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1.
The extent and kinetics of Np(V)O2+ adsorption from dilute aqueous solutions and seawater onto a variety of synthetic and natural solids were determined at 25°C and 1 atm total pressure. Extensive and complex adsorption reactions were found, contrary to speculations in the literature that NpO2+ should behave as a simple monovalent ion with a low affinity for surfaces. When normalized to adsorption per unit solid surface area, the ranking for the synthetic solids was aragonite ? calcite > goethite ? MnO2 ≈ clays. Natural materials generally followed the same behavior patterns as their synthetic counterparts. The dissolved/adsorbed ratio was found to be constant over a wide range (10?13–10?7M) of NpO2+ concentrations. At higher concentrations the extent of adsorption decreased until a solubility limit was reached at approximately 10?5 M.Solution composition had the most significant influence for NpO2+ adsorption on goethite, where much more extensive adsorption occurs in dilute solutions than in seawater. When seawater is added to a dilute solution, extensive desorption of NpO2+ from goethite occurs. Tests conducted on NpO2+ adsorbed on carbonates indicated that it remained in the V oxidation state.There is a growing consensus that Pu dissolved in natural waters also occurs dominantly in the V oxidation state as PuO2+ ion. Consequently, these results for NpO2+ may serve as a guide for Pu behavior when also in the V oxidation state. The fact that most adsorbed Pu is found in the III or IV oxidation states indicates that reduction of Pu may occur subsequent to adsorption in the V oxidation state.  相似文献   

2.
During the August 1993 Intergovernmental Oceanographic Commission's Contaminant Baseline Survey cruise to the high latitude North Atlantic, determinations of total dissolved sulfide (TDS=free sulfide, H2S(g)+HS−+S2−, plus dissolved metal–sulfide complexes), free sulfide, and carbonyl sulfide (OCS) were made along a horizontal transect and at six vertical profile stations. Unlike data from lower latitudes, the distributions of OCS and TDS were remarkably uniform, with surface water OCS averaging 108 pmol/l and TDS averaging 58 pmol/l; free sulfide was below the detection limits of 5 pmol/l at all stations. The vertical profiles of both OCS and TDS show surface maxima and rapid decreases into the major thermocline. For OCS this is indicative of production via photolysis of dissolved organic sulfur compounds, while TDS may be produced from the hydrolysis of OCS. The concentrations of OCS are similar to those found in coastal waters, and suggests that these sub-polar regions may be large OCS sources to the troposphere during summer. However, it is unclear whether higher concentrations of OCS precursors, a long photo period during summer, or slow rates of removal by hydrolysis due to low temperatures are responsible for the elevated OCS levels. TDS concentrations are primarily controlled by the rate of OCS hydrolysis, production by phytoplankton, and oxidative loss by oxygen and iodate. Both of the losses are affected by trace metal complexation, and to examine this, freshly collected seawater was amended by hydrogen sulfide gas and trace metal additions, and the concentration of free sulfide monitored as a function of metal concentration. This allowed the determinations of conditional stability constants for metal sulfides, with the log Kcond of Cd(HS)+ being 8.0±0.5, 7.0±0.6 for Ni(HS)+, and 7.4±0.7 for Zn(HS)+; attempts at measuring the Kcond of Cu(HS)+ were thwarted by the apparent reduction of Cu(II) to Cu(I) by sulfide. Using these constants in an equilibrium speciation model indicates that on average about 75% of the measured TDS was free, with the remaining fraction complexed with Ni, Cd, and Zn (in order of decreasing percentages). While closer to the field observations than would be found with stability constants reported by other workers, these values are still at variance with the actual speciation (i.e., <30% free). This suggests that the stability constants for Cd, Ni, and Zn are somewhat higher than found, thus reducing the concentration of free sulfide. Nevertheless, these speciation data are important for balancing the TDS budget since the loss by iodate oxidation of free sulfide exceeds all production estimates.  相似文献   

3.
In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et4NI and NaCl (for fulvic acid 0.1 < I /mol L− 1 < 0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5 < S < 45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na+, K+, Mg2+, Ca2+) and anions (Cl−, SO42−) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous speciation studies of synthetic polyelectrolytes (polyacrylic and polymethacrylic acids of different molecular weights). Results indicate that the SIT, Pitzer and Ion Pairing formation models used in studies of low molecular weight electrolytes may also be applied to polyelctrolytes with a few simple adjustments.  相似文献   

