VERTEX: manganese transport through oxygen minima

Manganese transport through a well-developed oxygen minimum was studied off central Mexico (18°N, 108°W) in October–November 1981 as part of the VERTEX (Vertical Transport and Exchange) research program. Refractory, leachable and dissolved Mn fractions associated with particulates caught in traps set at eight depths (120–1950 m) were analyzed. Particles entering the oxygen minimum had relatively large Mn loads; however, as the particulates sank further into the minimum, total Mn fluxes steadily decreased from 190 nmol m^?2 day^?1 at 120 m to 36 nmol m^?2 day^?1 at 400 m. Manganese fluxes then steadily increased in the remaining 800–1950 m, reaching rates of up to 230 nmol m^?2 day^?1 at 1950 m.Manganese concentrations were also measured in the water column. Dissolved Mn levels < 3.0 nmol kg^?1 were consistently observed within the 150–600 m depth interval. In contrast, suspended particulate leachable Mn amounts were especially low at those depths, and never exceeded 0.04 nmol kg^?1.The combined water column and particle trap data clearly indicate that Mn is released from particles as they sink through the oxygen minimum. Rate-of-change estimates based on trap flux data yield regeneration rates of up to 0.44 nmol kg^?1 yr^?1 in the upper oxygen minimum (120–200 m). However, only 30% of the dissolved Mn in the oxygen minimum appears to be from sinking particulate regeneration; the other 70% probably results from continental-slope-release-horizontal-transport processes.Dissolved Mn scavenges back onto particles as oxygen levels begin to increase with depth. Scavenging rates ranging from ?0.03 to ?0.09 nmol kg^?1 yr^?1 were observed at depths from 700 to 1950 m. These scavenging rates result in Mn residence times of 16–19 years, and scavenging rate constants on the order of 0.057 yr^?1. Manganese removal via scavenging on sinking particles below the oxygen minimum is balanced by Mn released along continental boundaries and transported horizontally via advective-diffusive processes.Manganese appears to be very weakly associated with particulates. Nevertheless, the amounts of Mn involved with sinking biogenic particles are large, and the resulting fluxes are on the same order of magnitude as those necessary to explain the excess Mn accumulating on the sea floor. The overall behavior of Mn observed in this, and other, studies strongly suggests some type of equilibrium occurring between dissolved and particulate phases. This equilibrium appears to shift in direct or indirect response to dissolved oxygen levels.     

Correlation between δ~(18)O,Sr/Ca and Mg/Ca of coral Acropora and seawater temperature from coral culture experiments

To be used as proxies of seawater surface temperature(SST), the δ 18Oc values and Sr/Ca and Mg/Ca ratios of scleractinian coral skeletons must be verified by coral culture experiments in the laboratory. This paper describes a coral culture experiment that was conducted at several seawater temperatures T(21–28°C) using a tandem aquarium system and the new method for depositing coral skeletons grown under controlled conditions. The δ 18Oc values and the Sr/Ca and Mg/Ca ratios of the cultured coral were measured. We concluded that the δ 18Oc values and Sr/Ca and Mg/Ca ratios of the cultured coral are clearly correlated with T. The linear regression curve is δ18Oc(‰)=δ0.1427δT(°C)δ0.1495(n=18, r=0.955, p0.0001), and the slope of δ0.1427‰/°C is at the low end of the range of published values(δ0.13–δ0.29‰/°C). The Sr/Ca ratio decreases with increasing T, whereas the Mg/Ca ratio increases with increasing T, indicating a negative correlation between Sr/Ca and Mg/Ca. Their linear regression curves are Sr/Ca(mmol/mol)=δ0.04156δT+10.59(n=15, r=0.789, p0.005) and Mg/Ca(mmol/mol)= 0.04974δT+2.339(n=17, r=0.457, p0.05), respectively, which demonstrate that when Mg/Ca and Sr/Ca are increased by one unit, T increases by 5.19°C and decreases by 15.62°C, respectively. These variations are significantly lower than published values.     

Correlations between13C and ΣCO2 in surface waters and atmospheric CO2

¹³C and ΣCO₂ data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ¹³C of the ΣCO₂ in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO₂ per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO₂, while the remainder is attributed to dissolution of calcium carbonate.The δ¹³C of the dissolved CO₂ in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO₂ at a mean temperature of 16°C. The δ¹³C and ΣCO₂ values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water.     

