Lead in corals: reconstruction of historical industrial fluxes to the surface ocean

Twentieth century environmental lead chronologies for the western North Atlantic, Pacific, and Indian Oceans have been reconstructed from annually-banded scleractinian corals. Measurements of lattice-bound Pb in sequential coral bands reveal temporal changes in surface water Pb concentrations and Pb isotopic distributions. Perturbations are observable in all specimens studied, attesting to global augmentation of environmental Pb by industrialization.In the western North Atlantic, Pb perturbations have occurred in direct response to the American industrial revolution and the subsequent introduction and phasing-out of alkyl Pb additives in gasoline. Surface ocean conditions near Bermuda may be reliably reconstructed from the coral data via a lead distribution coefficient of 2.3 for the species,Diploria strigosa. Based on²¹⁰Pb measurements, a similar distribution coefficient may be characteristic of corals in general. Surface Pb concentrations in the pre-industrial Sargasso Sea were about 15–20 pM. Concentrations rose to near 90 pM by 1923 as a result of metals manufacture and fossil fuel combustion. Beginning in the late 1940's, increased utilization of leaded gasoline eventually led to a peak concentration of 240 pM in 1971, representing an approximate 15-fold increase over background. Surface ocean concentrations are presently declining rapidly (128 pM in 1984) as a result of curtailed alkyl Pb usage. Lead isotopic shifts parallel the concentration record indicating that characteristic industrial and alkyl Pb source signatures have not changed appreciably in time. Industrial releases recorded in the Florida Keys reflect a weaker source and evidence of recirculated Pb (5–6 years old) from the North Atlantic subtropical gyre. An inferred background concentration of 38 pM suggests influence of shelf and/or resuspended inputs of Pb to these coastal waters.In remote areas of the South Pacific and Indian Oceans, industrial signals are fainter and the corals studied much younger than their Atlantic counterparts. Contemporary Pb concentrations implied by coral measurements (assumingK_D = 2.3) are 40–50 pM for surface waters near Tutuila and Galapagos in the South Pacific, and 25–29 pM near Mauritius in the Indian Ocean. A single coral band from Fiji (1920 ± 5yr) implies a pre-industrial surface water concentration of 16–19 pM Pb for the South Pacific. In view of reported surface water measurements and the North Atlantic coral data, the Pacific coral extrapolations may be slightly high. This could be a result of small variations inK_D among different coral genera, or incorporation of diagenetic Pb by corals sampled in coastal environments.     

Genesis of chlorine and sulphur in fumarolic emissions at Vulcano Island (Italy): assessment of pH and redox conditions in the hydrothermal system

Chlorine- and sulphur-bearing compounds in fumarole discharges of the La Fossa crater at Vulcano Island (Italy) can be modelled by a mixing process between magmatic gases and vapour from a boiling hydrothermal system. This allows estimating the compounds in both endmembers. Magma degassing cannot explain the time variation of sulphur and HCl concentrations in the deep endmember, which are more probably linked to reactions of solid phases at depth, before mixing with the hydrothermal vapours. Based on the P–T conditions and speciation of the boiling hydrothermal system below La Fossa, the HCl and S_tot contents in the hydrothermal vapours were used to compute the redox conditions and pH of the aqueous solution. The results suggest that the haematite–magnetite buffer controls the hydrothermal fO₂ values, while the pH has increased since the end of the 1970s. The main processes affecting pH values may be linked to Na–Ca exchanges between evolved seawater, feeding the boiling hydrothermal system, and local rocks. While Na is removed from water, calcium enters the solution, undergoes hydrolysis and produces HCl, lowering the pH of the water. The increasing water–rock ratio within the hydrothermal system lowers the Ca availability, so the aqueous solution becomes less acidic. Seawater flowing towards the boiling hydrothermal brine dissolves a large quantity of pyrite along its path. In the boiling hydrothermal system, dissolved sulphur precipitates as pyrite and anhydrite, and becomes partitioned in vapour phase as H₂S and SO₂. These results are in agreement with the paragenesis of hydrothermal alteration minerals recovered in drilled wells at Vulcano and are also in agreement with the isotopic composition of sulphur emitted by the crater fumaroles.     

