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1.
Fixed nitrogen is a key nutrient involved in regulating global marine productivity and hence the global oceanic carbon cycle. Oceanic nitrogen (N2) fixation is estimated to supply 8×1012 moles N y?1 to the ocean, approximately equal to current riverine and the atmospheric inputs of fixed N, and between 50 and 100% of current estimates of oceanic denitrification. However, the spatial and temporal variability of N2 fixation remains uncertain, mostly because of the normal low resolution sampling for diazotroph distribution and fixation rates. It is well established that N2 fixation, mediated by the enzyme nitrogenase, is a source of hydrogen (H2), but the extent to which it leads to supersaturation of H2 in oceanic waters is unresolved. Here, we present simultaneous measurements of upper ocean dissolved H2 concentration (nmol L?1), and rates of N2 fixation (μmol N m?3 d?1), determined using 15N2 tracer techniques (at 7 or 15 m), on a transect from Fiji to Hawaii. We find a significant correlation (r=0.98) between dissolved H2 and rates of N2 fixation, with the greatest supersaturation of H2 and highest rates of N2 fixation being observed in the subtropical gyres at the southern (～18°S) and northern (18°N) reaches of the transect. The lowest H2 saturation and N2 fixation were observed in the equatorial region between 8°S and 14°N. We propose that an empirical relationship between H2 supersaturations and N2 fixation measurements could be used to guide sampling for 15N fixation measurements or to aid the spatial interpolation of such measurements.  相似文献   

2.
The chemical speciation of iron was determined in the Southern Ocean along a transect from 48 to 70°S at 20°E. Dissolved iron concentrations were low at 0.1–0.6 nM, with average concentrations of 0.25±0.13 nM. Organic iron complexing ligands were found to occur in excess of the dissolved iron concentration at 0.72±0.23 nM (equivalent to an excess of 0.5 nM), with a complex stability of log KFeL′=22.1±0.5 (on the basis of Fe3+ and L′). Ligand concentrations were higher in the upper water column (top 200 m) suggesting in situ production by microorganisms, and less at the surface consistent with photochemical breakdown. Our data are consistent with the presence of stable organic iron-complexing ligands in deep global ocean waters at a background level of ∼0.7 nM. It has been suggested that this might help stabilise iron at levels of ∼0.7 nM in deep ocean waters. However, much lower iron concentrations in the waters of the Southern Ocean suggest that these ligands do not prevent the removal of iron (by scavenging or biological uptake) to well below the concentration of these ligands. Scavenging reactions are probably inhibited by such ligand competition, so it is likely that biological uptake is the chief cause for the further removal of iron to these low levels in waters that suffer from very low iron inputs.  相似文献   

3.
Recent studies of the nitrogen gas excess produced during water column denitrification have indicated that water column denitrification rates calculated using nitrate deficit-type methods could be a substantial underestimate. Since there are no other significant processes that produce (or consume) N2 in the oxygen deficient zone (ODZ), its excess above background can be used to estimate the amount of denitrification, avoiding assumptions made in nitrate deficit calculations of the composition of the respired organic matter and also uncertainties in the nitrogen removal pathways. Dissolved N2, Ar, and nutrient concentrations were measured at 2 stations in the ODZ of the eastern tropical South Pacific (ETSP) in order to compare the nitrogen gas excess with the dissolved inorganic nitrogen (DIN) deficit due to denitrification. In contrast with previous findings in the Arabian Sea ODZ, the shapes of the N2 excess and DIN deficit profiles were similar in the ETSP ODZ, with maxima at the top of the ODZ. Maximum DIN deficits at each station were 19 and 18 μM N compared to the maximum N2 excesses of 15 and 20 μM N, respectively. Given the same considerations of the volume and residence time for the oxygen deficient zone waters, denitrification rates for the ETSP estimated from the N2 excess would be comparable or no greater than 30% larger than the one determined using the DIN deficit. This implies that the source of the DIN removed from the ODZ is either deep sea nitrate or organic matter with an N:P ratio close to Redfield.  相似文献   