Isotopic evidence for meteoric-hydrothermal alteration of plutonic igneous rocks in the Yakutat Bay and Skagway areas,Alaska

Oxygen and hydrogen isotope ratios were measured on coexisting minerals from quartz diorites and quartz monzonites from a section across the Coast Range batholith in the Skagway area, Alaska, including a variety of outlying plutons west of the batholith in the Yakutat Bay-Mt. St. Elias region (latitudes 59–60°N). The extremely low and variable δ¹⁸Oand δD results indicate widespread meteoric-hydrothermal alternaiton of the Coast Range batholith, and to a lesser extent, of the Yakutat Bay plutons as well. In the Yakutat Bay area, the plutons with K—Ar ages younger than 50 m.y. have widely varying δD values of ?72 to ?148, compared to δD = ?69to?90 for all but one sample in the 50–225 m.y. age grouping (one biotite has δD = ?109). This suggests that the major meteoric-hydrothermal episodes in this area occurred during the Eocene and Miocene. This involved relatively small meteoric water/rock ratios(<0.1), as none of the δ¹⁸O values show any clear-cut evidence of alteration (δ¹⁸O_quartz= 7.4 ?11.8; δ¹⁸O_feldspar= 5.7?10.0). However, in the section across the Coast Range batholith, 85% of the plutonic rocks have very low δD values of ?100 to ?167, and the δ¹⁸O values are extremely variable δ¹⁸O_feldspar= + 10.3to?4.0 and Δ¹⁸O_{quartz-feldspar}= 0.4?10.5. These data indicate that a major portion of the batholith, particularly the quartz monzonite-rich eastern part, but also including many of the quartz diorite plutons as well, interacted with meteoric-hydrothermal convective systems that involved water/rock ratios of about 0.3–1.4. The quart diorite plutons are most depleted in¹⁸O near their northeast contacts against the younger quartz monzonite intrusions. The primary igneous δ¹⁸O values of the quartz diorites were apparently higher than those of the quartz monzonites; they are also unusually high in¹⁸O compared to most other analyzed quartz diorites, suggesting derivation from, exchange with, or assimilation of high-¹⁸O metasediments or altered volcanic rocks. These data and conclusions are very similar to those reached previously on a similar isotopic study of the Coast Range batholith in British Columbia, 700 km to the southeast at latitudes 54–55°N, except that in the Skagway area an even greater proportion of the batholith was apparently depleted in deuterium. This implies that deep (?5km?) circulation of meteoric groundwaters is probably a characteristic of the later stages of emplacement of the Cordilleran batholiths of western North America, suggesting that the eastern sections of these batholiths in particular were emplaced at relatively shallow depths.     

Helium-3 and manganese at the 21°N East Pacific Rise hydrothermal site

Water samples collected at the 21°N hydrothermal site on the East Pacific Rise crest, including Deep-Tow and hydrocast samples collected in 1977 and three hot vent water samples collected recently with the submersible “Alvin”, contain significant additions of³He,⁴He, and Mn. Although the vent water collections were at least 50-fold diluted with ambient seawater, they are up to 53 times enriched in³He and 7.4 times enriched in⁴He relative to saturated seawater, with concentrations of total dissolvable manganese (TDM) up to 310 μg/kg.³He and⁴He covary in the vent samples, with³He/⁴He about 8 times the atmospheric ratio, reflecting a mantle helium source. In contrast to the helium isotopes the Mn/³He ratio in the vent samples is variable, ranging from 4.3 × 10⁴ up to 1.0 × 10⁵ g/cm³. Profiles of³He/⁴He and TDM in the water column at 21°N show a sharp maximum ofδ(³He) = 47%and TDM= 0.69 μg/kg, much higher than the average values of 34% and 0.2 μg/kg for the deep water in this region. This spike in³He and Mn occurs at 2400 m depth, 200 m above the level of the 21°N vents, and 100 m higher than any local bathymetry, evidence for upward transport of the hydrothermal discharge via rising plumes of hot vent water. Two of the 21°N Deep-Tow samples associated with small (?0.010°C) temperature anomalies hadδ(³He) = 38%and TDM= 0.28 and 0.58 μg/kg, also slightly elevated relative to background. The Deep-Tow and hydrocast samples have lower Mn/³He ratios than average vent samples due to Mn removal by scavenging. Comparison of vent samples and water column measurements at 21°N indicate that the pure vent water could be detected using³He and Mn even when diluted ～10⁵ times with seawater, confirming that these two tracers are extremely sensitive indicators of submarine hydrothermal activity.     