Hydrogeochemistry of the Simav geothermal field, western Anatolia, Turkey

Thermal waters hosted by Menderes metamorphic rocks emerge along fault lineaments in the Simav geothermal area. Thermal springs and drilled wells are located in the Eynal, Çitgöl and Na a locations, which are part of the Simav geothermal field. Studies were carried out to obtain the main chemical and physical characteristics of thermal waters. These waters are used for heating of residences and greenhouses and for balneological purposes. Bottom temperatures of the drilled wells reach 163°C with total dissolved solids around 2225 mg/kg. Surface temperatures of thermal springs vary between 51°C and 90°C. All the thermal waters belong to Na–HCO₃–SO₄ facies. The cold groundwaters are Ca–Mg–HCO₃ type. Dissolution of host rock and ion-exchange reactions in the reservoir of the geothermal system shift the Ca–Mg–HCO₃ type cold groundwaters to the Na–HCO₃–SO₄ type thermal waters. Thermal waters are oversaturated at discharge temperatures for aragonite, calcite, quartz, chalcedony, magnesite and dolomite minerals giving rise to a carbonate-rich scale. Gypsum and anhydrite minerals are undersaturated with all of the thermal waters. Boiling during ascent of the thermal fluids produces steam and liquid waters resulting in an increase of the concentrations of the constituents in discharge waters. Steam fraction, y, of the thermal waters of which temperatures are above 100°C is between 0.075 and 0.119. Reservoir pH is much lower than pH measured in the liquid phase separated at atmospheric conditions, since the latter experienced heavy loss of acid gases, mainly CO₂. Assessment of the various empirical chemical geothermometers and geochemical modelling suggest that reservoir temperatures vary between 175°C and 200°C.     

On the characterization of aerosols using the Ångström exponent in the Athens area

Ground-based spectroradiometric measurements were taken in the atmosphere of Athens during May 1995 in order to investigate various atmospheric conditions. This study focuses on the Ångström exponent α, which is the slope of the logarithm of the aerosol optical depth (AOD) versus the logarithm of the wavelength, lnλ, and is commonly used to characterize the wavelength dependence of AOD and to provide some basic information on the aerosol size distribution. Using the Volz method, Ångström exponent values, α, were derived in five narrow spectral bands, 340–380, 380–440, 440–500, 500–670 and 670–870 nm. Also using both Volz and least-squares fit methods α values were derived for the whole spectrum 340-870 nm.The results show that α depends strongly on the wavelength interval used due to the curvature of the lnAOD versus lnλ line. Using the spectral dependence of the Ångström exponent and the relationship between α computed in different spectral bands with AOD, an attempt to investigate on the aerosol types is made. The results obtained are rather contradictory and the determination of a dominant aerosol type in the Athens area is not clear. Nevertheless, in the most cases the anthropogenic aerosols seem to be the dominant type with rather significant contributions of coarse-mode particles due to particle growing or due to mixing processes with other aerosol types.     

Neodymium isotopic study of Baffin Bay water: sources of REE from very old terranes

Water samples were collected from Baffin Bay and surrounding areas in order to evaluate this region as a potential source of Nd from old continental material to Atlantic water. The isotopic data ranged from ε_Nd(0) = −9.0 to −26 with most of the data around ε_Nd(0) = −20 compared with values of North Atlantic Deep Water (NADW) with ε_Nd(0) = −13.5. The concentration of Nd in Baffin Bay waters was as high as 6 × 10⁻¹² g/g compared with 2.5 × 10⁻¹² g/g for NADW. The combination of low ε_Nd and high Nd concentration indicates that Baffin Bay may be a significant source of Nd from very old crustal material. A simple box model was used to evaluate the contribution to the Nd budget of NADW and it was concluded that a substantial fraction of the Nd from ancient crustal sources that is required to maintain the isotopic composition of NADW could be supplied by Baffin Bay outflow.     

Subsidence history of the Bahama Escarpment and the nature of the crust underlying the Bahamas

Subsidence of the Bahama Escarpment, determined from deep-diving submersible and dredge samples, is used to constrain the nature of crust underlying the Bahamas. Horizontal disposition of the Hauterivian/Barremian (125 Ma) age boundary along the Bahama Escarpment is inconsistent with an underlying oceanic crust (either normal or thickened) here, and suggests that thinned continental crust underlies the Bahamas. Subsidence curves are then fit based on a stretched lithosphere model to a stratigraphic section (2000–4000 m) off Cat Island. This analysis indicates crustal thinning by a factor (β) of 2.0–2.5, resulting in present crustal thicknesses of 10–12 km. We propose that rifting beneath the Bahamas occurred from middle (175–180 Ma) to late (160 Ma) Jurassic time. The pre-extension Bahamas fit between North and South America and Africa in Early Jurassic time, eliminating overlap of the present Bahamas onto Africa in reconstructions of the North Atlantic.     

