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1.
The uptake of urea, nitrate and ammonium by phytoplankton was measured using 15N isotopes over a one-year period in Great South Bay, a shallow coastal lagoon. The bay is a unique environment for the study of nutrient uptake since ambient concentrations of NO3?NH4+ and urea remain relatively high through the year, and phytoplankton are probably never nutrient limited. Urea nitrogen averaged 52% of the total assimilated, while ammonium represented 33% and nitrate 13%. High rates of ammonium uptake occurred only at low urea concentrations (ca< 1-μg-atom urea l?1). Over the sampling period urea was present in relatively high concentrations, averaging 5·35 μg-atom N l?1, while means for ammonium and nitrate averaged 1·94 and 0·65 μg-atom N l?1, respectively. Total N uptake measured with 15N averaged about 3·3 times the calculated (from elemental ratios and 14C productivity measurements) N needs of the phytoplankton population. Highest nitrogen uptake occurred in the summer and coincided with the primary production maximum.  相似文献   

2.
Losses of 15N labelled nitrogen in a Spartina alterniflora salt marsh was measured over three growing seasons. Labelled NH4+N equivalent to 100 μg 15N g?1 of dry soil was added in four instalments over an eight week period. Recovery of the added nitrogen ranged from 93% 5 months after addition of the NH4+N to 52% at the end of the third growing season which represented a nitrogen loss equivalent to 3·4 gNm?2. The availability of the labelled NH4+N incorporated into the organic fraction was estimated by calculation of the rate of mineralization. The time required for mineralization of 1% of the tagged organic N increases progressively with succeeding cuttings of the S. alterniflora and ranged from 152 to 299 days. Only 2% of the nitrogen applied as 15N labelled plant material to the marsh surface in the fall could be accounted for in S. alterniflora the following season.  相似文献   

3.
The daily concentrations of NH4+, NO3?, and NO3? + NO2? within the North Inlet system are all negatively associated with tidal stage during the late summer, this association breaking down during the winter. The high concentrations of these constituents during low tide coupled with the lack of streamflow during the late summer suggests that there is an internal source for these species. Ammonium and orthophosphate most likely have their source in sediment diffusion from tidal creek sediments and/or seepage from the vegetated marsh surface during tidal exposure. It is hypothesized that high nitrate plus nitrite values at low tide are caused by nitrification within the tidal water or tidal creek sediments. During the summer there is evidence for a source of dissolved organic nitrogen and dissolved organic phosphorus within the North Inlet system, probably via diffusion from creek sediments. In general the main source of dissolved organic nitrogen is via stream-flow from the adjacent watershed. Particulate nitrogen and phosphorus concentrations are a function of: (1) wind and rain events which cause resuspension of particulate material from the tidal creek banks, (2) rain events which scour the marsh surface during tidal exposure, and (3) high tidal velocities which scour the creek bottoms.  相似文献   

4.
Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH2+ species were found to be insignificant relative to Fe(OH)2+ at p[H+] = ?log [H+] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of 1Kso = [Fe3+][H+]?3 = 4.7 · 105. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)30 species. The formation constant for this species can be calculated as 1β3 = [Fe(OH)30] [H+]3/[Fe3+] = 2.4 · 10?14. The Fe(OH)4? species is present at concentrations which are negligible compared to Fe(OH)2+ and Fe(OH)30 in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H+] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)2+ and Fe(OH)30 species.  相似文献   