Wetland nitrogen dynamics in an Adirondack forested watershed

Wetlands often form the transition zone between upland soils and watershed streams, however, stream–wetland interactions and hydrobiogeochemical processes are poorly understood. We measured changes in stream nitrogen (N) through one riparian wetland and one beaver meadow in the Archer Creek watershed in the Adirondack Mountains of New York State, USA from 1 March to 31 July 1996. In the riparian wetland we also measured changes in groundwater N. Groundwater N changed significantly from tension lysimeters at the edge of the peatland to piezometer nests within the peatland. Mean N concentrations at the peatland perimeter were 1·5, 0·5 and 18·6 µmol L^?1 for NH₄⁺, NO₃^? and DON (dissolved organic nitrogen), respectively, whereas peatland groundwater N concentration was 56·9, 1·5 and 31·6 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively. The mean concentrations of stream water N species at the inlet to the wetlands were 1·5, 10·1 and 16·9 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively and 1·6, 28·1 and 8·4 µmol L^?1 at the wetland outlet. Although groundwater total dissolved N (TDN) concentrations changed more than stream water TDN through the wetlands, hydrological cross‐sections for the peatland showed that wetland groundwater contributed minimally to stream flow during the study period. Therefore, surface water N chemistry was affected more by in‐stream N transformations than by groundwater N transformations because the in‐stream changes, although small, affected a much greater volume of water. Stream water N input–output budgets indicated that the riparian peatland retained 0·16 mol N ha^?1 day^?1 of total dissolved N and the beaver meadow retained 0·26 mol N ha^?1 day^?1 during the study period. Nitrate dominated surface water TDN flux from the wetlands during the spring whereas DON dominated during the summer. This study demonstrates that although groundwater N changed significantly in the riparian peatland, those changes were not reflected in the stream. Consequently, although in‐stream changes of N concentrations were less marked than those in groundwater, they had a greater effect on stream water chemistry—because wetland groundwater contributed minimally to stream flow. Copyright © 2004 John Wiley & Sons, Ltd.     

Chemistry of solutions from the 13°N East Pacific Rise hydrothermal site

Ten samples were recovered by the submersible “Cyana” submersible from two groups of hydrothermal vents located 2600 m deep along the East Pacific Rise at 13°N. The maximum measured temperature was 317°C and minimum pH 3.8. A systematic determination of major and trace elements has been carried out and mixing lines between a high-temperature component (HTC) and seawater are observed. The water chemistry of the HTC slightly differs for several elements at the two sites. This HTC is deprived of SO₄ and Mg and is greatly enriched in most other species. Maximum concentrations are (in units per kg):Cl = 0.72mol; Br = 1.1mmol; Na = 0.55mol; K = 29mmol; Rb = 14 μmol; Ca = 52mmol; Sr = 170 μmol; Mn = 750 μmol; Fe = 1mmol; Al = 15 μmol; Si = 21mmol. For many elements, the magnitude of the anomaly relative to seawater does not compare with the results obtained from the Galapagos or East Pacific Rise 21°N. The enrichment of cations relative to seawater is likely related to the huge Cl excess through charge balance. TheBr/Cl ratio is close to that for seawater. However, it is not clear whether the Cl excess is due to gas release or basalt hydration (formation of amphibole chlorite or epidote).P-T dependence of SiO₂ solubility suggests that water-rock interaction last occurred at a depth in excess of 1 km below the sea floor. A mixing line of⁸⁷Sr/⁸⁶Sr vs. Mg/Sr demonstrates that the HTCs have a nearly identical⁸⁷Sr/⁸⁶Sr ratio of 0.7041 for both sites. A water/rock ratio of about 5 is inferred, which differs from the 1.5 value obtained at 21°N.     

Cenozoic evolution of the sulfur cycle: Insight from oxygen isotopes in marine sulfate

We report new data on oxygen isotopes in marine sulfate (δ¹⁸O_SO4), measured in marine barite (BaSO₄), over the Cenozoic. The δ¹⁸O_SO4 varies by 6‰ over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The δ¹⁸O_SO4 does not co-vary with the δ³⁴S_SO4, emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the δ¹⁸O_SO4 over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The δ¹⁸O_SO4 also does not co-vary with the δ¹⁸O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the δ¹⁸O_SO4 to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the δ¹⁸O_SO4. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.     