4.
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   

5.
Thermodynamic considerations based on existing data from various laboratory studies of plutonium species in aqueous solution are used to predict the speciation of this radioactive pollutant in seawater. Oxidation-reduction data for plutonium suggest that Pu(VI) should be very dominant in seawater solution compared to Pu(IV), and that Pu(III) and Pu(V) should be absent. The disproportionation reactions and the alpha reduction mechanism are probably of no consequence to the oxidation state in seawater. However, the irreversible hydrolysis of Pu4+ and the associated formation of polymeric Pu(OH)4 colloids are important mechanisms of speciation control and plutonium removal to sediments, by adsorption onto suspended matter. Stability constants for plutonium complexation with inorganic ligands in seawater suggest that Pu(VI) dissolved in seawater will be dominantly PuO2CO3OH−.The theoretical predictions of plutonium speciation and behaviour in seawater are compared to the only available data on plutonium speciation in seawater (Nelson and Lovett, 1978). Good agreement between the predictions and field observations was obtained, within the limitations imposed by the scarcity of data on this subject.  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.
Measurements of sub-surface light attenuation (Kd), Secchi depth and suspended particulate material (SPM) were made at 382 locations in transitional, coastal and offshore waters around the United Kingdom (hereafter UK) between August 2004 and December 2005. Data were analysed statistically in relation to a marine water typology characterised by differences in tidal range, mixing and salinity. There was a strong statistically significant linear relationship between SPM and Kd for the full data set. We show that slightly better results are obtained by fitting separate models to data from transitional waters and coastal and offshore waters combined. These linear models were used to predict Kd from SPM. Using a statistic (D) to quantify the error of prediction of Kd from SPM, we found an overall prediction error rate of 23.1%. Statistically significant linear relationships were also evident between the log of Secchi depth and the log of Kd in waters around the UK. Again, statistically significant improvements were obtained by fitting separate models to estuarine and combined coastal/offshore data – however, the prediction error was improved only marginally, from 31.6% to 29.7%. Prediction was poor in transitional waters (D = 39.5%) but relatively good in coastal/offshore waters (D = 26.9%).SPM data were extracted from long term monitoring data sites held by the UK Environment Agency. The appropriate linear models (estuarine or combined coastal/offshore) were applied to the SPM data to obtain representative Kd values from estuarine, coastal and offshore sites. Estuarine waters typically had higher concentrations of SPM (8.2–73.8 mg l−1) compared to coastal waters (3.0–24.1 mg l−1) and offshore waters (9.3 mg l−1). The higher SPM values in estuarine waters corresponded to higher values of Kd (0.8–5.6 m−1). Water types that were identified by large tidal ranges and exposure typically had the highest Kd ranges in both estuarine and coastal waters. In terms of susceptibility to eutrophication, large macrotidal, well mixed estuarine waters, such as the Thames embayment and the Humber estuary were identified at least risk from eutrophic conditions due to light-limiting conditions of the water type.  相似文献   

8.
《Marine Chemistry》2007,103(1-2):84-96
An isotope dilution method has been developed to determine by gas chromatography/mass spectrometry (GC/MS) the rates of ammonium and nitrite oxidation in severely oligotrophic marine waters. The method is based on the formation of sudan-1 from nitrite, or from nitrate following reduction to nitrite. Samples were collected by solid phase extraction and purified by high performance liquid chromatography (HPLC). A deuterated sudan-1 internal standard was synthesized, purified by HPLC and used for quantitative analysis. Concentrations of NO2− and NO3− were generally < 2 nmol/kg and < 5 nmol/kg respectively, typical of oligotrophic surface waters, and turnover times for the inorganic N pools ranged from < 1 day to > 10 days. Significant rates of nitrification were measured in the surface oligotrophic ocean, with rates of ammonium and nitrite oxidation generally within the range of 10–500 pmol/kg/h. Consequently, a significant proportion of daily NO3− assimilation by marine phytoplankton is regenerated, and not new. In a case study of the oligotrophic gyre of the North Atlantic, the influence of NH4+ regeneration and nitrification on f-ratio values suggests that in the oligotrophic ocean, f-ratio values may be significantly, and sometimes grossly, overestimated.  相似文献   