5.
Equilibrium constants for copper(II)-carbonate and -bicarbonate species have been determined at 25°C from consideration of malachite, Cu2(OH)2CO3(s), solubility in UV-photo-oxidized perchlorate solutions of 0.72 m ionic strength. The ratios of total dissolved copper, T(Cu), to free copper(II) ion, [Cu 2+], in 30 malachite saturated experimental solutions of 1–10 × 10?3eq kg?1 H2O initial total alkalinity (TAi in the pH range 5.0–9.3 were fitted to a copper(II)-ion speciation model. The experimental data indicate the existence of CuCO3+, CuHCO3+ and Cu(OH)CO3? in addition to the hydrolys and Cu(OH)CO3? in addition to the hydrolysis products in the range of conditions defined by this study. The stoichiometric equilibrium constants, applicable to seawater at 0.72 m ionic strength, 25°C and 1 atm are
βCuCO3=[CuCO03][Cu2+][CO2?3]=(1.59±0.03)×106
βCuHCO3=[CuHCO+3][Cu2+][HCO?3]=(2.3±0.3)×102
1βCu(OH)CO3=[Cu(OH)CO?3H[Cu2+][CO2?3]=(7.6±0.3)×10?4
A speciation model employing the equilibrium constants determined in this study and copper(II) hydrolysis constants from previous work suggests that the inorganic speciation in seawater (pH = 8.2, TA = 2.3 meq kg ?1, 25°C) is dominated by the CuCO30 complex (82%) and that only 2.9% of the total inorganic copper exists as the free copper(II) ion. Hydrolysis products, CuOH+ and Cu(OH)20, account for 6.5% while CuHCO3+ and Cu(OH)CO3? species comprise 1.0 and 6.3% of the total inorganic copper, respectively.  相似文献   

6.
The apparent ionization constants for silicic acid, k1 and k2, and the ionic product of water, kw, have been determined in 0.05, 0.1, 0.2, 0.4 and 2.0 M Na(CI) media at 25°C. The medium dependence of these constants was found to fit equations of the form
logki=logKi+aiI12(1+I12)+biI
where K1 is the ionization constant in pure water, αi and bi are parameters of which bi has been adjusted to present data. The following results were obtained (αi, bi): pK1 = 9.84, (1.022, ?0.11); pK2 = 13.43, (2.044, ?0.20); and pKw = 14.01 (1.022, ?0.22). ki values are collected in Tables I and II. Attempts have been made to explain the medium dependence of k1 and k2 with weak sodium silicate complexing according to the equilibria
Na++SiO(OH)?3?NaSiO(OH)3;k11
Na++SiO2(OH)22?NaSiO2(HO)?2; k21
giving k11 = 0.37M?1 and k21= 3.0M?1. However, these weak interactions cannot be interpreted unambiguously from potentiometric data at different 1-levels. Probably the medium dependence could equally well be expressed by variations in the activity coefficients.The measurements were performed as potentiometric titrations using a hydrogen electrode. The average number of OH- reacted per Si(OH)4, Z, has been varied within the limits 0 ? Z ? 1.1 and B1, the total concentration of Si(OH)4, between 0.001 M and 0.008 M. k1 was evaluated from experimental data with B ? 0.003 M, and k2 with B ? 0.008 M and Z ? 0.95.  相似文献   

7.
The photolysis of nitrate in seawater by sunlight has been re-examined using abiotic seawater and naturally occurring concentrations. Photochemical formation of nitrite from nitrate was observed. First-order nitrate photolysis rate coefficients calculated from nitrite appearance (corrected for concomitant nitrite photolysis) ranged from 0 to 2.3 yr?1, median 0.7 yr?1. The coefficients did not correlate well with water chemistry, but decreased with increasing light dose. A first-order rate coefficient of 0.4 yr?1 was calculated for the primary photochemical process NO3? + hυ = NO2? + O(3P) under sea surface equatorial insolation and cloudiness conditions. However, no significant nitrate concentration decreases could be detected, suggesting an upper limit for the net first-order nitrate loss rate coefficient of 0.3 yr?1. The data thus imply some conversion in the reverse sense: NO2? + hυ →→ NO3?.If our median rate estimate applies to surface oceanic conditions, nitrate photolysis proceeds at roughly 0.02–0.5% of the rate of N incorporation during primary production. It is thus not a significant NO3-N sink. Since such reactive species as oxygen atoms, nitrogen dioxide, and hydroxyl radicals are produced, the reaction may have significant consequences in seawater. However, nitrite photolysis is almost certainly a more significant process.The results show internal inconsistencies and our rates are markedly different from those calculated using data from other studies. Nitrate photolysis rates are theoretically concentration- and light dose-dependent. Whether these dependencies explain the apparent discrepancies is unclear, as methodological effects may also be involved. The system requires further study.  相似文献   

