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1.
New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σt16.2) and anoxic layers (σt16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σt16.2±0.2 kg m−3. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σt16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.  相似文献   

2.
The spatial distributions of dissolved manganese and nutrients were examined in the Columbia River plume off Oregon and Washington during the summer of 2004 and 2005 as part of the River Influence on Shelf Ecosystems (RISE) program. Factors influencing the hydrochemical characteristics of the freshly formed and aged Columbia River plume were investigated. Hydrographic data and nutrient concentrations were used to delineate three distinct water sources for the Columbia River Plume: California Current surface water, coastal upwelled water, and Columbia River water. The warm, intermediate salinity, nutrient poor California Current water contains low levels of dissolved manganese (< 5 nM) and silicic acid (< 5 μM), and is depleted in nitrate. The cold, high salinity, nutrient rich, freshly upwelled water is highly variable (2–20 nM) in dissolved manganese and can be as high as  45 μM in silicic acid and  30 μM nitrate. The variable Columbia River has summer temperatures ranging from  13 to 24 °C, high silicic acid concentrations (ranging from  120 to 200 μM), and lower nitrate concentrations (ranging from  2 to 20 μM). During the summer, the concentrations of silicic acid and dissolved manganese can exceed 100 μM and 200 nM, respectively, in near-field Columbia River plumes. These values are markedly greater than those of surface coastal waters (even during upwelling conditions). As the plume advects and mixes, the concentrations of these two constituents remain relatively high within plume waters. The concentrations of dissolved manganese in the near-field plume vary with tidal amplitude, exhibiting much higher concentrations for a given salinity during spring tides than during neap tides. For example, the Columbia River plume at a salinity of 20 has a concentration of dissolved manganese of  240 nM during spring tides, as compared to only  60 nM during low amplitude tides. Silicic acid concentrations in the near-field plume remain relatively constant throughout the tidal month. Calculations indicate there is roughly an equivalent yearly delivery of dissolved manganese and silicic acid to the coastal waters off Oregon and Washington by upwelled waters and by the Columbia River plume.  相似文献   

3.
From observations of ice cover, temperature, salinity, currents and nitrate, it is evident that along-shelf variability was significant over the middle shelf of the eastern Bering Sea, but less distinct than that observed in the cross-shelf domains. Along the 70-m isobath, three zones were evident in the summer: the southeastern cold pool (centered at 57°N); an intermediate zone, consisting of warmer water, with weaker stratification; and the northern cold pool, extending northward from 58°N. Small-scale (20 km) horizontal features that persisted for months were common. Nutrient concentrations were related to salinity and were replenished more uniformly over the southern shelf, than north of the Pribilof Islands. Although mean currents were weak (1 cm s−1), short energetic advective events impacted the temperature and salinity structure.  相似文献   

4.
Dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) measured in deep profiles in the N-E Atlantic and in the N-W Mediterranean in the period 1984–2002 are described. After accurate validation, they show close agreement with those previously published.Classic profiles were obtained, with concentrations decreasing in deep waters. In the Mediterranean and in the Atlantic comparable concentrations were found in the 1500–2000 m waters, 44–46 μmol l−1 DOC, 2.6–2.8 μmol l−1 DON and 0.02–0.03 μmol l−1 DOP. In the surface layers, DOC concentrations were higher, but DON and DOP concentrations lower, in the Mediterranean than in the Atlantic, leading to higher element ratios in the Mediterranean. In autumn, values were, respectively, DOC:DON 17 vs. 14, DOC:DOP 950 vs. 500 and DON:DOP 55 vs. 35. The data suggest an increase in DOC and DON in the North Atlantic Central Water over 15 years, which may be linked to the North Atlantic climatic oscillations.Refractory DOM found in the 1500–2000 m layer exhibited C:N:P ratios of 1570:100:1. The labile+semi-labile (=non-refractory) DOM (nrDOM) pool was computed as DOM in excess of the refractory pool. Its contribution to total DOM above the thermocline in the open sea amounted to 25–35% of DOC, 30–35% of DON, and 60–80% of DOP. Element ratios of the nrDOM varied among stations and were lower than those of refractory DOM, except for C:N in the Mediterranean: nrDOC:nrDON 10–19, nrDOC:nrDOP 160–530 and nrDON:nrDOP 15–38. The specific stoichiometry of DOM in the Mediterranean led us to postulate that overconsumption of carbon is probably a main process in that oligotrophic sea.By coupling non-refractory DOM stoichiometry and relationships between the main DOM elements in the water column, the relative mineralization of C, N and P from DOM was studied. Below the thermocline, the preferential removal of phosphorus with regard to carbon from the semi-labile DOM can be confirmed, but not the preferential removal of nitrogen. In the ocean surface layers, processes depend on the oceanic area and can differ from deep waters, so preferential carbon removal seems more frequent. Bacterial growth efficiency data indicate that bacteria are directly responsible for mineralization of a high proportion of DON and DOP in the deep water.  相似文献   