9.
Various investigators reported a decrease in pH as seawater is concentrated. A similar phenomenon was reported for Dead Sea waters which are about ten times more saline than seawater. The reasons for the low pH values of Dead Sea waters (pH 5.9–6.5), which precipitate CaCO3, were investigated by determining the apparent dissociation constants of carbonic acid in these brines. A new method, based on alkalinity titration and least-squares fitting, was used to estimate the proton activity coefficient (γH+) and the first and second dissociation constants of carbonic acid (K1′, K2′) in natural and artificial Dead Sea waters. It was found that as the salt content increases, pK′1 and pK′2 values progressively decrease whereas γH+ sharply increase. At the highest salinity investigated (TDS = 330 gl?1) γH+ pK′1 and pK′2 values are 24.5, 5.09 and 6.23, respectively, as compared to about 0.8, 5.9, 9.1 respectively for normal seawater (19‰ chlorinity) at the same temperature (30°C).The implication of the results of this study regarding solubility of CaCO3 and the general behavior of the carbonate system in hypersaline solutions is discussed.  相似文献   

10.
The Arcachon lagoon is a 156 km2 temperate mesotidal lagoon dominated by tidal flats (66% of the surface area). The methane (CH4) sources, sinks and fluxes were estimated from water and pore water concentrations, from chamber flux measurements at the sediment–air (low tide), sediment–water and water–air (high tide) interfaces, and from potential oxidation and production rate measurements in sediments. CH4 concentrations in waters were maximal (500–1000 nmol l−1) in river waters and in tidal creeks at low tide, and minimal in the lagoon at high tide (<50 nmol l−1). The major CH4 sources are continental waters and the tidal pumping of sediment pore waters at low tide. Methanogenesis occurred in the tidal flat sediments, in which pore water concentrations were relatively high (2.5–8.0 μmol l−1). Nevertheless, the sediment was a minor CH4 source for the water column and the atmosphere because of a high degree of anaerobic and aerobic CH4 oxidation in sediments. Atmospheric CH4 fluxes at high and low tide were low compared to freshwater wetlands. Temperate tidal lagoons appear to be very minor contributor of CH4 to global atmosphere and to open ocean.  相似文献   

11.
The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH4+ L− 1 d− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH4+ m− 2 d− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.  相似文献   

12.
This study investigates the biogeochemical processes that control the benthic fluxes of dissolved nitrogen (N) species in Boknis Eck – a 28 m deep site in the Eckernförde Bay (southwestern Baltic Sea). Bottom water oxygen concentrations (O2−BW) fluctuate greatly over the year at Boknis Eck, being well-oxygenated in winter and experiencing severe bottom water hypoxia and even anoxia in late summer. The present communication addresses the winter situation (February 2010). Fluxes of ammonium (NH4+), nitrate (NO3−) and nitrite (NO2−) were simulated using a benthic model that accounted for transport and biogeochemical reactions and constrained with ex situ flux measurements and sediment geochemical analysis. The sediments were a net sink for NO3− (−0.35 mmol m−2 d−1 of NO3−), of which 75% was ascribed to dissimilatory reduction of nitrate to ammonium (DNRA) by sulfide oxidizing bacteria, and 25% to NO3− reduction to NO2− by denitrifying microorganisms. NH4+ fluxes were high (1.74 mmol m−2 d−1 of NH4+), mainly due to the degradation of organic nitrogen, and directed out of the sediment. NO2− fluxes were negligible. The sediments in Boknis Eck are, therefore, a net source of dissolved inorganic nitrogen (DIN = NO3− + NO2− + NH4+) during winter. This is in large part due to bioirrigation, which accounts for 76% of the benthic efflux of NH4+, thus reducing the capacity for nitrification of NH4+. The combined rate of fixed N loss by denitrification and anammox was estimated at 0.08 mmol m−2 d−1 of N2, which is at the lower end of previously reported values. A systematic sensitivity analysis revealed that denitrification and anammox respond strongly and positively to the concentration of NO3− in the bottom water (NO3−BW). Higher O2−BW decreases DNRA and denitrification but stimulates both anammox and the contribution of anammox to total N2 production (%Ramx). A complete mechanistic explanation of these findings is provided. Our analysis indicates that nitrification is the geochemical driving force behind the observed correlation between %Ramx and water depth in the seminal study of Dalsgaard et al. (2005). Despite remaining uncertainties, the results provide a general mechanistic framework for interpreting the existing knowledge of N-turnover processes and fluxes in continental margin sediments, as well as predicting the types of environment where these reactions are expected to occur prominently.  相似文献   

13.
Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, Kd, which varies from 0.67 × 105 to 3.38 × 106 ml g−1 for suspended particle concentrations of 2–64 mg l−1. The Kd values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for Kd values of 105, 106 and 107 ml g−1 with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with Kd value 107 ml g−1 and C0 values 16 × 10−6 mg ml−1 and 92 × 10−6 mg ml−1. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries.  相似文献   

