO₃⁻-rich shelf water intruded into the bottom layer in the bay from the shelf. This bottom intrusion was intensified by the large river discharge. The nitrogen isotope ratio (δ¹⁵N) of NO₃⁻ (4–5‰) in the bottom bay water was same as that in the deeper NO₃⁻ over the shelf, indicating the supply of new nitrogen to the bay. The warm and NO₃⁻-poor shelf water intruded into the middle layer via the mixing region at the bay mouth when the Kuroshio water distributed in the coastal areas off Ise Bay in 2005. The regenerated NO₃⁻ with isotopically light nitrogen (δ¹⁵N=−1‰) was supplied from the shelf to the bay. This NO₃⁻ is regenerated by the nitrification in the upper layer over the shelf. The contribution rate of regenerated NO₃⁻ over the shelf to the total NO₃⁻ in the subsurface chlorophyll maximum layer in the bay was estimated at 56% by a two-source mixing model coupled with the Rayleigh equation.     

Coupling of early diagenetic processes and sedimentary dynamics in tropical shelf environments: the Gulf of Papua deltaic complex

Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 10 and 20 m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 0.5–1 m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (100–200, but up to 800 μM). Sediments are reactive, with surficial ΣCO₂ production 0.1–0.3 mM d⁻¹ and benthic O₂ fluxes 23±15 mmol m⁻² d⁻¹ (upper 20 cm). The highest rates occur within inner topset deposits (10–20 m) and near the high accumulation rollover region of the topset–foreset beds (40–50 m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O₂ usually penetrates 2–5 mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (350–400 μmol g⁻¹) is typically diagenetically reduced in the upper 0.5 m. Pore water can be measureably depleted at depths >0.5 m, but dissolved H₂S generally remains below detection over the upper 1–2 m. As in other deltaic topset regions, concentration gradients often indicate that compared to many marine deposits of similar sediment accumulation rates, relatively refractory C_org is supplied to the SO₄ reducing zone. Sedimentary C/S ratios are 4–6 within the suboxic topset regions but decrease to <3 in offshore foreset beds where sulfidic diagenesis dominates. Only 15–20% of the diagenetically reduced Fe(II) is pyritic and a maximum of 10–25% is carbonate, implying that most Fe(II) is associated with authigenic or lithogenic silicates or oxides. The dominance of suboxic, nonsulfidic diagenetic processes reflect coupling between delivery of oxide-rich terrestrial debris, remobilization and reoxidation of deposits, and repetitive entrainment/remineralization of both labile and refractory organics. Distinct sedimentary indicators of reactive, suboxic mobile mud belts within tropical climatic zones are: abundant total highly reactive Fe (ΣFeR )>300 μmol g⁻¹; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR0.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)<0.2); C/S 4–8; and C_org/particle surface area <0.4 (mg C m⁻²). These depositional environments must be most common in tropical climates during high sea stand.     

Efficient trapping of organic carbon in sediments on the continental margin with high fluvial sediment input off southwestern Taiwan