4.
Five vertical profiles of silver (Ag) in the subarctic northeast Pacific are presented. Dissolved (< 0.2 μm) Ag concentrations within the surface mixed layer range from 6–25 pM, with the highest observed values at the most coastal site. Elevated Ag concentrations at this station are most likely attributable to the estuarine circulation in the Juan de Fuca Strait. One open-ocean station (P20) exhibited a strong surface Ag maximum. The station was located at the edge of a Haida eddy which raises the possibility that such eddies transport Ag seaward from the coastal zone. Ag concentrations in the deep waters ranged from 60–80 pM. These measurements are consistent with other recent Ag data collected in the Pacific. Ag profiles throughout the Pacific Ocean yield a strong positive correlation between Ag concentration and dissolved silicic acid concentration. However, Ag is depleted relative to silicic acid at intermediate depths where dissolved O2 concentrations are low, implying a possible removal of Ag from oxygen-depleted waters by scavenging and/or precipitation.  相似文献   

5.
We have developed, deployed, and tested a novel probe for study of the geochemistry of sediment pore waters based upon Raman spectroscopy. The Raman technique has already been used successfully for in situ measurements of targets of scientific interest including gas and hydrothermal vents and complex gas hydrates, but sediment geochemistry has so far been an intractable problem since the sediments themselves are strongly fluorescent and typically only very small sample volumes are obtainable. The 35 cm long probe extracts pore fluids through a 10 μm sintered metallic frit and draws the sample through a 2 mm diameter channel into a sapphire windowed optical cell within which the laser beam is focused and the spectrum recorded. The dead volume of the system is ～1 ml and the instrument is ROV deployable with activation of probe insertion and sample withdrawal under direct operator control. The unique features of this mode of detection include observation of the sulfate gradient in marine pore waters as an indicator of diagenesis, direct measurement of the dissolved sulfide species H2S and HS?, and measurement of dissolved methane; all of which are of primary geochemical interest. Quantitative analysis is achieved by area ratio to known water peaks and from standard calibration curves with a precision of ±5%. We find only very small fluorescence from pore waters measured in situ, but observe rapid increases in fluorescence from cores returned to the surface and exposed to oxygen.  相似文献   

6.
We found similar microbial degradation rates of labile dissolved organic matter in oxic and suboxic waters off northern Chile. Rates of peptide hydrolysis and amino acid uptake in unconcentrated water samples were not low in the water column where oxygen concentration was depleted. Hydrolysis rates ranged from 65 to 160 nmol peptide L−1 h−1 in the top 20 m, 8–28 nmol peptide L−1 h−1 between 100 and 300 m (O2-depleted zone), and 14–19 nmol peptide L−1 h−1 between 600 and 800 m. Dissolved free amino acid uptake rates were 9–26, 3–17, and 6 nmol L−1 h−1 at similar depth intervals. Since these findings are consistent with a model of comparable potential activity of microbes in degrading labile substrates of planktonic origin, we suggest, as do other authors, that differences in decomposition rates with high and low oxygen concentrations may be a matter of substrate lability. The comparison between hydrolysis and uptake rates indicates that microbial peptide hydrolysis occurs at similar or faster rates than amino acid uptake in the water column, and that the hydrolysis of peptides is not a rate-limiting step for the complete remineralization of labile macromolecules. Low O2 waters process about 10 tons of peptide carbon per h, double the amount processed in surface-oxygenated water. In the oxygen minimum zone, we suggest that the C balance may be affected by the low lability of the dissolved organic matter when this is upwelled to the surface. An important fraction of dissolved organic matter is processed in the oxygen minimum layer, a prominent feature of the coastal ocean in the highly productive Humboldt Current System.  相似文献   