5.
Jingfeng Wu   《Marine Chemistry》2007,103(3-4):370-381
A low-blank pre-concentration procedure is described for the analysis of picomolar iron (Fe) in seawater by isotope dilution high-resolution inductively coupled plasma mass-spectrometry (HR-ICPMS). The procedure uses a two-step Mg(OH)2 co-precipitation procedure to extract Fe from a 50 ml seawater sample into a 100 μl 4% nitric acid (HNO3) solution followed by HR-ICPMS measurement. The high pre-concentration ratio ( 500:1) achieved by the procedure minimizes the Fe blank due to ICPMS instrumental Fe background and results in a detection limit of  2 pM and a precision of  4% at the 50 pM Fe level. The measurement of a low-Fe seawater sample spiked with gravimetric Fe standard shows that the method can clearly distinguish 0.01 nM Fe from 0.02 nM Fe in seawater with high accuracy. The method is demonstrated by the analysis of dissolved Fe in the equatorial Pacific Ocean.  相似文献   

6.
Sources and discharges of dissolved organic carbon (DOC) from the central Sumatran river Siak were studied. DOC concentrations in the Siak ranged between 560 and 2594 μmol l−1 and peak out after its confluence with the river Mandau. The Mandau drains part of the central Sumatran peatlands and can be characterized as a typical blackwater river due to its high DOC concentration, its dark brown-coloured, acidic water (pH 4.4–4.7) and its low concentration of total suspended matter (12–41 mg l−1). The Mandau supplies about half of the DOC that enters the Siak Estuary where it mixes conservatively with ocean water. The DOC input from the Siak into the ocean was estimated to be 0.3 Tg C yr−1. Extrapolated to entire Indonesia the data suggest a total Indonesian DOC export of 21 Tg yr−1 representing 10% of the global riverine DOC input into the ocean.  相似文献   

7.
This study presents a sea-level curve from 9500 to 6500 cal BP for the farfield location of Singapore, on the Sunda Shelf in southeast Asia. The curve is based on more than 50 radiocarbon dates from elevations of +1.43 m to −15.09 m representing sea-level index points in intertidal mangrove and shallow marine sediments deposited by sea-level rise accompanying deglaciation. The results indicate that mean sea level rose rapidly from around −17 m at 9500 cal BP to around −3 m by 8000 cal BP. After this time, the data suggest (but do not unequivocally prove) that the rate of sea-rise slowed for a period of 300–500 years centred on 7700 cal BP, shortly after the cessation of meltwater input to the oceans from the northern hemisphere. Renewed sea-level rise amounting to 3–5 m began around 7400 cal BP and was complete by 7000 cal BP. The existence of an inflection in the rate of sea-level rise, with a slow-down centred on 7700 cal BP, is broadly consistent with other available sea-level curves over this interval and is supported by evidence of stable shorelines and delta initiation elsewhere at this time, as well as evidence of comparatively rapid retreat of the West Antarctic ice sheet beginning around 7500 cal BP. ‘Stepped’ sea-level rise occurring shortly after 7500 cal BP and also earlier during deglaciation may have served to focus significant post-glacial episodes of human maritime/coastal dispersal, into comparatively narrow time intervals.  相似文献   