Dynamics of seasonal recharge beneath a semiarid vegetation on the gnangara mound,Western Australia

To estimate seasonal changes in recharge to the underlying sandy aquifer, the soil water dynamics of the unsaturated zone was monitored down to a depth of 20 m over a period of three years (1985 to 1987). The measurements were made by a neutron probe at eight locations beneath a native vegetation in a semiarid region, Western Australia, receiving precipitation of 775 mm yr^?1. A relatively simple method, based on the analyses of sequentially measured soil water profiles involving utilization of zero flux plane in the unsaturated zone, is presented and used to compute seasonal recharge rates. Drainage fluxes (recharge rates) below two specified depths were estimated. These were: R₁ (water flux at a depth of 10 m, just below the maximum rooting depth) and R₂ (water flux at a depth of 18 m, just above the water table). These two estimates were significantly different both on a seasonal and annual basis, but their cumulative values for the three year period were very similar. While the annual precipitation varied from 525 to 850 mm yr^?1, the corresponding spatially averaged R₁ varied from 34 to 149 mm yr^?1, and R₂ varied from 65 to 80 mm yr^?1. A significant difference in recharge between the upslope and downslope positions on a hillslope was ascribed to differences in vegetation density of the understorey and differences in hydraulic properties of subsoils. For the three year period, the average R₁ and R₂ were 13 per cent and 10 per cent of the precipitation respectively. These values compare favourably with a long-term estimate based on an environmental tracer technique.     

Oxygen self-diffusion in forsterite: Implications for the high-temperature creep mechanism

The diffusivity of¹⁸O in forsterite Mg₂SiO₄ has been measured in the temperature range 1150–1600°C. The activation energy of oxygen self-diffusion in this silicate is found to equal0.32 ± 0.04MJ/mol(77 ± 10kcal/mol), and there is no dependence of the diffusivity upon the oxygen partial pressure surrounding the samples. The diffusion profiles were analysed either with an ion probe or by means of the¹⁸O(p, α)¹⁵N nuclear reaction. The latter method made use of a resonance in the nuclear cross-section in the case of diffusion profiles shorter than 100 nm (1000Å); for diffusion profiles up to 4 μm the same reaction was used, but in a non-resonant mode. New data on creep in forsterite and natural olivine are also given, including the influence of the oxygen partial pressurep_O2 which is zero for forsterite and proportional to(p_O2)¹⁶ for natural olivine. From this set of data we infer the possible relationship between diffusion and creep for these materials. This relationship may be more complicated than that predicted by simple climb mechanism.     

Turnover of Eastern Caribbean deep water from 14C measurements

A¹⁴C balance for the Eastern Caribbean deep water indicates the average inflow of Atlantic water into the basin to be 2.3 × 10⁵ m³/sec (±30%), or about 2–4 times the values estimated previously. The balance uses a model representation of the deep-water turnover, and is based on¹⁴C concentrations at a station in the Venezuelan Basin which average Δ¹⁴C= 89‰ below 800 m depth with a total range of only 9‰, as well as on a¹⁴C concentration of the Atlantic inflow of Δ¹⁴C= ?71%. as obtained from measurements outside the Antilles Arch. The turnover time of the basin water below 2500 m depth is 55 years, which corresponds to an average upwelling velocity at this depth of about 35 m/year. With such upwelling, the temperature profile below 1800 m (the depth of the sill determining the inflow of new water) requires a vertical eddy diffusivity of about 5 cm²/sec. The oxygen consumption, and silica and CO₂ regeneration, rates below 2500 m depth are obtained as ?0.18, + 0.08, and + 0.2 μmole kg^?1 yr^?1, respectively. The CO₂ regeneration has but a negligible effect on the¹⁴C balance.     