7.
Net community biological production in the euphotic zone of the ocean fuels organic matter and oxygen export from the upper ocean, which has a large influence on the atmospheric pressure of carbon dioxide and is the driving force for metabolite distributions in the sea. We determine the net annual biological oxygen production in the mixed layer of the northeast subarctic Pacific Ocean from in situ O2 and N2 measurements. Temperature, salinity, total gas pressure and O2 were measured every 3 h for 9 months in 2007 at about 3 m depth on a surface mooring at Station P (50°N, 145°W). The concentration of nitrogen gas, N2, determined from separate total gas pressure and pO2 measurements, was used as an inert tracer of the physical processes that induce gas departure from thermodynamic equilibrium with the atmosphere. We use a simple model of the ocean’s mixed layer along with the nitrogen concentration to constrain the importance of bubbles, gas exchange and horizontal advection, which are then used in the oxygen mass balance to derive net biological oxygen production. The mixed-layer oxygen mass balance is dominated by exchange with the atmosphere, and we determine a mean summertime oxygen production of 24 mmol O2 m?2 d?1. The annual pattern in the difference between the supersaturation of oxygen and nitrogen in the surface waters reveals very little net oxygen production during the winter at this location. The calculated annual net community production (NCP) of carbon from this new method, 2.5 mol m?2 yr?1, agrees to within its error of about×40% with previous determinations at this location from oxygen mass balance, NO3? draw down and 234Th measurements. This value is either indistinguishable from or lower than annual NCP measurements in the subtropical North Pacific, indicating that there is no experimental evidence for differences in annual NCP between the subarctic and subtropical North Pacific Ocean.  相似文献   

8.
We discuss nitrous oxide (N2O) and methane (CH4) distributions in 49 vertical profiles covering the upper ∼300 m of the water column along two ∼13,500 km transects between ∼50°N and ∼52°S during the Atlantic Meridional Transect (AMT) programme (AMT cruises 12 and 13). Vertical N2O profiles were amenable to analysis on the basis of common features coincident with Longhurst provinces. In contrast, CH4 showed no such pattern. The most striking feature of the latitudinal depth distributions was a well-defined “plume” of exceptionally high N2O concentrations coincident with very low levels of CH4, located between ∼23.5°N and ∼23.5°S; this feature reflects the upwelling of deep waters containing N2O derived from nitrification, as identified by an analysis of N2O, apparent oxygen utilization (AOU) and NO3−, and presumably depleted in CH4 by bacterial oxidation. Sea-to-air emissions fluxes for a region equivalent to ∼42% of the Atlantic Ocean surface area were in the range 0.40–0.68 Tg N2O yr−1 and 0.81–1.43 Tg CH4 yr−1. Based on contemporary estimates of the global ocean source strengths of atmospheric N2O and CH4, the Atlantic Ocean could account for ∼6–15% and 4–13%, respectively, of these source totals. Given that the Atlantic Ocean accounts for around 20% of the global ocean surface, on unit area basis it appears that the Atlantic may be a slightly weaker source of atmospheric N2O than other ocean regions but it could make a somewhat larger contribution to marine-derived atmospheric CH4 than previously thought.  相似文献   