8.
Nutrient and oxygen data collected in the southern Aegean Sea (Cretan Sea) and the straits of the Cretan Arc, during the four seasonal PELAGOS cruises in 1994–1995, are investigated and compared with data collected from 1987 to 1992 within the same area. During the cruises of the PELAGOS Project, nutrient enrichment of the intermediate layers of the Cretan Sea was observed, as a result of intrusion of ‘nutrient-rich, oxygen-poor’ Transition Mediterranean Water (TMW) compensating the Cretan Deep Water (CDW) outflow. TMW occupied the intermediate layers of the entire Cretan Sea. The concentrations of nutrients within this layer were often two times higher than those observed in the same area during previous studies undertaken before 1992 (increase 2.5 μmol/l of nitrate, 0.05 μmol/l of phosphate and 2.5μmol/l of silicate). The decrease of oxygen in this layer is about 0.8ml/l (35 μmol/l). Outflow of CDW occurs principally through the Antikithira and Kassos Straits (the two deeper straits of the Cretan Arc); it results in an increase of oxygen content but a decrease in the nutrient content of water in the deep and bottom layers outside the Cretan Sea. The major mesoscale features in the area have a major influence of the distributions and exchanges of nutrients and oxygen through the straits of the Cretan Arc. The surface and the intermediate layers were richer in nutrients and poorer in oxygen in spring (March 1994), than in autumn (September 1994).  相似文献   

9.
The dissolved organic carbon pool (DOC) is among the largest reservoir of reduced carbon on our planet. The demonstration that DOC polymers remain in assembly/dispersion equilibrium forming microscopic hydrogels has a broad range of critical implications. Previous studies estimate that  10% of DOC could be assembled as gels, yielding values of  7 × 1016 g of organic carbon present as microscopic hotspots of high substrate concentration. This huge mass of reduced carbon emphasizes the need to develop reliable methods to systematically investigate the budget of self-assembled marine gels (SAG), and their role in biogeochemical cycling. However, a quantitative method to measure SAG in seawater has not been available. Here we present the validation of a simple assay to measure the mass of organic carbon assembled as microgels in native seawater. This method is based on the ratio of Chlortetracycline (CTC) fluorescence quenching between Ca bound to non-assembled organic molecules and molecules assembled as microgels. This assay can be readily implemented on board using a low cost fluorometer and provisions to measure TOC.  相似文献   

10.
The Wadden Sea (North Sea, Europe) is a shallow coastal sea with high benthic and pelagic primary production rates. To date, no studies have been carried out in the Wadden Sea that were specifically designed to study the relation between pelagic respiration and production by comparable methods. Because previous studies have suggested that the import of primary-produced pelagic organic matter is important for benthic Wadden Sea carbon budgets, we hypothesised that on an annual average the northern Wadden Sea water column is autotrophic. To test this hypothesis, we studied annual dynamics of primary production and respiration at a pelagic station in a shallow tidal basin (List Tidal Basin, northern Wadden Sea). Since water depth strongly influences production estimates, we calculated primary production rates per unit area in two ways: on the basis of the mean water depth (2.7 m) and on the basis of 1 m depth intervals and their respective spatial extent in the List Tidal Basin. The latter more precise estimate yielded an annual primary production of 146 g C m− 2 y− 1. Estimates based on the mean water depth resulted in a 40% higher annual rate of 204 g C m− 2 y− 1. The total annual pelagic respiration was 50 g C m− 2 y− 1. The P/R ratio varied between seasons: from February to October the water column was autotrophic, with the highest P/R ratio of 4–5 during the diatom spring bloom in April/May. In autumn and winter the water column was heterotrophic. On an annual average, the water column of the List Tidal Basin was autotrophic (P/R 3). We suggest that a large fraction of the pelagic produced organic matter was respired locally in the sediment.  相似文献   