On the validity of Boltzmann's distribution law for the charges of aerosol particles in electrical equilibrium

Summary The validity ofBoltzmann's energy distribution law as applied to the charge distribution of monodisperse aerosols, i.e. aerosols which contain particles of one size only, was studied with improved equipment now available.Since monodisperse aerosols with particle size of about 10^–6 cm cannot yet be produced and because aerosols in general contain particles of different sizes, polydisperse aerosols stored in a large gasometer were used for the investigation. The composition and the average radius of these aerosols heterogeneous in particle size were determined by the Exhaustion Method employing a diffusion battery without end-pieces or connecting tubing.The experimental curve found for the ratio of the uncharged (N ₀) to the charged (N) nuclei versus radius (r) of the particles deviates for all investigated radii between 0.5 and 4.0·10^–6 cm from the theoretical curve of a monodisperse aerosol computed according to the Boltzmann law. For radii smaller than about 1.4·10^–6 cmN ₀/N is smaller than that given by Boltzmann's law, for radii greater than 1.4·10^–6 cm larger, or, in other words, forr<1.4·10^–6 cm the number of charged nuclei found in the aerosols investigated is greater than that predicted byBoltzmann's law, and forr>1.4·10^–6 cm smaller.The deviations from the theoretical curve forr>1.4·10^–6 cm can be fully explained by the polydispersity of the aerosols used; forr<1.4·10^–6 cm the deviations are too big to be attributed to polydispersity. From this it must be concluded thatBoltzmann's distribution law is not valid for the charge distribution of homogenous aerosols containing nuclei with radii smaller than about 1.4·10^–6 cm.The equivalent radius as deduced from a substitute monodisperse aerosol in charge equilibrium for which theBoltzmann law is assumed valid, deviates in the range of 1.0·10^–6<r<3.0·10^–6 cm (or 90%>100N ₀/Z>55%) on the average by up to 35% from the actual mean radius of the investigated polydisperse aerosols computed from the radii of their singly sized components.

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Zusammenfassung Die Gültigkeit desBoltzmannschen Gesetzes der Energieverteilung für die Ladungsverteilung von monodispersen Aerosolen, das heisst Aerosolen, welche Teilchen von nur einer Grösse enthalten, wurde mit den jetzt zur Verfügung stehenden verbesserten Mitteln studiert.Da monodisperse Aerosole mit Teilchengrössen von ungefähr 10^–6 cm noch nicht erzeugt werden können und Aerosole im allgemeinen Teilchen von verschiedenen Grössen enthalten, wurden für die jetzige Untersuchung polydisperse Aerosole, welche in einem grossen Gasometer gespeichert waren, benützt. Die Zusammensetzung und der mittlere Radius dieser Aerosole mit heterogener Teilchengrösse wurden nach der Exhaustions-Methode unter Benützung einer Diffusionsbatterie ohne Endstücke oder Verbindungsröhren bestimmt.Die experimentell gefundene Kurve, welche das Verhältnis der ungeladenen (N ₀) und geladenen (N) Kerne als Funktion des Radius (r) darstellt, weicht für alle untersuchten Radien zwischen 0.5 und 4.0·10^–6 cm von der theoretischen Kurve eines monodispersen Aerosols, wie sie nachBoltzmann's Gesetz berechnet wird, ab. Für Radien kleiner als ungefähr 1.4·10^–6 cm ist das VerhältnisN ₀/N kleiner als es durchBoltzmann's Gesetz gegeben wird, für Radien grössen als 1.4·10^–6 cm grösser oder, mit anderen Worten, fürr<1.4·10^–6 cm ist die Zahl der geladenen Teilchen, die in den untersuchten Aerosolen gefunden wurde, grösser als die vonBoltzmann's Gesetz vorausgesagte, und fürr>1.4·10^–6 cm kleiner.Die Abweichungen von der theoretischen Kurve fürr>1.4·10^–6cm können vollkommen durch die Polydispersität der benützten Aerosole erklärt werden; fürr<1.4·10^–6 cm sind die Abweichungen zu gross, als dass sie der Polydispersität zugeschrieben werden könnten. Daraus muss geschlossen werden, dassBoltzmann's Verteilungsgesetz für die Ladungsverteilung eines homogenen Aerosols, welches Kerne mit Radien kleiner als ungefähr 1.4·10^–6 cm enthält, nicht gültig ist.Der äquivalente Radius, wie er von einem im Ladungsgleichgewicht befindlichen, monodispersen Ersatz-Aerosol, für welchesBoltzmann's Gesetz als gültig angenommen wird, abgeleitet werden kann, weicht im Bereich von 1.0·10^–6<r<3.0·10^–6 cm (oder 90%>N ₀/Z>55%) durchschnittlich bis zu 35% vom tatsächlichen mittleren Radius des untersuchten polydispersen Aerosols ab.

