Stable isotope composition of dissolved sulfate and hydrogen sulfide in the Black Sea

The stable isotope ratio of sulfur (³⁴S/³²S) in dissolved sulfate and hydrogen sulfide was measured for 20 water samples from two deep hydrocasts from the south-central Black Sea. The isotope ratio of total reduced sulfur was also measured for surface sediment collected below each hydrocast. The range in the δ³⁴S measurements for sulfate was +18.20 to $\text{+20.17‰}$ and for hydrogen sulfide ?38.71 to $\text{?4.85‰}$. The distribution pattern for δ ³⁴S in both sulfate and sulfide appears to be the result of in situ sulfate reduction.     

A potentiometric study of ferric ion complexes in synthetic media and seawater

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 ${}^1\text{β}{}_1\text{and}{}^1\text{β}{}_2$ 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 ${}^1\text{β}{}_1\text{= 1.93 · 10}{}^{\mathrm{?3}}\text{and}{}^1\text{β}{}_2\text{= 8.6 · 10}{}^{\mathrm{?8}}$. 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.     

Solubility of hydrous ferric oxide and iron speciation in seawater

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 ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. 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 ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. 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.     

Copper(II) interaction with carbonate species based on malachite solubility in perchlorate medium at the ionic strength of seawater

Equilibrium constants for copper(II)-carbonate and -bicarbonate species have been determined at 25°C from consideration of malachite, Cu₂(OH)₂CO_3(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 (TA_i 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

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.     

Sulfur Isotopes in the Upper Part of the Black Sea Anoxic Zone

New data are reported on the sulfur isotope composition and concentration of sulfide and sulfate in the upper part of the Black Sea anoxic zone as a function of the potential water density. The observations were performed at a station with the coordinates 44.489° N and 37.869° E three times a week every two days. A local negative deficiency in sulfate concentration up to 1.7% related to the sulfate reduction processes was recorded. This anomaly in sulfate concentration was short-lived and did not affect the sulfur isotope composition. In the upper part of the anaerobic zone, the δ³⁴S(SO₄) value varied from 21.2 to 21.5‰, which could have occurred from mixing of water masses from the oxic zone (21.1‰) and the Bottom Convective Layer (23.0 ± 0.2‰). The sulfur isotope composition of sulfide ranged from ?40.8% at a depth of 250 m to ?39.4‰ at the upper boundary of the anoxic zone with a H₂S content of only 2.7 μM. Two models (mass balance and fractionation of sulfur isotopes using the Rayleigh equation) are considered to explain the differences in δ³⁴S(H₂S) values observed.     

A comparison of lignin and stable carbon isotope compositions in quaternary marine sediments

Organic matter in four Quaternary sediment cores from the Gulf of Mexico and one core from the Washington State coast have been analyzed for lignin and stable carbon isotope compositions. Holocene sequences of all five cores contain organic matter with high relative abundances of ¹³C ($\text{δ}{}^{13}\text{C = ?19.0 to ?22.5\% versus PDB}$) and low lignin concentrations, both of which are consistent with a marine origin. Distinctly lower ¹³C concentrations ($\text{δ}{}^{13}\text{C = ?24.0 to ?25.5\%}$) occur in underlying glacial-age sequences from four of the five cores, including the core from the Washington coast where such trends are previously unreported. Although the carbon isotopic compositions of these Pleistocene sediments are typical of predominantly land-derived organic matter, they contain only about 5% of the lignin found in modern sediments of similar $\text{δ}{}^{13}\text{C}$ from adjacent continental shelves. The lignin-poor organic matter in the glacial-age deposits appears to be either marine-derived or terrigenous material that likely was depleted in vascular plant debris at the time of deposition.     

Equilibrium and structural studies of silicon(iv) and aluminium(iii) in aqueous solution. V. Acidity constants of silicic acid and the ionic product of water in the medium range 0.05–2.0 M Na(CI) at 25°C

The apparent ionization constants for silicic acid, k₁ and k₂, and the ionic product of water, k_w, 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

$\text{log}\text{k}{}_{\mathrm{i}}\text{=}\text{log}\text{K}{}_{\mathrm{i}}\text{+a}{}_{\mathrm{i}}\text{I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(1+I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)+b}{}_{\mathrm{i}}\text{I}$

where K₁ is the ionization constant in pure water, α_i and b_i are parameters of which b_i has been adjusted to present data. The following results were obtained (α_i, b_i): pK₁ = 9.84, (1.022, ?0.11); pK₂ = 13.43, (2.044, ?0.20); and pK_w = 14.01 (1.022, ?0.22). k_i 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

$\text{Na}{}^{\mathrm{+}}\text{+}\text{SiO(OH)}{}^{\mathrm{?}}{}_3\text{?}\text{NaSiO(OH)}{}_3\text{;k}{}_{11}$

$\text{Na}{}^{\mathrm{+}}\text{+}\text{SiO}{}_2\text{(OH)}{}^2{}_2\text{?}\text{NaSiO}{}_2\text{(HO)}{}^{\mathrm{?}}{}_2\text{; k}{}_{21}$

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.     