9.
Photochemical production rates of hydrogen peroxide (H2O2) were determined in Antarctic waters during two research cruises. The first cruise was from mid-October to mid-November, 1993, in the confluence of the Weddell and Scotia Seas, and the second cruise was in December, 1994, along the coast of the Antarctic Peninsula. During these cruises, midday sea-surface production rates ranged from 2.1 to 9.6 nM h−1, with an average rate of 4.5 nM h−1. Production rates were consistently smaller than rates determined at lower latitudes (>9 nM h−1), primarily due to the colder temperatures and lower ultraviolet irradiances in polar waters. In situ production rates were determined with a free-floating drifter that was deployed for 12–14 h. Production rates, averaged over the deployment time, were highest at or near the surface (ca. 2.4–3.5 nM h−1) and decreased rapidly with depth to 0.1–0.7 nM h−1 at 10–20 m. The decrease in production rates with depth generally paralleled the decrease in ultraviolet irradiance in the water column. Production rates of hydrogen peroxide in Antarctic seawater were largely controlled by the ultraviolet irradiance in the water column, although there was some evidence for production in the blue region of the solar spectrum. A laboratory study was conducted to determine the wavelength dependence of the apparent quantum yield for the photochemical formation of hydrogen peroxide in Antarctic waters. Apparent quantum yields determined at 0°C decreased from 0.74×10−3 mol einstein−1 at 290 nm to 1.0×10−5 mol einstein−1 410 nm. At 20°C, apparent quantum yields for the photochemical production of hydrogen peroxide were within a factor of two of apparent quantum yields determined in temperate waters at 20–25°C. Sunlight-normalized H2O2 production rates were determined as a function of wavelength using noontime irradiance data from Palmer Station, Antarctica. A decrease in stratospheric ozone from 336 to 151 Dobson units resulted in a predicted 19–42% increase in the photoproduction of H2O2 at the sea surface in Antarctic waters. The magnitude of this increase depends on the concentration and absorbance characteristics of dissolved organic matter in the photic zone, as well as on other factors such as cloudiness and decreasing solar zenith angle that tend to lower photochemical rates offsetting increases due to stratospheric ozone depletion.  相似文献   

10.
We studied the seasonal, diel, and vertical distribution of phytoplankton N2 fixation to understand the relative contributions of unicellular and filamentous nitrogen fixers (diazotrophs) to N2 fixation and nitrogen recycling in the northern South China Sea (SCS) and the neighboring upstream Kuroshio. N2-fixation rates were measured by the 15N2 tracer technique (addition by bubble) on unicellular (<10 or 20 µm) and the filamentous diazotrophs (>10 or 20 µm, mostly Trichodesmium and Richelia) fractionated by 10- or 20-µm mesh sizes. The mean depth-integrated total (unicellular+filamentous) N2-fixation rates in the SCS (51.7±6.2 µmol N m−2 d−1) averaged 1/3 of that in the Kuroshio (142.7±29.6 µmol N m−2 d−1), with higher rates in the winter than in other seasons in the SCS and the opposite seasonal pattern in the Kuroshio. Unicellular diazotrophs contributed 65% of the total N2 fixation in the SCS, which were negatively correlated with surface temperature and, as for total N2 fixation, were higher in the winter when Trichodesmium spp. were scarce. In comparison, the unicellular diazotrophs contributed 50% of total N2 fixation in the Kuroshio, and their contributions were not significantly correlated with surface temperature. In both the SCS and the Kuroshio, the unicellular N2 fixation was more important during the night than during the day, and in the deep euphotic layer than in the surface layer, even in the daytime. Our results show that the unicellular diazotrophs were important N2 fixers and contributed significantly to N2 fixation in the tropical marginal seas, more so in the SCS than the Kuroshio.  相似文献   

11.
Benthic fluxes of dissolved inorganic carbon, total alkalinity, oxygen, nutrients, nitrous oxide and methane were measured in situ at three sites of Río San Pedro salt marsh tidal creek (Bay of Cádiz, SW Spain) during three seasons. This system is affected by the discharges of organic carbon and nutrients from the surrounding aquaculture installations. Sediment oxygen uptake rates and inorganic carbon fluxes ranged respectively from 16 to 79 mmol O2 m? 2 d? 1 and from 48 to 146 mmol C m? 2 d? 1. Benthic alkalinity fluxes were corrected for the influence of NH4+ and NO3? + NO2? fluxes, and the upper and lower limits for carbon oxidation rates were inferred by considering two possible scenarios: maximum and minimum contribution of CaCO3 dissolution to corrected alkalinity fluxes. Average Cox rates were in all cases within ± 25% of the upper and lower limits and ranged from 40 to 122 mmol C m? 2 d? 1. Whereas carbon mineralization did not show significant differences among the sites, Cox rates varied seasonally and were correlated with temperature (r2 = 0.72). During winter and spring denitrification was estimated to account for an average loss of 46% and 75%, respectively, of the potentially recyclable N, whereas during the summer no net removal was observed. A possible shift from denitrification to dissimilatory nitrate reduction to ammonium (DNRA) during this period is argued. Dissolved CH4 and N2O fluxes ranged from 5.7 to 47 μmol CH4 m? 2 d? 1 and 4.3 to 49 μmol N–N2O m? 2 d? 1, respectively, and represented in all cases a small fraction of total inorganic C and N flux. Overall, about 60% of the total particulate organic matter that is discharged into the creek by the main fish farm facility is estimated to degrade in the sediments, resulting in a significant input of nutrients to the system.  相似文献   