Accumulation rates of marine and terrigenous organic carbon in the continental margin sediments off southwestern Taiwan were estimated from the measured concentrations and isotopic compositions of total organic carbon (TOC) and previously reported sedimentation rates. Surficial sediments were collected from the study area spanning from the narrow shelf near the Kaoping River mouth to the deep slope with depths reaching almost 3000 m. The average sediment loading of Kaoping River is 17 Mt/yr, which yields high sediment accumulation rates ranging from 0.08 to 1.44 g cm⁻² yr⁻¹ in the continental margin. About half of the discharged sediments were deposited on the margin within 120 km of the river mouth. Carbon isotopic compositions of terrestrial and marine end-members of organic matter were determined, respectively, based on suspended particulate matter (SPM) collected from three major rivers in the southwestern Taiwan and from an offshore station. All samples were analyzed for the TOC content and its isotopic composition (δ¹³C_org). The SPM samples were also analyzed for the total nitrogen (TN) content. TOC content in marine sediments ranges from 0.45% to 1.35% with the highest values on the upper slope near the Kaoping River mouth. The TOC/TN ratio of the SPM samples from the offshore station is 6.8±0.6, almost identical to the Redfield ratio, indicating their predominantly marine origin; their δ¹³C_org values are also typically marine with a mean of −21.5±0.3‰. The riverine SPM samples exhibit typical terrestrial δ¹³C_org values around −25‰. The δ¹³C_org values of surficial sediments range from −24.8‰ to −21.2‰, showing a distribution pattern influenced by inputs from the Kaoping River. The relative contributions from marine and terrestrial sources to sedimentary organic carbon were determined by the isotope mixing model with end-member compositions derived from the riverine and marine SPM. High fluvial sediment inputs lead to efficient trapping of organic carbon over a wide range of water depth in this continental margin. The marine organic accumulation rate ranges from 1.6 to 70 g C m⁻² yr⁻¹ with an area weighted mean of 4.2 g C m⁻² yr⁻¹, which is on a par with the mean terrestrial contribution and accounts for 2.3% of mean primary production. The depth-dependent accumulation rate of marine organic carbon can be simulated with a function involving primary productivity and mineral accumulation rate, which may be applicable to other continental margins with high sedimentation rates. Away from the nearshore area, the content of terrigenous organic carbon in surficial sediments decreases with distance from the river mouth, indicating its degradation in marine environments.     

The ClBrI composition of 3.23 Ga modified seawater: implications for the geological evolution of ocean halide chemistry

Fluid inclusion leachates obtained from vug and vein quartz samples from an Archean (3.23 Ga) Fe-oxide hydrothermal deposit in the west-central part of the Barberton greenstone belt, South Africa, were analyzed by ion chromatography for chloride, bromide, and iodide. The deposit, known as the ironstone pods, formed by seafloor hydrothermal activity and fluid discharge. Quartz is dominated by type I liquid-vapor, aqueous inclusions with a bimodal salinity distribution (0–0.25 M_Cl⁻ and 0.9–1.8 M_Cl⁻). Bulk analytical salinities range from 0.45 to 0.99 M_Cl⁻ represent averages of type I inclusions. Bulk fluid inclusion bromide and iodide concentrations are 1.44–3.32 mM and 0.01–0.12 mM, respectively. For comparison, modern seawater has halogen contents of 590 mM chloride, 0.9 mM bromide, and 0.5 μM total iodine. In the fluids from the ironstone pods, bromide and iodide are enriched relative to chloride, when compared with modern seawater.Approximate Br⁻Cl⁻ and I⁻Cl⁻ ratios of 3.2 Ga Barberton seawater are 2.5 × 10⁻³ and 40 × 10⁻⁶, respectively. Dispersion to higher values was caused principally by reaction with organic sediments whose trends are similar to those seen for modern vent fluids at unsedimented and sedimented ridges, relative to modern seawater. These halide ratios are greater than those of modern seawater, suggesting a change in the halide ratios of seawater over geological time. The analytical data are consistent with a model in which marine organic sedimentation has fractionated bromine and iodine out of seawater relative to chloride, thereby causing the halide ratios of seawater to decrease from high early and mid-Archean values towards their present day values.     

Distribution and speciation of mercury in surficial sediments from main mangrove wetlands in China

The purpose of this study was to establish the distribution, speciation and bioavailability of mercury in mangrove sediments. A systemic survey of surficial sediments from 13 mangrove wetlands of China was carried out. Hg concentrations ranged from 2.3–903.6 ng g⁻¹, with an average value of 189.4 ng g⁻¹. Of the 13 areas surveyed, the Hg content in sediments was similar to background levels in 6 areas but was much higher in the other seven areas. Hg levels were affected by natural and anthropogenic factors, including terrestrial pollutants, geomorphic properties, and indirectly by economic status. Hg levels were positively correlated with organic matter, pH, and silt and clay fractions, but Hg was negatively correlated with sand fraction. In most mangrove wetlands, Hg existed primarily in the form of volatile Hg. Hg is easily bioaccumulated in mangrove wetlands and may be the natural source of Hg emissions to the atmosphere.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.