Stable isotopic compositions and controlling factors of precipitation and atmospheric vapour in the headwaters of the Shule River

Stable isotopic compositions of precipitation (δ¹⁸O_p, δ²H_p and d-excess_p) and atmospheric vapour (δ¹⁸O_v, δ²H_v and d-excess_v) with high spatial–temporal resolution are crucial in revealing hydrologic cycle. Based on the variation characteristics of δ¹⁸O_p/δ¹⁸O_v, δ²H_p/δ²H_v and d-excess_p/d-excess_v in the headwaters of the Shule River (HSR) on hourly and daily scales from June to September 2018, this study analysed the relationships between δ¹⁸O_p/δ²H_p and δ¹⁸O_v/δ²H_v combined with the equilibrium fractionation model, as well as δ¹⁸O_p/δ¹⁸O_v and meteorological factors. The slopes of local meteoric water line (LMWL) and the δ²H_v-δ¹⁸O_v fitting equation were similar (7.96 and 7.94) with both intercepts exceeding 10, reflecting the great contribution of recycling moisture. The values of δ¹⁸O_v/δ²H_v were lower than δ¹⁸O_p/δ²H_p but with consistent variation patterns throughout the period. The equilibrium simulation results suggested that precipitation and atmospheric vapour almost approached isotopic equilibrium state, especially during monsoon intrusion period. Affected by monsoon intrusion, the slopes and intercepts of the LMWLs and the δ²H_v-δ¹⁸O_v fitting equations were smaller than those during non-monsoon period and d-excess and δ¹⁸O were negatively correlated. Relative humidity had significant negative correlations with δ¹⁸O_p and δ¹⁸O_v in the whole period, however, the positive correlations between δ¹⁸O_p/δ¹⁸O_v and temperature were observed during non-monsoon and monsoon intrusion period, respectively. Our results demonstrated that precipitation and atmospheric vapour isotopic compositions exhibited consistency under the influence of diverse moisture sources, while more complex relationships were found between δ¹⁸O_p/δ¹⁸O_v and meteorological factors. This research provided evidence for using the isotopic compositions of atmospheric vapour to indicate moisture sources, and can improve understanding of the water cycle and eco-hydrological process from the perspective of the interaction between water and gas phases of the inland river basin in northwest China.     

Stable and radiogenic isotopes as tracers for the origin,mixing and subsurface history of fluids in submarine shallow-water hydrothermal systems

The shallow-water hydrothermal system in Tutum Bay on the west side of Ambitle Island, Papua New Guinea provides us with an exceptional opportunity to study isotope systematics in a near shore setting. Compared to seawater, the hydrothermal fluids in Tutum Bay have lower values for δD, δ¹⁸O, δ¹³C, and ⁸⁷Sr and higher values for ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄). The δ¹⁸O and δD records for vents 1 and 4 indicate that fluid compositions remained stable over an extended period. Interpretation of isotope data clearly demonstrates the predominantly meteoric origin of Tutum Bay hydrothermal fluids, despite their location in a marine environment. δ¹⁸O and δD values are identical to mean average annual precipitation in eastern Papua New Guinea. The hypothesis that these fluids are a simple product of mixing between seawater and onshore hydrothermal fluids from the Waramung (W-1) and Kapkai (W-2) thermal areas has been rejected, because the observed δ³⁷Cl, ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄) values cannot be explained by a simple mixing model. The application of δ¹⁸O(SO₄) and δ¹³C thermometers in combination with ³H values corroborates the three-step model of Pichler et al. [Pichler, T., Veizer, J., Hall, G.E.M., 1999. The chemical composition of shallow-water hydrothermal fluids in Tutum Bay, Ambitle Island, Papua New Guinea and their effect on ambient seawater. Marine Chemistry 64 (3) 229–252], where (1) phase separation in the deep reservoir beneath Ambitle Island produces a high temperature vapor that rises upward and subsequently reacts with cooler ground water to form a low pH, CO₂-rich water of approximately 150–160 °C, (2) caused by the steep topography, this CO₂-rich fluid moves laterally towards the margin of the hydrothermal system where it mixes with the marginal upflow of the deep reservoir fluid. This produces a dilute chloride water of approximately 165 °C, and (3) possibly the entrainment of minor amounts of ground or seawater during its final ascent.     

Latitudinal patterns of export production recorded in surface sediments of the Chilean Patagonian fjords (41–55°S) as a response to water column productivity