南海神狐海域沉积物自生黄铁矿和石膏S同位素特征及对甲烷渗漏强度的示踪

The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane(AOM) coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor(cmbsf) in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values(δ~(34) S) of pyrite vary greatly(from –46.6‰ to –12.3‰ V-CDT) and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction(OSR) and is influenced by AOM with depth.The relative high abundance and δ~(34) S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone(SMTZ).The sulfur isotopic composition of gypsum(from–25‰ to –20.7‰) is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO_2,iron(Ⅲ) and oxygen driven by the SMTZ location shift to great depths.The δ~(34) S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.     

Apparent dissociation constants of hydrogen sulfide in chloride solutions

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 $\text{p}\text{K}{}_1\text{′ = 2.527 ? 0.169 Cl}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{+ 1359.96/T}$. 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, S^2?, in describing equilibria in marine waters be dropped in favor of a formulation involving the bisulfide ion, HS^?.     

The density and expansibility of artificial seawater solutions from 0 to 40°C and 0 to 21‰ chlorinity

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, $\text{d = d}{}^0\text{+}\text{A}{}_{\mathrm{V}}\text{′ Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{V}}\text{′ Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and an equation based on the Debye-Hückel limiting law, $\text{d = d}{}^0\text{+}\text{A}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{+ C}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}{}^2$ where A_V′, B_V′, A_V, B_V and C_V 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 Cl_V is the volume chlorinity — $\text{Cl}{}_{\mathrm{V}}\text{= Cl (‰) × density}$. 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 $\text{α = α}{}^0\text{+}\text{A}{}_{\mathrm{E}}\text{′ Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{E}}\text{′ Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{α = α}{}^0\text{+}\text{A}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{+ C}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}{}^2$ where A_E′, B_E′, A_E, B_E and C_E 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.     

Spatial variation in shallow sediment methane sources and cycling on the Alaskan Beaufort Sea Shelf/Slope

The MITAS (Methane in the Arctic Shelf/Slope) expedition was conducted during September, 2009 onboard the U.S. Coast Guard Cutter (USCGC) Polar Sea (WAGB-11), on the Alaskan Shelf/Slope of the Beaufort Sea. Expedition goals were to investigate spatial variations in methane source(s), vertical methane flux in shallow sediments (<10 mbsf), and methane contributions to shallow sediment carbon cycling. Three nearshore to offshore transects were conducted across the slope at locations approximately 200 km apart in water column depths from 20 to 2100 m. Shallow sediments were collected by piston cores and vibracores and samples were analyzed for sediment headspace methane (CH₄), porewater sulfate (SO₄²⁻), chloride (Cl⁻), and dissolved inorganic carbon (DIC) concentrations, and CH₄ and DIC stable carbon isotope ratios (δ¹³C). Downward SO₄²⁻ diffusion rates estimated from sediment porewater SO₄²⁻ profiles were between −15.4 and −154.8 mmol m⁻² a⁻¹ and imply a large spatial variation in vertical CH₄ flux between transects in the study region. Lowest inferred CH₄ fluxes were estimated along the easternmost transect. Higher inferred CH₄ flux rates were observed in the western transects. Sediment headspace ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ values ranged from −138 to −48‰, suggesting strong differences in shallow sediment CH₄ cycling within and among sample locations. Measured porewater DIC concentrations ranged from 2.53 mM to 79.39 mM with δ¹³C_DIC values ranging from −36.4‰ to 5.1‰. Higher down-core DIC concentrations were observed to occur with lower δ¹³C where an increase in ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ was measured, indicating locations with active anaerobic oxidation of methane. Shallow core CH₄ production was inferred at the two western most transects (i.e. Thetis Island and Halkett) through observations of low ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ coupled with elevated DIC concentrations. At the easternmost Hammerhead transect and offshore locations, ${\mathrm{\delta }}^{13}{\text{C}}_{{\text{CH}}_4}$ and DIC concentrations were not coupled suggesting less rapid methane cycling. Results from the MITAS expedition represent one of the most comprehensive studies of methane source(s) and vertical methane flux in shallow sediments of the U.S. Alaskan Beaufort Shelf to date and show geospatially variable sediment methane flux that is highly influenced by the local geophysical environment.     

Nitrate photolysis in seawater by sunlight

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 $\text{NO}{}_3{}^{\mathrm{?}}\text{+}\text{h}\text{υ =}\text{NO}{}_2{}^{\mathrm{?}}\text{+ O(}{}^3\text{P)}$ 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.     

Nitrogen losses from a Louisiana Gulf Coast salt marsh

Losses of ¹⁵N labelled nitrogen in a Spartina alterniflora salt marsh was measured over three growing seasons. Labelled $\text{NH}{}_4{}^{\mathrm{+}}\text{N}$ 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 $\text{NH}{}_4{}^{\mathrm{+}}\text{N}$ 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 $\text{NH}{}_4{}^{\mathrm{+}}\text{N}$ 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.     