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The research reported in this article has been supported in part by the Geophysics Research Directorate of the Air Force Cambridge Research Laboratories, through the European Office of the Air Force Research Division, United States Air Force under Contract AF 61(052)-26, by the United States Department of Army, through its European Research Office, Contract DA-91-591-EUC-1282 & 1657 and by the Instrumentation Engineering Physics & Analysis Laboratory of the General Electric Co., Schenectady, New York under Retainer Agreement.     

Tephrochronology of the Kamchatka–Kurile and Aleutian arcs: evidence for volcanic episodicity

Volcanic ash layers in North Pacific deep-sea sediment provide a record of episodic explosive volcanism in the Kamchatka–Kurile and Aleutian arcs over the past five million years. We counted 450 ash layers, determined layer thickness and cumulative ash thickness to quantify the flux of ash with time. We use this record to investigate the eruptive history of these arcs, test the reliability of the marine ash record, and inquire into the regional episodicity of North Pacific explosive volcanic history. Episodes of explosive volcanism occurred at approximately 0.2–0.5, 0.7–0.9, 1.5–1.7, and 2.5–2.65 Ma in the Kamchatka arc and 0.15–0.4, 1.7–1.8, 2.55–2.65, and at 3.0–3.1 Ma in the eastern Aleutian arc. These generally coeval eruptive episodes suggest that the pulses in explosive volcanism in the North Pacific enumerated here and recognized by others are regionally episodic over a wide portion of the Pacific rim and not just a response to local volcanogenic processes.     

Correlations between13C and ΣCO2 in surface waters and atmospheric CO2

¹³C and ΣCO₂ data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ¹³C of the ΣCO₂ in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO₂ per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO₂, while the remainder is attributed to dissolution of calcium carbonate.The δ¹³C of the dissolved CO₂ in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO₂ at a mean temperature of 16°C. The δ¹³C and ΣCO₂ values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water.     

Downstream composition changes of acidic volcanic waters discharged into the Banyupahit stream, Ijen caldera, Indonesia

The crater lake of Kawah Ijen volcano contains extremely low pH (<0.4) waters with high SO₄ (70000 mg/kg), Cl (21000 mg/kg), F (1500 mg/kg), Al (5000 mg/kg), Fe (2000 mg/kg) and trace metal (Cu 0.5, Zn 4, Pb 3 mg/kg) contents. These brines seep outward through the western crater rim and reappear on the other side as streamlets, which form the headwaters of the Banyupahit stream. The Banyupahit first mixes with fresh rivers and thermal springs in the Ijen caldera and then irrigates a coastal agricultural plain which is 30 km from the summit crater.We discuss the downstream composition changes affecting the Banyupahit waters by using stable isotope, chemical and mineralogical data collected from sites along the stream length. The saturation of the stream waters with respect to minerals was evaluated with SOLVEQ and WATEQ4F and compared with the geochemical observations. An aluminous mineralogy (alunogen, pickeringite, tamarugite and kalinite) develops in the upper part of the Banyupahit due to concentration of the headwaters by evaporation. Downstream attenuation of dissolved element concentrations results principally from dilution and from mineral precipitation. The stream pH changes from 0 at the source to >4 close to the mouth. The δD and δ¹⁸O values and the relative SO₄–Cl–F contents of the Banyupahit waters indicate that the tributaries are mostly meteoric. Dissolved SO₄ in the acidic stream come only from the crater lake seepages and are not involved later in microbially mediated reactions, as shown by their δ³⁴S and δ¹⁸O values. Re-equilibration of the stream SO₄ oxygen-isotope composition with H₂O from tributaries does not occur.Calcium, SiO₂, Al, Fe, K and SO₄ behave non-conservatively in the stream waters. Gypsum, silica (amorphous or poorly ordered), a basic aluminum hydroxysulfate (basaluminite?), K-jarosite and amorphous ferric hydroxide may exert a solubility control on these elements along the entire stream length, or in certain stream sections, consistent with the thermochemical model results. Downstream concentration trends and mineral saturation levels suggest that precipitation of Sr-, Pb-rich barite and celestite consume Ba, Sr and Pb, whereas dissolved Cu, Pb and Zn may adsorb onto solid particles, especially after the junctions of the acidic stream with non-acidic rivers. We calculated that significant fluxes of SO₄, F, Cl, Al, SiO₂, Ti, Mn and Cu may reach the irrigation system, possibly causing serious environmental impacts such as soil acidification and induration.     