14.
Chlorofluorocarbon (CFC) 11 and 12 transports across the transoceanic World Ocean Circulation Experiment (WOCE) A25 section in the subpolar North Atlantic are derived from an inverse model using hydrographic and ADCP data (Lherminier et al., 2007). CFC and anthropogenic carbon (CANT) advective transports contrary to expected are uncoupled: CANT is transported northeastwards (82±39 kmol s?1) mainly within the overturning circulation, while CFC-11 and CFC-12 are transported southwestwards (?24±4 and ?11±2 mol s?1, respectively) as part of the large-scale horizontal circulation. The main reason for this uncoupled behaviour is the complex CFC vs. CANT relation in the ocean, which stems from the contrasting temperature relation for both tracers: more CANT dissolves in warmer waters with a low Revelle factor, while CFC’s solubility is higher in cold waters. These results point to CANT and CFC having different routes of uptake, accumulation and transport within the ocean, and hence: CANT transport would be more sensitive to changes in the overturning circulation strength, while CFC to changes in the East Greenland Current and Labrador Sea Water formation in the Irminger Sea. Additionally, CANT and CFCs would have different sensitivities to circulation and climate changes derived from global warming as the slowdown of the overturning circulation, increase stratification due to warming and changes in wind stress.  相似文献   

15.
Iodide oxidation to iodate in near-surface waters of the open oceans is an elusive process, and an unequivocal demonstration of it would simplify modelling of the marine iodine system. In the open ocean, the upward advection of iodate complicates any mathematical treatment of the problem. In this context, the high concentration (0.1 μM) of iodate in the Black Sea surface waters suggested that this Sea might be a place where oxidation might be demonstrated. Hydrologically, the surface waters of the Black Sea appear to be downstream of the deeper waters and, given the latter's anoxicity, the surface waters seemed likely to gain most of their iodine as iodide by upward advection. To test this further, prior to experimentation, an iodine budget for the near-surface waters, based upon the latest hydrological model of the Sea was prepared; this predicts a minimum oxidation flux of 3.89×10−4 mol I m−2 a−1. The chemistry of this oxidation is discussed in the light of existing knowledge of the sulfide system. It is argued that as the redox potential of the IO3−/I− and I2/I− couples at pHs typical of the Black Sea (7.75) are much higher than that of the sulfate–sulfide couple, iodide is probably oxidized in the near-surface domain. This contrasts with sulfide oxidation in the suboxic zone. The possible role of nitrifying bacteria in the oxidation is discussed.  相似文献   

16.
The interactions of Fe(II) and Fe(III) with the inorganic anions of natural waters have been examined using the specific interaction and ion pairing models. The specific interaction model as formulated by Pitzer is used to examine the interactions of the major components (Na+, Mg2+, Ca2+, K+, Sr2+, Cl−, SO4−, HCO3−, Br−, CO32−, B(OH)4−, B(OH)3 and CO2) of seawater and the ion pairing model is used to account for the strong interaction of Fe(II) and Fe(III) with major and minor ligands (Cl−, SO42−, OH−, HCO3−, CO32− and HS−) in the waters. The model can be used to estimate the activity and speciation of iron in natural waters as a function of composition (major sea salts) and ionic strength (0 to 3 M). The measured stability constants (KFeX*) of Fe(II) and Fe(III) have been used to estimate the thermodynamic constants (KFeX) and the activity coefficient of iron complexes (γFeX) with a number of inorganic ligands in NaClO4 medium at various ionic strengths: In(KFeX/γFeγX) = InKFeX − In(γFeX) The activity coefficients for free ions (γFe, γx) needed for this extrapolation have been estimated from the Pitzer equations. The activity coefficients of the ion pairs have been used to determine Pitzer parameters (BFeX, BFeX0, CFeXφ) for the iron complexes. These results make it possible to estimate the stability constants for the formation of Fe(II) and Fe(III) complexes over a wide range of ionic strengths and in different media. The model has been used to determine the solubility of Fe(III) in seawater as a function of pH. The results are in good agreement with the measurements of Byrne and Kester and Kuma et al. When the formation of Fe organic complexes is considered, the solubility of Fe(III) in seawater is increased by about 25%.  相似文献   