12.
Atmospheric dry deposition of nitrogen (N) and dinitrogen (N2) fixation rates were assessed in 2004 at the time-series DYFAMED station (northwestern Mediterranean, 43°25′N, 7°52′E). The atmospheric input was monitored over the whole year. Dinitrogen fixation was measured during different seasonal trophic states (from mesotrophy to oligotrophy) sampled during nine cruises. The bioavailability of atmospherically deposited nutrients was estimated by apparent solubility after 96 h. The solubility of dry atmospheric N deposition was highly variable (from ∼18% to more than 96% of total N). New N supplied to surface waters by the dry atmospheric deposition was mainly nitrate (NO3−) (∼57% of total N, compared to ∼6% released as ammonium (NH4+)). The mean bioavailable dry flux of total N was estimated to be ∼112 μmol m−2 d−1 over the whole year. The NO3− contribution (70 μmol NO3− m−2 d−1) was much higher than the NH4+ contribution (1.2 μmol NH4+ m−2 d−1). The N:P ratios in the bioavailable fraction of atmospheric inputs (122.5–1340) were always much higher than the Redfield N:P ratio (16). Insoluble N in atmospheric dry deposition (referred to as “organic” and believed to be strongly related to anthropogenic emissions) was ∼40 μmol m−2 d−1. N2 fixation rates ranged from 2 to 7.5 nmol L−1 d−1. The highest values were found in August, during the oligotrophic period (7.5 nmol L−1 at 10 m depth), and in April, during the productive period (4 nmol L−1 d−1 at 10 m depth). Daily integrated values of N2 fixation ranged from 22 to 100 μmol N m−2 d−1, with a maximum of 245 μmol N m−2 d−1 in August. No relationship was found between the availability of phosphorus or iron and the observed temporal variability of N2 fixation rates. The atmospheric dry deposition and N2 fixation represented 0.5–6% and 1–20% of the total biological nitrogen demand, respectively. Their contribution to new production was more significant: 1–28% and 2–55% for atmospheric dry deposition and N2 fixation, respectively. The dry atmospheric input was particularly significant in conditions of water column stratification (16–28% of new production), while N2 fixation reached its highest values in June (46% of new production) and in August (55%).  相似文献   

13.
We report dissolved iron (Fed) concentrations measured in the upper 600 m in the central region of the Gulf of California (GC) under spring conditions. Our results showed the complex nature of Fe cycling within the GC. In the northern region of the study area, surface waters were relatively enriched, with Fed concentrations >5.0 nM, which can be partially explained by an atmospheric source. These concentrations are 12 times higher than those found in the adjacent Pacific Ocean. In contrast, Fed depth profiles in the southern region did not show any Fed surface enrichment (concentrations <1.5 nM) because of particle scavenging and higher stratification of the water-column. The most southern station in our area of study was the most stratified and showed an excess Fed and PO4 with respect to NO3, conditions favorable for nitrogen fixation. This station also showed the least negative surface value of N* of all stations. However, despite the adequate levels of Fed and PO4 at that location, the surface temperature (22.6 °C) was probably not high enough for diazotrophs to develop. A slight increase in Fed levels in intermediate waters at the southern region was associated with the oxygen minimum zone. Finally, our results suggest that remineralization of organic matter is probably the major source of Fed in subsurface waters of the GC.  相似文献   