Tracing effects of decalcification on solute sources in a shallow groundwater aquifer, NW Germany

δ⁸⁷Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO₃-type groundwater prevails. δ⁸⁷Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ⁸⁷Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ⁸⁷Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ⁸⁷Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr²⁺. In contrast, more than 95% of Sr²⁺ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO₃-type groundwater. The surprisingly high content of carbonate-derived Sr²⁺ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.     

Rare earth elements in the pore waters of reducing nearshore sediments

The REE are mobile during early diagenesis in reducing nearshore sediments of Buzzards Bay leading to greatly enhanced concentrations in pore waters, e.g. 815 pmol kg⁻¹ Nd and 1910 pmol kg⁻¹ Ce within 30 cm of the sediment-seawater interface, about 10–50 times local seawater values. Two principal diagenetic reactions have been identified. Preferential Ce enrichment (positive Ce anomalies) and preferential heavy REE enrichment (light REE removal) in the pore waters is associated with redox cycling of Fe and Mn within the upper few centimeters of the sediment. Release of REE, without fractionation, from sediments and addition to pore waters occurs deeper within the sediment column. The impact on the bulk sediment chemistry is undetectable but the porewater gradients imply that there are significant dissolved REE fluxes, both internal to the sediment system and across the sediment-seawater interface.     

Oxygen isotope fractionation in dissolved oxygen in the deep sea

¹⁸O variations in dissolved oxygen have been measured at five stations from the eastern equatorial Pacific, at the GEOSECS-I and -II intercalibration stations in the North Pacific and North Atlantic, and along an Antarctic-South Pacific section from MONSOON expedition. Relative to atmospheric oxygen, dissolved oxygen in the ocean is enriched in¹⁸O up to a maximum of 14‰, the extreme enrichments occurring in the oxygen-minimum region of the eastern Pacific. The vertical diffusion-advection model has been used to determine the isotopic fractionation of deep-water in-situ oxygen consumption ascribed to bacterial metabolism. The single-stage enrichment, ε, in Pacific Deep Water below 1 km is 10‰ (α = 0.99,¹⁶O consumed preferentially). The model calculations show that the isotopic data cannot be fit without the introduction of a fractionation factor, just as the dissolved oxygen data cannot be fit without an in-situ consumption parameter. The consistency of the positive sign for ε and the negative source term for O₂, observed in all deep Pacific profiles analyzed to date, provide strong evidence that vertical transport and in-situ consumption terms dominate the horizontal tracer flux terms, and indicate the presence of a significant “deep metabolism” in abyssal ocean waters.     

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

Regional energetics over the North Pacific,South China Sea and the Indonesian seas during winter

The energy equation was applied to four limited regions to investigate the basic mechanisms through which area-averaged eddy kinetic energy is maintained during the northern winter. The regions selected for this study are as follows: extratropical North Pacific (24.2°N–44.6°N, 130°E–150°W), tropical eastern North Pacific (0°–19.6°N, 170°W–110°W), South China Sea and. Bay of Bengal (0°–19.6°N, 80°E–140°E), and Timor Sea and eastern Indian Ocean (0°–19.6°S, 80°E–140°E). The zonally averaged upper flows over the first region were found to be barotropically stable. In contrast, they were barotropically unstable over the second region; namely, eddy motions over the tropical eastern North Pacific are maintained by receiving energy from zonal flows via barotropic interaction. The third and fourth regions are characterized by the importance of the conversion process between eddy available potential and eddy kinetic energy.Contribution No. 77-5, Department of Meteorology, University of Hawaii, USA.     