8.
An investigation of ferric ion complexing has been conducted in synthetic media and seawater at 25°C. Formation constants were potentiometrically determined for the species FeCl2+, FeCl2+, FeOH2+, and Fe(OH)2+ at an ionic strength of 0.68 m. Formation constants for the ferric chloride complexes were determined as Clβ1 = 2.76 and Clβ2 = 0.44. In a study of the reaction Fe3+ + nH2O ? Fe(OH)n(3?n)+ + nH+ in NaClO4, NaNO3 and NaCl the formation constants 1β1and1β2 were shown to be relatively independent of medium when the effects of nitrate and chloride complexing were taken into account. The average values obtained for these constants are 1β1 = 1.93 · 10?3and1β2 = 8.6 · 10?8. Reasonable agreement with these values was obtained when these constants were determined in seawater by accounting for the effects of chloride, fluoride and sulfate complexing.  相似文献   

9.
A 22-month study was conducted to determine the exchange of nitrogen and phosphorus between a mesohaline vegetated marsh in the Carter's Creek area of Virginia and the surrounding estuary, focusing on the role of the vegetated marsh surface in the processing of these constituents. On an annual basis there was a removal of NH4+, PO43?, NO3?, dissolved organic nitrogen, dissolved organic phosphorus, particulate nitrogen and particulate phosphorus from the tidal water as it resided on the vegetated marsh. Only nitrite was transported from the marsh to the estuary. Most of the nitrogen and phosphorus species showed distinct seasonal trends with respect to the direction of transport except nitrate and orthophosphate. The ammonium flux data indicates that this nutrient was removed from the inundating water during late spring and fall, with a slight release of this constituent into the tidal water during the late summer. The transport of nitrite was from the estuary to the marsh for most of the year except during the fall. The large release of this nutrient into the tidal water at this time is associated with the senescence of the marsh vegetation. There was a large removal of DON from the tidal water during the fall, while the flux of DOP was from the estuary to the marsh for most of the year except during the summer. The largest removal of particulate nitrogen and phosphorus from the tidal water occurred during the summer months when the turbidity of the tidal water was highest, especially when wave scouring of the mudflats brings material into the water column. A loss of particulate nitrogen from the marsh to the estuary was evident during the fall and winter.  相似文献   

10.
The nitrogen relations of Enteromorpha spp. growing on intertidal mud flats have been examined over a twelve-month period. Nitrogen assimilation rates using 15N have been used to calculate the production of the alga and were between 0·046 and 0·217 mg NH4+N (g dry wt alga)?1 h?1 A considerable quantity of the alga was buried beneath the sediment over the growth season and was calculated to be equivalent to an input of up to 9·52 g N m?2 per month and 32 g N m?2 over one complete growth season. Based on carbon, this latter value represented an input of approximately 320 g C m?2 annually. Low rates of nitrogenase activity (acetylene reduction) were found to be associated with the Enteromorpha. The organisms responsible for the nitrogenase activity were probably heterotrophic bacteria but they did not contribute significant quantities of nitrogen to the alga.  相似文献   