The Chilean Patagonian fjords region (41–56°S) is characterized by highly complex geomorphology and hydrographic conditions, and strong seasonal and latitudinal patterns in precipitation, freshwater discharge, glacier coverage, and light regime; all of these directly affect biological production in the water column. In this study, we compiled published and new information on water column properties (primary production, nutrients) and surface sediment characteristics (biogenic opal, organic carbon, molar C/N, bulk sedimentary δ¹³C_org) from the Chilean Patagonian fjords between 41°S and 55°S, describing herein the latitudinal pattern of water column productivity and its imprint in the underlying sediments. Based on information collected at 188 water column and 118 sediment sampling sites, we grouped the Chilean fjords into four main zones: Inner Sea of Chiloé (41° to ～44°S), Northern Patagonia (44° to ～47°S), Central Patagonia (48–51°S), and Southern Patagonia (Magellan Strait region between 52° and 55°S). Primary production in the Chilean Patagonian fjords was the highest in spring–summer, reflecting the seasonal pattern of water column productivity. A clear north–south latitudinal pattern in primary production was observed, with the highest average spring and summer estimates in the Inner Sea of Chiloé (2427 and 5860 mg C m^?2 d^?1) and Northern Patagonia (1667 and 2616 mg C m^?2 d^?1). This pattern was closely related to the higher availability of nutrients, greater solar radiation, and extended photoperiod during the productive season in these two zones. The lowest spring value was found in Caleta Tortel, Central Patagonia (91 mg C m^?2 d^?1), a site heavily influenced by glacier meltwater and river discharge loaded with glacial sediments. Biogenic opal, an important constituent of the Chilean fjord surface sediments (Si_OPAL ～1–13%), reproduced the general north–south pattern of primary production and was directly related to water column silicic acid concentrations. Surface sediments were also rich in organic carbon content and the highest values corresponded to locations far away from glacier influence, sites within fjords, and/or semi-enclosed and protected basins, reflecting both autochthonous (water column productivity) and allochthonous sources (contribution of terrestrial organic matter from fluvial input to the fjords). A gradient was observed from the more oceanic sites to the fjord heads (west–east) in terms of bulk sedimentary δ¹³C_org and C/N ratios; the more depleted (δ¹³C_org ?26‰) and higher C/N (23) values corresponded to areas close to rivers and glaciers. A comparison of the Chilean Patagonian fjords with other fjord systems in the world revealed high variability in primary production for all fjord systems as well as similar surface sediment geochemistry due to the mixing of marine and terrestrial organic carbon.     

Studies on Primary Productivity and some Hydrochemical Aspects of a Polluted Water-body of the Himalayan Jhelum Valley

The lake without any outlet (11 ha, 55000 m³, z_max 2,25 m) has a weak thermal stratification with maximum surface temperatures of 32.5 °C. The annual variation of temperature and depth of visibility is unimodal, with the maxima or minima in August. Phytoplankton consists mainly of Cyanophyceae. The primary production determined by the light-dark bottle technique (oxygen method) varies in the annual variation between 0.3… 0.5 g m^?2 d^?1 C (winter) and 3.4… 4.6 g m^?2 d^?1 C (summer); as the annual means of 1975 and 1976 there were found 1.9 and 2.4 g m^?2 d^?1 C, resp., gross production at a utilization of 0.42… 2.85% of the radiation energy. The chemism is a well-buffered hydrogen-carbonate water (pH 8.1… 9.0) with 74… 90 mg/1 Na and 20.5… 31.5 mg/1 K and with a good nutrient supply (20… 40 μg/1 PO₄—P and 100… 240 μg/1 NO₃—N) at the same time.     