14.
The goal of this study was to explore how net community production (NCP) is influenced by the relationship between primary production and community respiration in the western Arctic Ocean. Plankton NCP and respiration were determined by measuring changes in oxygen in light and dark bottle incubations, respectively. Rates of NCP averaged over shelf, slope and basin waters were positive in summer 2002 (57±191 mmol O2 m−2 d−1) and spring 2004 (85±86 mmol O2 m−2 d−1) and negative in summer 2004 (−25±176 mmol O2 m−2 d−1). Determinations of NCP obtained from bottle incubations were similar to rates inferred from in situ changes in dissolved inorganic carbon. An examination of the spatial variability of primary production and community respiration indicated that respiration is distributed more uniformly than primary production. A spatial offset between photosynthesis and respiration from the shelf to the Arctic basin was present in spring 2004, but was not seen at other times. NCP and the potential for export appear to be dependent on an uncoupling of primary production and community respiration. NCP continued into the summer after the stock of NO3− had been depleted. Our data suggest that the uniform distribution of respiration relative to primary production is an important factor influencing NCP and the potential for export in the western Arctic.  相似文献   

15.
Measurements of dissolved inorganic carbon (DIC), pH, total alkalinity (TA), and partial pressure of CO2 (pCO2) were conducted at a total of 25 stations along four cross shelf transects in the East China Sea (ECS) in January 2008. Results showed that their distributions in the surface water corresponded well to the general circulation pattern in the ECS. Low DIC and pCO2 and high pH were found in the warm and saline Kuroshio Current water flowing northeastward along the shelf break, whereas high DIC and pCO2 and low pH were mainly observed in the cold and less saline China Coastal Current water flowing southward along the coast of Mainland China. Difference between surface water and atmospheric pCO2 (ΔpCO2), ranging from ~ 0 to ? 111 μatm, indicated that the entire ECS shelf acted as a CO2 sink during winter with an average flux of CO2 of ?13.7 ± 5.7 (mmol C m? 2 day? 1), and is consistent with previous studies. However, pCO2 was negatively correlated with temperature for surface waters lower than 20 °C, in contrast to the positive correlation found in the 1990s. Moreover, the wintertime ΔpCO2 in the inner shelf near the Changjiang River estuary has appreciably decreased since the early 1990s, suggesting a decline of CO2 sequestration capacity in this region. However, the actual causes for the observed relationship between these decadal changes and the increased eutrophication over recent decades are worth further study.  相似文献   

16.
Solid sediment, pore and epibenthic waters were collected from the Thau lagoon (France) in order to study the post-depositional partition and mobility of mercury in organic rich sediment. Total Hg (HgT) and monomethylmercury (MMHg) profiles were produced in both dissolved and solid phases. The distribution of HgT in the solid phase appeared to be related to the historical changes in the Hg inputs into the lagoon. HgT was in equilibrium between solid and solution phases in the sulfidic part of the cores, with a mean log Kd of 4.9 ± 0.2. The solid phase appeared to be a source of HgT for pore water in the upper oxic to suboxic parts of the cores. The MMHg represented a small fraction of HgT: 3–15% and 0.02–0.80% in the dissolved and solid phases, respectively. Its distribution was characterized by a main peak in the superficial sediments, and another deeper in the core within the sulfide-accumulating zone. In addition, high dissolved MMHg concentrations and methylated percentage were found in the epibenthic water. Ascorbate (pH 8) dissolution of the sediments and analyses of the soluble fraction suggest that the amorphous oxyhydroxides played a major role in controlling total and methylmercury mobility throughout the sediment–water interface. These features are discussed in terms of sources, transfer and transformations. Diffusive fluxes of HgT and MMHg from sediment to the water column for the warm period were estimated to be 40 ± 15 and 4 ± 2 pmol m−2 d−1, respectively.  相似文献   