11.
A field investigation was carried out to collect data of inner bar migration. Profiles were measured once or twice a week for a two-year period at Naka Beach, Ibaraki Prefecture, Japan. It was found that the onshore migration of inner bars could be described by two dimensionless quantities as: 5D(Hb)max < (Hb)maxgT2max < 20D(Hb)max where (Hb)max is the maximum value of daily average breaker height during one interval between surveys, Tmax is the average wave period of the day giving (Hb)max, D is the mean size of the beach sediment, and g is the acceleration due to gravity. Analyses based on surfzone sediment dynamics yields v?(wDb) = 2 × 10?11 ((H?bD)3, where v? is the average speed of onshore bar-migration, b is the bar height, H?b is the average breaker height, and w is the fall velocity of the beach sediment. Nomographs for the speed of landward migrating bars are also presented.  相似文献   

12.
The addition of various concentrations (1, 10 and 20 mM) of Group VI anions to sediment slurry resulted in inhibition of the rate of sulphate reduction at the two higher concentrations, the degree of inhibition being in the order of molyb-date (MoO4=)>selenate(SeO4=)>tungstate(WO4=). The addition of 20 mM concentrations of these inhibitors almost entirely eliminated sulphate reduction. Doubling the sulphate concentration while using the highest concentration of inhibitors (20 mM) led to the re-establishment of some sulphate reduction in the SeO4= and WO4= treated slurries whereas no such reversal was noticed with MoO4=. These observations suggested that SeO4= and WO4= are competitive inhibitors of sulphate reduction, while MoO4= is a non-competitive inhibitor.  相似文献   

13.
The density of artificial seawater has been measured with a magnetic float densitometer at 1 atm. from 0 to 40°C (in 5° intervals) and from 0 to 21‰ chlorinity. The densities at each temperature have been fitted to a modified Root (1933) equation, d = d0 + AV′ ClV + BV′ ClV32 and an equation based on the Debye-Hückel limiting law, d = d0 + AV ClV + BV ClV32 + CV ClV2 where AV′, BV′, AV, BV and CV are temperature-dependent constants (related to the ion-water and ion-ion interactions of the major components), d0 is the density of pure water and ClV is the volume chlorinity — ClV = Cl (‰) × density. The densities fit these equations to ±9 p.p.m. from 0 to 25°C and ±18 p.p.m. from 30 to 40°C. The densities for artificial seawater are in good agreement with our measurements of Copenhagen seawater and the results for natural seawater obtained from Knudsen's tables.The expansibilities of the artificial seawater mixtures have been calculated from the temperature dependence of the densities. The resulting expansibilities at each temperature were fitted to the equations α = α0 + AE′ ClV + BE′ ClV32 and α = α0 + AE ClV + BE ClV32 + CE ClV2 where AE′, BE′, AE, BE and CE are constants (related to the effect of temperature on the ion-water and ion-ion interactions of the major components) and α0 is the expansibility of pure water. The expansibilities fit these equations to ±1 p.p.m. and at 35‰ S agree within ±1 p.p.m. with the expansibilities obtained for natural seawater from Knudsen's tables.Theoretical density and expansibility constants have been determined from the apparent equivalent volumes and expansibilities of the major components of seawater by using the additivity principle. The average deviations of the calculated densities and expansibilities are, respectively, ±20 and ±3 p.p.m. over the entire temperature range.  相似文献   

14.
Examination of the consequences of the stoichiometric association constant K1a = 41.7 for MgSO4 in seawater as advocated by Johnson and Pytkowicz (1979) leads to a thermodynamic association constant Ka = 212.6, a value 32% greater than KA = 160 derived from conductance data. Use of Ka = 160 leads to a K1a in essential agreement with the value of 10.2 reported by Kester and Pytkowicz (1969).  相似文献   