Carbon pools and fluxes in the China Seas and adjacent oceans

The China Seas include the South China Sea, East China Sea, Yellow Sea, and Bohai Sea. Located off the Northwestern Pacific margin, covering 4700000 km~2 from tropical to northern temperate zones, and including a variety of continental margins/basins and depths, the China Seas provide typical cases for carbon budget studies. The South China Sea being a deep basin and part of the Western Pacific Warm Pool is characterized by oceanic features; the East China Sea with a wide continental shelf, enormous terrestrial discharges and open margins to the West Pacific, is featured by strong cross-shelf materials transport; the Yellow Sea is featured by the confluence of cold and warm waters; and the Bohai Sea is a shallow semiclosed gulf with strong impacts of human activities. Three large rivers, the Yangtze River, Yellow River, and Pearl River, flow into the East China Sea, the Bohai Sea, and the South China Sea, respectively. The Kuroshio Current at the outer margin of the Chinese continental shelf is one of the two major western boundary currents of the world oceans and its strength and position directly affect the regional climate of China. These characteristics make the China Seas a typical case of marginal seas to study carbon storage and fluxes. This paper systematically analyzes the literature data on the carbon pools and fluxes of the Bohai Sea,Yellow Sea, East China Sea, and South China Sea, including different interfaces(land-sea, sea-air, sediment-water, and marginal sea-open ocean) and different ecosystems(mangroves, wetland, seagrass beds, macroalgae mariculture, coral reefs, euphotic zones, and water column). Among the four seas, the Bohai Sea and South China Sea are acting as CO_2 sources, releasing about0.22 and 13.86–33.60 Tg C yr~(-1) into the atmosphere, respectively, whereas the Yellow Sea and East China Sea are acting as carbon sinks, absorbing about 1.15 and 6.92–23.30 Tg C yr~(-1) of atmospheric CO_2, respectively. Overall, if only the CO_2 exchange at the sea-air interface is considered, the Chinese marginal seas appear to be a source of atmospheric CO_2, with a net release of 6.01–9.33 Tg C yr~(-1), mainly from the inputs of rivers and adjacent oceans. The riverine dissolved inorganic carbon (DIC) input into the Bohai Sea and Yellow Sea, East China Sea, and South China Sea are 5.04, 14.60, and 40.14 Tg C yr~(-1),respectively. The DIC input from adjacent oceans is as high as 144.81 Tg C yr~(-1), significantly exceeding the carbon released from the seas to the atmosphere. In terms of output, the depositional fluxes of organic carbon in the Bohai Sea, Yellow Sea, East China Sea, and South China Sea are 2.00, 3.60, 7.40, and 5.92 Tg C yr~(-1), respectively. The fluxes of organic carbon from the East China Sea and South China Sea to the adjacent oceans are 15.25–36.70 and 43.93 Tg C yr~(-1), respectively. The annual carbon storage of mangroves, wetlands, and seagrass in Chinese coastal waters is 0.36–1.75 Tg C yr~(-1), with a dissolved organic carbon(DOC) output from seagrass beds of up to 0.59 Tg C yr~(-1). Removable organic carbon flux by Chinese macroalgae mariculture account for 0.68 Tg C yr~(-1) and the associated POC depositional and DOC releasing fluxes are 0.14 and 0.82 Tg C yr~(-1), respectively. Thus, in total, the annual output of organic carbon, which is mainly DOC, in the China Seas is 81.72–104.56 Tg C yr~(-1). The DOC efflux from the East China Sea to the adjacent oceans is 15.00–35.00 Tg C yr~(-1). The DOC efflux from the South China Sea is 31.39 Tg C yr~(-1). Although the marginal China Seas seem to be a source of atmospheric CO_2 based on the CO_2 flux at the sea-air interface, the combined effects of the riverine input in the area, oceanic input, depositional export,and microbial carbon pump(DOC conversion and output) indicate that the China Seas represent an important carbon storage area.     

Mantle-derived carbon in Hercynian granites. Stable isotopes signatures and C/He associations in the thermomineral waters,N-Portugal

Na–HCO₃–CO₂-rich thermomineral waters issue in the N of Portugal, within the Galicia-Trás-os-Montes region, linked to a major NNE-trending fault, the so-called Penacova-Régua-Verin megalineament. Along this tectonic structure different occurrences of CO₂-rich thermomineral waters are found: Chaves hot waters (67 °C) and also several cold (16.1 °C) CO₂-rich waters. The δ²H and δ¹⁸O values of the thermomineral waters are similar to those of the local meteoric waters. The chemical composition of both hot and cold mineral waters suggests that water–rock reactions are mainly controlled by the amount of dissolved CO₂ (g) rather than by the water temperature. Stable carbon isotope data indicate an external CO₂ inorganic origin for the gas. δ¹³C_CO2 values ranging between ? 7.2‰ and ? 5.1‰ are consistent with a two-component mixture between crustal and mantle-derived CO₂. Such an assumption is supported by the ³He/⁴He ratios measured in the gas phase, are between 0.89 and 2.68 times the atmospheric ratio (Ra). These ratios which are higher than that those expected for a pure crustal origin (≈ 0.02 Ra), indicating that 10 to 30% of the He has originated from the upper mantle. Release of deep-seated fluids having a mantle-derived component in a region without recent volcanic activity indicates that extensive neo-tectonic structures originating during the Alpine Orogeny are still active (i.e., the Chaves Depression).     