17.
《Marine Chemistry》2007,103(1-2):30-45
The chemistry of dissolved Fe(III) was studied in the Scheldt estuary (The Netherlands). Two discrete size fractions of the dissolved bulk (< 0.2 μm and < 1 kDa) were considered at three salinities (S = 26, 10 and 0.3).Within the upper estuary, where fresh river water meets seawater, the dissolved Fe concentration decreases steeply with increasing salinity, for the fraction < 0.2 μm from 536 nM at S = 0.3 to 104 nM at S = 10 and for the fraction < 1 kDa from 102 nM to 36 nM Fe. Further downstream, in the middle and lower estuary, this decrease in the Fe concentration continues, but is far less pronounced. For all samples, the traditionally recognised dissolved strong organic Fe-binding ligand concentrations are lower than the dissolved Fe concentrations.Characteristics of dissolved Fe-binding ligands were determined by observing kinetic interactions with adsorptive cathodic stripping voltammetry. From these kinetic experiments we concluded that apart from the well-known strong Fe-binding organic ligands (L, logK′ = 19–22) also weak Fe-binding ligands (P) existed with an α value (binding potential = K′ · [P]) varying between 1011.1 and 1011.9. The presence of this relatively weak ligand explained the high concentrations of labile Fe present in both size fractions in the estuary. This weak ligand can retard or prevent a direct precipitation after an extra input of Fe.The dissociation rate constants of the weak ligand varied between 0.5 × 10− 4 and 4.3 × 10− 4 s− 1. The rate constants of the strong organic ligand varied between kd = 1.5 × 10− 3–17 × 10− 2 s− 1 and kf = 2.2 × 108–2.7 × 109 M− 1 s− 1. The dissociation rate constant of freshly amorphous Fe-hydroxide was found to be between 4.3 × 10− 4 and 3.7 × 10− 3 s− 1, more labile or equal to the values found by Rose and Waite [Rose, A.L., Waite, T.D., 2003a. Kinetics of hydrolysis and precipitation of ferric iron in seawater. Environ. Sci. Technol., 37, 3897–3903.] for freshly precipitated Fe in seawater.Kinetic rate constants of Fe with the ligand TAC (2-(2-Thiazolylazo)-p-cresol) were also determined. The formation rate constant of Fe(TAC)2 varied between 0.1 × 108 and 3.6 × 108 M− 1 s− 1, the dissociation rate constant between 0.2 × 10− 5 and 17 × 10− 5 s− 1 for both S = 26 and S = 10. The conditional stability constant of Fe(TAC)2 (βFe(TAC)2′) varied between 22 and 23.4 for S = 10 and S = 26 more or less equal to that known from the literature (logβFe(TAC)2′ = 22.4; [Croot, P.L., Johansson, M., 2000. Determination of iron speciation by cathodic stripping voltammetry in seawater using the competing ligand 2-(2-Thiazolylazo)-p-cresol (TAC). Electroanalysis, 12, 565–576.]). However, at S = 0.3 the logβFe(TAC)2′ was 25.3, three orders of magnitude higher. Apparently the application of TAC to samples of low salinity can only be done when the correct βFe(TAC)2′ is known.  相似文献   

18.
Photochemical mineralization of dissolved organic matter (DOM) plays an important role in the cycling of carbon in estuarine systems. A key to modeling this process is knowledge of apparent quantum yields (AQYs) for the photochemical products. Here we determined spectral AQYs for carbon dioxide (CO2) and carbon monoxide (CO), the main products of DOM photomineralization, along the main axis of the Delaware Estuary. Apparent quantum yields for CO2 photoproduction were determined shipboard using a multi-spectral irradiation system. Carbon monoxide AQYs were determined in stored samples by employing a narrow band spectral irradiation system. A single AQY spectrum described carbon dioxide photochemical production within the estuary whereas CO AQY spectra varied with salinity, suggesting different precursors and mechanisms for the production of these two species. CO2 AQYs were used along with shipboard measurements of DOM absorbance and solar irradiance to calculate photoproduction rates. Calculated CO2 photoproduction rates agreed with directly measured rates (2 to 4 μM CO2 d? 1) within experimental error, supporting the further development and use of AQYs to calculate regional-scale photochemical fluxes.  相似文献   