15.
Laboratory investigations were conducted on the formation of NaF° ion-pairs at the ionic strength of seawater using specific ion electrodes. Sodium and fluoride ion electrodes produced results which are consistent with the ion-pairing model for these ionic interactions. The stoichiometric association constant for NaF°, K1NaF, was determined at 15, 25, and 35°C. It was assumed that K1NaF was a function of temperature, pressure, and ionic strength but not of solution composition. The value for K1NaF at 25°C and I = 0.7 m is 0.045 ± 0.006. K1NaF increased with decreasing temperature. This result was used to recompute values of K1MgF and K1CaF accounting for the presence of NaF° ion-pairs. The value for K1NaF indicates that 1.1% of the fluoride in seawater is ion-paired with sodium at 25°C and 35‰ salinity. This fraction increases to approximately 2% at the lower temperatures found in the deep ocean. The percentage of free fluoride in natural seawater was measured at 15, 25, and 35°C to verify the speciation calculated from equilibrium constants.  相似文献   

16.
The three dissociation constants of phosphoric acid have been determined in seawater media over the temperature and ionic strength ranges 5–30°C and 0.3-0.9 m. The results obtained fitted the equations (concentrations in mol per kg of solution):
pK1P=-75T+2.16-0.35I12 (rmsdeviation 0.034)
pK2P=737.6T++4.176-0.851I12 (rmsdeviation 0.015)
pK3P=2404T+1.31-0.87I12 (rmsdeviation 0.17)
The results are only in moderate agreement with those of Kester and Pytkowicz (1967). The reason for this lies partly in differences between the pH scales adopted and partly in the poor precision inherent in their method.  相似文献   

17.
The various assumptions implicit in the calculation of acid dissociation constants (based on ionic medium standard states) from potentiometric titrations using a cell with liquid junction (i.e. a pH measuring cell) have been examined. It was concluded that results can be obtained having an accuracy commensurate with the experimental precision. It has been shown that although the precise composition of the medium is a function of the hydrogen ion concentration (because of the protolytic nature of some of the ions in the media, e.g., sulphate and fluoride), the effect of such variations in the medium composition can be compensated for when defining the activity of hydrogen ion on an ionic medium standard state by defining the concentration of hydrogen ion as:
[H]SWS=h(1 + βHSO4ST + βHFET)
where βHSO4 and βHF are the relevant association constants and ST and FT are the total concentrations of sulphate and fluoride, respectively.This approach was used to obtain values for the ionic product of water (KW) in artificial seawater media at various temperatures and ionic strengths. These were fitted to give the equation (molal concentration units):
pKw= 3441.0T+2.256-0.709112 (rms deviation 0.01)
where I is the formal ionic strength of the artificial seawater medium and T is the absolute temperature. The values obtained are in reasonable agreement with those found by previous workers.  相似文献   

18.
Spectrophotometric measurements are reported for the first apparent dissociation constant of hydrogen sulfide in seawater over the temperature range 7.5–25°C and 2–35.8‰ salinity. These data are described by the expression pK1′ = 2.527 ? 0.169 Cl13 + 1359.96/T. The second apparent dissociation constant in potassium chloride solution was estimated potentiometrically using a sulfide specific ion electrode. A value of ~13.6 was found for pK2′ at a KCl concentration of 0.67 M. It is suggested that explicit reference to the sulfide ion, S2?, in describing equilibria in marine waters be dropped in favor of a formulation involving the bisulfide ion, HS?.  相似文献   

19.
Domestic and industrial sewage is discharged at a depth of 60 m near Whites Point on the San Pedro Shelf, Southern California borderland. A density-stratified thermocline, above the outfall at a depth of 20 to 30 m, is thought to prevent most effluent particles from reaching shallower depths and recreational facilities. In this investigation, measurement of the natural abundance of nitrogen isotopes (15N14N) is used to determine the level of sewage contribution to flocculent suspended material persisting at water depths of 7, 13 and 20 m. Organic nitrogen at 20 m depth was shown to be predominantly of sewage-origin and at 7 m, predominantly of marine origin. Organic nitrogen at 13 m depth and within 3 km of the outfall pipes is predominantly sewage in origin.Stable isotope composition of sulphur (32S34S) in the flocculent material indicates that the effluent particles contain metabolic sulphur, incorporated from dissolved seawater, as well as bacterially produced mineral sulphide.  相似文献   

20.
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