11.
A series of experiments was conducted to evaluate the appropriateness of cross-flow ultrafiltration (CFUF) techniques for the determination of the phase speciation of monomethyl mercury (MeHg) in natural waters. Spiral-wound cartridge (Amicon S1Y1) and Miniplate (Amicon) were evaluated for their nominal molecular weight cut-offs of 1 and 10 kDa, respectively. The ultrafiltration behavior of standard macromolecules showed that the permeation of high molecular weight (HMW) organic macromolecules was not significant when a concentration factor (CF)>15 was used. The retention of low molecular weight (LMW) molecules was significant, especially at a low CF<5, suggesting that the use of a high CF (15) will minimize the retention of LMW molecules. Sorptive losses of MeHg in the solution phase to the 1 kDa membrane were negligible, but MeHg bound to HMW macromolecules was still retained (20%), even with a preconditioned membrane. The mass balance recovery of MeHg during ultrafiltration averaged 101±15% (n=7) and 105±14% (n=5) for the 1 and 10 kDa membranes, respectively. Sample storage over 24 h caused significant coagulation (47%) of the <10 kDa MeHg into the 10 kDa–0.45 μm colloidal or the particulate MeHg pool. The 1 kDa–0.45 μm colloidal MeHg in Galveston Bay and the Trinity River water samples accounted for 40–48% of the filter-passing MeHg, although the most abundant fraction (52–60%) of MeHg was the truly dissolved fraction (<1 kDa). The partition coefficient between the colloidal (1 kDa–0.45 μm) and truly dissolved MeHg (average log KC=5.2) was higher than the partition coefficient based on particle/filter-passing (average log KD=4.6) or particle/truly dissolved MeHg (average log KP=4.8), suggesting that MeHg has stronger affinity for natural colloids than macroparticulate materials (>0.45 μm).  相似文献   

12.
The dissociation constants (pK1 and pK2) for methionine have been measured in artificial seawater as a function of salinity (S = 5 to 35) and temperature (5 to 45 °C). The seawater pK2 values were lower than the values in NaCl at the same ionic strength while the pK1 values in seawater were lower only at S = 35. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been used to determine the formation of Mg2+ complexes and Pitzer interaction parameters for Mg2+ with methionine. The seawater model with the interaction parameters accounts for the differences between the value of pK1 and pK2 between NaCl and seawater. This study demonstrates that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.  相似文献   

13.
Quasi-synoptic observations of the horizontal and vertical structure of a cold-core cyclonic mesoscale eddy feature (Cyclone Noah) were conducted in the lee of Hawai’i from November 4–22, 2004 as part of the E-Flux interdisciplinary collaborative research program. Cyclone Noah appears to have spun up to the southwest of the ‘Alenuihaha Channel (between Maui and Hawai’i) as a result of strong and persistent northeasterly trade winds through the channel. Shipboard hydrographic surveys 2.5 months later suggest that Noah weakened and was in a hypothesized spin-down phase of its life cycle. Although the initial surface expression of Noah was limited in scale to 40 km in diameter and, as evidenced by surface temperatures, 2–3 °C cooler than the surrounding waters, depth profiles revealed a fully developed semi-elliptical shallow feature (200 m), 144 km long and 90 km wide (based on sigma-t=23 kg m−3) with tangential speeds of 40–80 cm s−1, and substantial isopycnal doming. Potential vorticity distribution of Noah suggests that radial horizontal flow of the core water was inhibited from the surface to depths of 75 m, with high vorticity confined above the sigma-t=23.5 kg m−3 isopycnal surface. Upward displacements of isopycnal surfaces in the eddy's center (50 m) were congruent with enhanced pigment concentrations (0.50 mg m−3). Comparisons of the results obtained for E-Flux I (Noah) and E-Flux III (Opal) suggest that translation characteristics of cyclonic Hawaiian lee eddies may be important in establishing the biogeochemical and biological responses of the oligotrophic ocean to cyclonic eddies.  相似文献   