19.
Measurements of dissolved gases (O2, N2O), nutrients (NO3−, NO2−, PO43−), and oceanographic variables were performed off northern Chile (∼21°S) between March 2000 and July 2004, in order to characterize the existing oxygen minimum zone (OMZ) and identify processes involved in N2O cycling. Both N2O and NO3− displayed sharp, shallow peaks with concentrations of up to 124 nM (1370% saturation) and 26 μM, respectively, in association with a strong oxycline that impinges on the euphotic zone. NO2− accumulation below the oxycline's base reached up to 9 μM. The vertical distribution of physical and chemical parameters and the existing relationships between apparent oxygen utilization (AOU), apparent N2O production (ΔN2O), and NO3− revealed three main layers within the upper OMZ. The first layer, or the upper part of the oxycline, is located between the base of the mixed layer and the mid-point of the oxycline (around σt=25.5 kg m−3). There the O2 declines from ∼250 to ∼50 μM, and strong (but opposing) O2 and NO3− gradients and their associated AOU–ΔN2O and AOU–NO3− relationships indicate that nitrification produces N2O and NO3− in the presence of light. The second layer, or lower part of the oxycline, represents the upper OMZ boundary and is located between the middle and the base of the oxycline (25.9<σt<26.1 kg m−3). In this layer NO3− reduction begins at O2 levels ranging from ∼50 to ∼11 μM and accumulation of 41–68% of the ΔN2O pool occurs. The accumulation of N2O (but not of NO2− or NH4+) and the observed AOU–ΔN2O and AOU–NO3− relationships (which are opposite to those of the overlying first layer) suggest that a coupling between nitrification and NO3− reduction is involved in N2O cycling in this second layer. The third layer is the OMZ core, where the O2 concentration remains constant (O2<11 μM). It coincides with σt>26.2 kg m−3, which is typical of Equatorial Subsurface Water (ESSW). In this layer, N2O and NO3− continue to decrease, but a large NO2− accumulation is observed. Considering all the data, a biogeochemical model for the upper OMZ off northern of Chile is proposed, in which nitrification and denitrification differentially mediate N2O cycling in each layer.  相似文献   

20.
One hundred twelve rainwater samples collected from 1986 to 2003 at the signal station of Cap Ferrat (France, NW Mediterranean coast) were analysed for phosphate and silicate contents. This sampling site is affected by a European urban-dominated background material, with episodic Saharan dust inputs. The input of dissolved inorganic phosphorus (DIP) and dissolved inorganic silicon (DISi) was calculated. The most significant loadings of DIP and DISi were selected in order to assess their potential impact on phytoplankton dynamics, particularly in oligotrophic conditions, when surface waters are nutrient-depleted. The theoretical new production triggered by DIP and DISi inputs (NPatmo) was estimated through Redfield calculations. The maximum theoretical DIP-triggered NPatmo was up to 670 mg C m−2 in October, at the end of the oligotrophic period (135 mg C m−3 in the 5 m-thick surface layer). During the same period, the daily integrated primary production measured at the DYFAMED site (NW Mediterranean Sea) was on average 219 mg C m−2 d−1 within the 0–100 m depth water column, while the mean daily primary production in the 5 m-thick surface layer was 1.6 mg C m−3 d−1. However, high NPatmo due to high DIP inputs might be episodically limited by lower DISi inputs, which may consequently lead to episodic preferential growth of non-siliceous phytoplanktonic species.  相似文献   

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