17.
A new sample treatment was developed for the determination of dissolved cadmium in Tagus estuarine waters, based on focused ultrasound in conjunction with small volumes in the extraction steps for Cd pre-concentration. Cadmium was first pre-concentrated using a classical approach (APDC as the complexing agent and MIBK as the organic phase) and then back-extracted into HNO3 with the aid of focused ultrasound, which reduced the acid concentration by more than one order of magnitude (from 4 to 0.1 mol L− 3). This sample treatment was accomplished in less than 5 min, using low sample volume (20 mL), and low-volume, low-concentration reagents. The pre-concentration factor used in this work was 25, but different sample/organic volume ratios may be used in order to increase that value. The limit of detection and the limit of quantification in Tagus water samples were 0.03 nmol L− 1 and 0.1 nmol L− 3, respectively. Recoveries from spiked Tagus water were higher than 90%. The procedure was validated using the reference estuarine water NRC-SLEW-3. In the solubilization of Cd particulate, bath ultrasonication was used in conjunction with HNO3 + HCl, followed by H2O2, which took about 2 instead of the usual 12 h (cooling included) when high-pressure microwave digestion is used.  相似文献   

18.
The absorption of anthropogenic CO2 and atmospheric deposition of acidity can both contribute to the acidification of the global ocean. Rainfall pH measurements and chemical compositions monitored on the island of Bermuda since 1980, and a long-term seawater CO2 time-series (1983–2005) in the subtropical North Atlantic Ocean near Bermuda were used to evaluate the influence of acidic deposition on the acidification of oligotrophic waters of the North Atlantic Ocean and coastal waters of the coral reef ecosystem of Bermuda. Since the early 1980's, the average annual wet deposition of acidity at Bermuda was 15 ± 14 mmol m− 2 year− 1, while surface seawater pH decreased by 0.0017 ± 0.0001 pH units each year. The gradual acidification of subtropical gyre waters was primarily due to uptake of anthropogenic CO2. We estimate that direct atmospheric acid deposition contributed 2% to the acidification of surface waters in the subtropical North Atlantic Ocean, although this value likely represents an upper limit. Acidifying deposition had negligible influence on seawater CO2 chemistry of the Bermuda coral reef, with no evident impact on hard coral calcification.  相似文献   

19.
The aqueous speciation of rhenium at the temperatures on or near the Earth's surface, especially in anoxic environments, is not well known. For the first time, the relative importance of ReO4− and the neutral rhenium species, Re(OH)40, is thermodynamically modeled in anoxic environments at ambient temperature where ReS2 or its solid solution(s) is likely to control the solubility. This thermodynamic model suggests that ReO4− is an insignificant species in anoxic environments. In comparison to observed total rhenium concentrations in anoxic waters (from ∼3 to ∼30 pmol/kg), the contribution from ReO4− would be less than 10−8 ppb (∼4×10−5 pmol/kg). In contrast, the neutral rhenium species is an important species in anoxic environments. At ΣH2S=10−4 molal, 10−2 ppb (∼40 pmol/kg) of Re(OH)40 can exist in equilibrium with ReS2 in the HS− field at a pH of about 9 or under the oxygen fugacity conditions imposed by the HS−/SO42− redox couple, demonstrating its importance in anoxic environments. Applications of the present study to the Black Sea indicate that rhenium concentrations in the anoxic water column at depths ranging from 105 to ∼390 m can be successfully modeled as Re(OH)40, implying that the dominant species in solution may be Re(OH)40.  相似文献   

20.
For several decades, prokaryotic and eukaryotic inhibitors have been used to exclude bacteria from microalgal cultures and for investigating prey-predator relationships. Recently there has been considerable interest in using specific inhibitors for studying the interactions between bacteria and phytoplankton, by selective repression of either organism’s activity. The effectiveness of chemical inhibitors must be tested before applying them to natural communities to partition metabolic activities between functional groups. Six different antibiotics selected from the most commonly reported in the literature were tested, at concentrations varying from 12.5 to 100 mg L−1, for their effect on bacterial growth and functional diversity of natural communities from Mediterranean coastal waters. Penicillin and streptomycin each at a final concentration of 100 mg L−1 significantly reduced bacterial growth within 2 h. There was a greater impact on bacterial functional diversity when both antibiotics were mixed together. This mixture did not have any significant effect on the growth of selected cultured phytoplankton strains, whereas the eukaryote inhibitor cycloheximide at 100 mg L−1 reduced growth within 2 h of incubation. The penicillin–streptomycin mixture and cycloheximide alone successfully partitioned NH4+ and NO3− uptake between bacteria and phytoplankton bi-weekly sampled in a coastal lagoon in Autumn, where bacterial contribution to total NH4+ and NO3− uptake averaged 46 and 41%, respectively. The use of specific inhibitors may be a valuable method for studying interactions, such as competition and mutualism, or lack of interaction between the different components of microbial communities and could be used to study their relative importance in biogeochemical fluxes.  相似文献   

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