14.
Benthic foraminiferal biomass, density, and species composition were determined at 10 sites in the Gulf of Mexico. During June 2001 and 2002, sediment samples were collected with a GoMex box corer. A 7.5-cm diameter subcore was taken from a box core collected at each site and sliced into 1-cm or 2-cm sections to a depth of 2 or 3 cm; the >63-μm fraction was examined shipboard for benthic foraminifera. Individual foraminifers were extracted for adenosine triphosphate (ATP) using a luciferin–luciferase assay, which indicated the total ATP content per specimen; that data was converted to organic carbon. Foraminiferal biomass and density varied substantially (2–53 mg C m−2; 3600–44,500 individuals m−2, respectively) and inconsistently with water depth: although two 1000-m deep sites were geographically separated by only 75 km, the foraminiferal biomass at one site was relatively low (9 mg C m−2) while the other site had the highest foraminiferal biomass (53 mg C m−2). Although most samples from Sigsbee Plain (>3000 m) had low biomass, one Sigsbee site had >20 mg foraminiferal C m−2. The foraminiferal community from all sites (i.e. bathyal and abyssal locales) was dominated by agglutinated, rather than calcareous or tectinous, species. Foraminiferal density never exceeded that of metazoan meiofauna at any site. Foraminiferal biomass, however, exceeded metazoan meiofaunal biomass at 5 of the 10 sites, indicating that foraminifera constitute a major component of the Gulf's deep-water meiofaunal biomass.  相似文献   

15.
The Darwin Mounds are a series of small (5 m high, 75–100 m diameter) sandy features located in the northern Rockall Trough. They provide a habitat for communities of Lophelia pertusa and associated fauna. Suspended particulate organic matter (sPOM) reaching the deep-sea floor, which could potentially fuel this deep-water coral (DWC) ecosystem, was collected during summer 2000. This was relatively “fresh” (i.e. dominated by labile lipids such as polyunsaturated fatty acids) and was derived largely from phytoplankton remains and faecal pellets, with contributions from bacteria and microzooplankton. Labile sPOM components were enriched in the benthic boundary layer (10 m above bottom (mab)) relative to 150 mab. The action of certain benthic fauna that are exclusively associated with the DWC ecosystem (e.g. echiuran worms) leads to the subduction of fresh organic material into the sediments. The mound surface sediments are enriched in organic carbon, relative to off-mound sites. There is no evidence for hydrocarbon venting at this location.  相似文献   

16.
In this study, seasonal and annual variability in the use of estuarine and ocean beaches by young-of-the-year bluefish, Pomatomus saltatrix, was evaluated by indices of abundance in coastal areas of southern New Jersey (1998–2000). Biological and physical factors measured at specific sites were correlated with bluefish abundance to determine the mechanisms underlying habitat selection. In addition, integrative and discrete indicators of bluefish growth were used to examine spatio-temporal dynamics in habitat quality and its effect on habitat selection by multiple cohorts of bluefish. Intra-annual recruitment to coastal areas of southern New Jersey was episodic, and resulted from the ingress of spring-spawned bluefish (hatch-date April) to estuarine beaches in late May to early June, followed by the recruitment of summer-spawned fish (hatch-date early July) to ocean beaches from July to October. Bluefish utilized estuarine and ocean beaches in a facultative manner that was responsive to dynamics in prey composition and temperature conditions. The recruitment and residency of bluefish in the estuary (1998–1999) and ocean beaches (1998), for example, was coincidental with the presence of the Atlantic silverside Menidia menidia and bay anchovy Anchoa mitchilli, the principal prey species for bluefish occupying these respective habitat-types. Bluefish abundance in the estuary (2000) and ocean beaches (1999–2000) was also correlated with water temperature, with the greatest catches of juveniles coinciding with their optimal growth temperature (24 °C). Bluefish growth, estimated as the slope of age–length relationships and daily specific growth rates, equaled 1.27–2.63 mm fork length (FL) d−1 and 3.8–8.7% body length increase d−1, respectively. The growth of sagittal otoliths was also used as a proxy for changes in bluefish size during and shortly before their time of capture. Accordingly, otolith growth rates of summer-spawned bluefish were greater at ocean beaches relative to the estuary and were explained by the more suitable temperature conditions found at ocean beaches during the mid- to late summer. Notwithstanding the fast growth of oceanic summer-spawned bluefish, individuals spawned in the spring were still larger in absolute body size at the end of the summer growing season (240 and 50–200 mm FL for spring- and summer-spawned bluefish, respectively). The size discrepancy between spring- and summer-spawned bluefish at the onset of autumn migrations and during overwintering periods may account for the differential recruitment success of the respective cohorts.  相似文献   