Particulate aluminium fluxes in the eastern Atlantic

The atmospheric, primary down-column and sedimentary fluxes of particulate aluminium (Al_p) have been calculated for a number of regions in the Atlantic Ocean.The vertical down-column flux of Al_p from Atlantic surface waters exhibits a strong geographical variation, and its magnitude is influenced by supply mechanisms, which control the surface Al_p concentrations, and primary production, which affects the rate of down-column transport. Overall, the down-column transport of Al_p is greatest in the marginal regions of the Atlantic. In the eastern margins the highest surface water concentrations are found in the region lying between ～30°N and ～10°N, i.e. under the general path of the northeast trades. In this region there is excellent agreement between the dry (i.e. 1 cm^?1 s^?1 deposition velocity) atmospheric flux (～80 000 ng Al_p cm^?2 y^?1), the primary vertical down-column flux ($\text{? 70 000}\text{ng Al}{}_{\mathrm{p}}\text{cm}{}^{\mathrm{?2}}\text{y}{}^{\mathrm{?1}}$) and the sediment flux (～90 000 ng Al_p cm^?2 y^?1). In the regions to the north (i.e. ～40°N to ～30°N) and to the south (i.e. ～10°N to ～5°S) the primary down-column Al_p flux decreases to an average of ～19 000 μg cm^?2 y^?1, which makes a direct maximum contribution of ～20% of the sediment Al_p requirement. In the open-ocean South Atlantic the primary down-column flux of Al_p is ～3300 μg cm^?2 y^?1, this is similar to the dry (i.e. 1 cm^?1 s^?1 deposition velocity) atmospheric flux, and contributes ～20% of the Al_p required by the underlying deep-sea sediment.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3− and SiO2(OH)22−. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH^? was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 ? B ? 0.008 M and 2.5 ? -log[H⁺] ? 11.7, respectively. Within these ranges the formation of SiO(OH)₃^? and SiO₂(OH)₂^2? with formation constants log β_?11(Si(OH)₄ ? SiO(OH)₃^? + H⁺) = ?9.472 ±0.002 and log β_?21(Si(OH)₄ ? SiO₂(OH)₂^2? + 2H⁺) = ?22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with $\text{-}\text{log[H}{}^{\mathrm{+}}\text{] ? 10.7}$ their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

The significance of oxygen as oxides and hydroxides in controlling the abundance and residence times of elements in seawater

A model is presented which signifies the role of oxygen (as oxides and hydroxides) in controlling the composition of seawater. Using the regression equations

$\text{log}\text{K}{}_{\mathrm{SW}}\text{=-0.77+0.03ΔO}{}^{\mathrm{2-}}\text{M}\text{and}\text{[M]}{}_{\mathrm{SW}}\text{=K}{}_{\mathrm{SW}}\text{[M]}{}_{\mathrm{crust}}$

$\text{log}\text{t}\text{=4.73+0.04ΔO}{}^{\mathrm{2-}}\text{M}$

respective concentration and residence times for the unknown elements can be estimated. Geometric and statistical indices of Legget and Williams (1981) are used to evaluate the accuracy of the model. This reveals from the known values of ΔO^2?M that the present model estimates log $\text{t}{}_{\mathrm{y}}$ values within a factor of 1.77. The predicted oceanic residence times for Am, Ir, Ra and Rh are 3.6 × 10², 3.7 × 10², 2.2 × 10⁵ and 6.4 × 10² years, respectively.     

Postdepositional injections of uranium-rich solutions into East Pacific Rise sediments

An 8.5 m long apparently undisturbed core from a hilltop on the crest of the East Pacific Rise has uranium and thorium isotope distributions that are very unusual. The core is very poor in ²³²Th, and very rich in U, particularly at the 500-cm level, where a value of about 150 ppm is reached. At the same depth the ²³⁰Th_xs reaches very large negative values. These facts could be accounted for if one assumes that solutions rich in U and poor in Th had been postdepositionally injected into the sediments about 90,000–110,000 years ago. The top of the sediment received much of its U from seawater, judging from the ${}^{234}\text{U}{}^{238}\text{U}$ ratio. Possibly carbonate rich solutions were the carriers of the injected uranium.     

Some new results on statistical properties of wind waves

For wind waves modelled by a stationary Gaussian process ζ(t) (ζ = height above m.w.l. of one point of the free surface) it is shown that, in a time interval including an instant t_m where a maximum ζ_m occurs, the ratio between ζ(t) and ζ_m tends with probability approaching one, to the ratio Ψ(t ? t_m)/Ψ(O), as $\text{ζ}{}_{\mathrm{m}}\text{/Ψ}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(}\text{O}\text{)}$ tends to infinity, Ψ(t) being the autocovariance of the process.Starting from this result, it is possible to find analytically the characteristic periods of the highest waves in a sea with a given energy spectrum. These periods, calculated according to period definitions of three methods of wave record analysis, are found to be in remarkably good agreement with data from Bretschneider¹ and Svasek.²