Early diagenesis in sediments from the eastern equatorial Pacific,I. Pore water nutrient and carbonate results

Interstitial waters were extracted from cores at three locations in the eastern equatorial Pacific and analyzed for nutrients, dissolved carbonate species, Mn and Fe. From the depth variation in pore water chemistry, we infer that organic matter oxidation reactions occur with depth in the following sequence: O₂ reduction, NO₃^? and MnO₂ reduction, and then ferric iron reduction. From NO₃^? results we infer that O₂ is largely or totally consumed within the top few centimeters of sediment. NO₃^? is completely reduced at a sediment depth of 20 cm at a site near the crest of the East Pacific Rise, but is preserved at levels of 20–30 μmol/kg at 40 cm depth at a Guatemala Basin site.We have calculated the alkalinity for pore water samples assuming ions diffuse according to relative ionic diffusion coefficients, that the stoichiometry of organic matter oxidation reactions is that of “Redfield” organic matter, and that the pore waters are saturated throughout with respect to CaCO₃. The measured alkalinity increase is only about half of the predicted value. The difference is probably a result of either enhanced mixing of the pore water in the top few centimeters of sediments by biological or physical processes, or the occurrence of an inorganic reaction which consumes alkalinity.At depths of oxygen and nitrate reduction in the sediments, the ion concentration product of CaCO₃ is the same, within the analytical error, as the solubility product of Ingle et al. [34] at 1 atm and 4°C. This result indicates CaCO₃ resaturation on pressure change during coring. Where pore water Mn concentrations become measurable, the ion concentration product increases, indicating either supersaturation with respect to calcite or that another phase is controlling the carbonate solubility.     

Variability of nutrients and carbon dioxide in the Antarctic Intermediate Water between 1990 and 2014

Antarctic Intermediate Water (AAIW) formation constitutes an important mechanism for the export of macronutrients out of the Southern Ocean that fuels primary production in low latitudes. We used quality-controlled gridded data from five hydrographic cruises between 1990 and 2014 to examine decadal variability in nutrients and dissolved inorganic carbon (DIC) in the AAIW (neutral density range 27 < γ _n <? 27.4) along the Prime Meridian. Significant positive trends were found in DIC (0.70 ± 0.4 μmol kg^??1 year^??1) and nitrate (0.08 ± 0.06 μ mol kg^??1 year^??1) along with decreasing trends in temperature (??0.015 ± 0.01^°C year^??1) and salinity (??0.003 ± 0.002 year^??1) in the AAIW. Accompanying this is an increase in apparent oxygen utilization (AOU, 0.16 ± 0.07 μ mol kg^??1 year^??1). We estimated that 75% of the DIC change has an anthropogenic origin. The remainder of the trends support a scenario of a strengthening of the upper-ocean overturning circulation in the Atlantic sector of the Southern Ocean in response to the positive trend in the Southern Annular Mode. A decrease in net primary productivity (more nutrients unutilized) in the source waters of the AAIW could have contributed as well but cannot fully explain all observed changes.     

Sources and distribution of organic matter in northern Patagonia fjords,Chile (∼44–47°S): A multi-tracer approach for carbon cycling assessment

We investigated the provenance of organic matter in the inner fjord area of northern Patagonia, Chile (～44–47°S), by studying the elemental (organic carbon, total nitrogen), isotopic (δ¹³C, δ¹⁵N), and biomarker (n-alkanoic acids from vascular plant waxes) composition of surface sediments as well as local marine and terrestrial organic matter. Average end-member values of N/C, δ¹³C, and δ¹⁵N from organic matter were 0.127±0.010, ?19.8±0.3‰, and 9.9±0.5‰ for autochthonous (marine) sources and 0.040±0.018, ?29.3±2.1‰, and 0.2±3.0‰ for allochthonous (terrestrial) sources. Using a mixing equation based on these two end-members, we calculated the relative contribution of marine and terrestrial organic carbon from the open ocean to the heads of fjords close to river outlets. The input of marine-derived organic carbon varied widely and accounted for 13–96% (average 61%) of the organic carbon pool of surface sediments. Integrated regional calculations for the inner fjord system of northern Patagonia covered in this study, which encompasses an area of ～4280 km², suggest that carbon accumulation may account for between 2.3 and 7.8×10⁴ ton C yr^?1. This represents a storage capacity of marine-derived carbon between 1.8 and 6.2×10⁴ ton yr^?1, which corresponds to an assimilation rate of CO₂ by marine photosynthesis between 0.06 and 0.23×10⁶ ton yr^?1. This rate suggests that the entire fjord system of Patagonia, which covers an area of ～240,000 km², may represent a potentially important region for the global burial of marine organic matter and the sequestration of atmospheric CO₂.