17.
Geochemical estimates of N2 fixation in the North Atlantic often serve as a foundation for estimating global marine diazotrophy. Yet despite being well-studied, estimations of nitrogen fixation rates in this basin vary widely. Here we investigate the variability in published estimates of excess nitrogen accumulation rates in the main thermocline of the subtropical North Atlantic, testing the assumptions and choices made in the analyses. Employing one of these previously described methods, modified here with improved estimates of excess N spatial gradients and ventilation rates of the main thermocline, we determine a total excess N accumulation rate of 7.8 ± 1.7 × 1011 mol N yr− 1. Contributions to excess N development include atmospheric deposition of high N:P nutrients (adding excess N at a rate of 3.0 ± 0.9 × 1011 mol N yr− 1 for  38% of the total), high N:P dissolved organic matter advected into and mineralized in the main thermocline (adding excess N at 2.2 ± 1.1 × 1011 mol N yr− 1 for  28% of the total), and, calculated by mass balance of the excess N field, N2 fixation (adding excess N at 2.6 ± 2.2 × 1011 mol N yr− 1 for  33% of the total). Assuming an N:P of 40 and this rate of excess N accumulation due to the process, N2 fixation in the North Atlantic subtropical gyre is estimated at  4 × 1011 mol N yr− 1. This relatively low rate of N2 fixation suggests that i) the rate of N2 fixation in the North Atlantic is greatly overestimated in some previous analyses, ii) the main thermocline is not the primary repository of N fixed by diazotrophs, and/or iii) the N:P ratio of exported diazotrophic organic matter is much lower than generally assumed. It is this last possibility, and our uncertainty in the N:P ratios of exported material supporting excess N development, that greatly lessens our confidence in geochemical measures of N2 fixation.  相似文献   

18.
The trophic structure of zooplankton was investigated in Fram Strait (north western Svalbard) in spring and autumn of 2003. Depth-stratified zooplankton samples were collected at 12 stations on the shelf (200 m), across the shelf-slope (500 m) and over deep water (>750 m), using a Multiple Plankton Sampler equipped with 0.180-mm mesh size nets.Higher zooplankton abundance and estimated biomass were found in the shelf area. Abundance and biomass were two times higher in August, when sea-surface temperature was higher than in May. Herbivores dominated numerically in May, and omnivores in August, suggesting a seasonal sequence of domination by different trophic groups. Cirripedia nauplii and Fritillaria borealis prevailed in spring, whereas copepod nauplii and Calanus finmarchicus were numerically the most important herbivores in autumn. Small copepods, Oithona similis and Triconia borealis, were the most numerous omnivorous species in both seasons, but their abundances increased in autumn. Chaetognatha (mainly Eukrohnia hamata) accounted for the highest abundance and biomass among predatory taxa at all deep-water stations and during both seasons. Regarding vertical distribution, herbivores dominated numerically in the surface layer (0–20 m), and omnivores were concentrated somewhat deeper (20–50 m) during both seasons. Maximum abundance of predators was found in the surface layer (0–20 m) in spring, and generally in the 20–50 m layer in autumn. This paper presents the first comprehensive summary of the zooplankton trophic structure in the Fram Strait area. Our goals are to improve understanding of energy transfer through this ecosystem, and of potential climate-induced changes in Arctic marine food webs.  相似文献   

19.
Methods are described for the rapid (11 min) automated shipboard analysis of dissolved sulfur hexafluoride (SF6) in small volume (200 cm3) seawater samples. Estimated precision for the SF6 measurements is 2% or 0.02 fmol kg−1 (whichever is greater). The method also allows for the simultaneous measurement of chlorofluorocarbon-11 (CFC11) and chlorofluorocarbon-12 (CFC12) on the same water sample, with significantly improved sensitivity over previous analytical methods.  相似文献   

20.
The dissociation constants (pK1, pK2 and pK3) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK3 in the Na–Mg–Cl solutions have been attributed to the formation of Mg2+ complexes with Cys2− anions
Mg2+ + Cys2− = MgCys
The stability constants have been fitted to
after corrections are made for the interaction of Mg2+ with H+.The pK1 seawater measurements indicate that H3Cys+ interacts with SO42−. The Pitzer parameters β0(H3CysSO4), β1(H3CysSO4) and C(H3CysSO4) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK2 and pK3 in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK1, pK2 and pK3 that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.  相似文献   

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