Combined amino acids in Pacific Ocean waters

Filtration and extraction indicate that the bulk of the combined amino acids in Pacific Ocean waters are a constituent of a dissolved component, and that they cannot be efficiently extracted from seawater by the macroreticular XAD-2 resin. In deep waters of the Pacific Ocean, alanine accounts for～60–70% of the combined amino acids, while in surface waters alanine makes up only～30% of the combined amino acid fraction. Serine is present in the combined fraction in surface waters, but is essentially absent in deep waters. These differences in the serine and alanine abundances between surface and deep waters are possibly the result of the dehydration of serine, which produces racemic alanine. Threonine can also undergo dehydration producing racemicα-amino-n-butyric acid, a non-biological amino acid which has been detected in deep waters of the Pacific Ocean. Estimates of the rate of serine and threonine dehydration in the oceans suggest that these reactions may have half-lives at 0°C of less than 100 years. As a consequence of dehydration, the dissolved organic material in which this diagenetic reaction has occurred may have reduced biological degradability.     

Leakage of Active Crater lake brine through the north flank at Rincón de la Vieja volcano, northwest Costa Rica, and implications for crater collapse

The Active Crater at Rincón de la Vieja volcano, Costa Rica, reaches an elevation of 1750 m and contains a warm, hyper-acidic crater lake that probably formed soon after the eruption of the Rio Blanco tephra deposit approximately 3500 years before present. The Active Crater is buttressed by volcanic ridges and older craters on all sides except the north, which dips steeply toward the Caribbean coastal plains. Acidic, above-ambient-temperature streams are found along the Active Crater's north flank at elevations between 800 and 1000 m. A geochemical survey of thermal and non-thermal waters at Rincón de la Vieja was done in 1989 to determine whether hyper-acidic fluids are leaking from the Active Crater through the north flank, affecting the composition of north-flank streams.Results of the water-chemistry survey reveal that three distinct thermal waters are found on the flanks of Rincón de la Vieja volcano: acid chloride–sulfate (ACS), acid sulfate (AS), and neutral chloride (NC) waters. The most extreme ACS water was collected from the crater lake that fills the Active Crater. Chemical analyses of the lake water reveal a hyper-acidic (pH0) chloride–sulfate brine with elevated concentrations of calcium, magnesium, aluminum, iron, manganese, copper, zinc, fluorine, and boron. The composition of the brine reflects the combined effects of magmatic degassing from a shallow magma body beneath the Active Crater, dissolution of andesitic volcanic rock, and evaporative concentration of dissolved constituents at above-ambient temperatures. Similar cation and anion enrichments are found in the above-ambient-temperature streams draining the north flank of the Active Crater. The pH of north-flank thermal waters range from 3.6 to 4.1 and chloride:sulfate ratios (1.2–1.4) that are a factor of two greater than that of the lake brine (0.60). The waters have an ACS composition that is quite different from the AS and NC thermal waters that occur along the southern flank of Rincón de la Vieja.The distribution of thermal water types at Rincón de la Vieja strongly indicates that formation of the north-flank ACS waters is not due to mixing of shallow, steam-heated AS water with deep-seated NC water. More likely, hyper-acidic brines formed in the Active Crater area are migrating through permeable zones in the volcanic strata that make up the Active Crater's north flank. Dissolution and shallow subsurface alteration of north-flank volcanoclastic material by interaction with acidic lake brine, particularly in the more permeable tephra units, could weaken the already oversteepened north flank of the Active Crater. Sector collapse of the Active Crater, with or without a volcanic eruption, represents a potential threat to human lives, property, and ecosystems at Rincón de la Vieja volcano.     

Submarine groundwater discharge into the coast revealed by water chemistry of man-made undersea liquefied petroleum gas cavern

The occurrence of submarine groundwater discharge (SGD) as well as its supply of many nutrients and metals to coastal seawaters is now generally known. However, previous studies have focused on the chemical and radiological analysis of groundwater, surface seawater, shallow marine sediments and their pore waters, as well as the measurement of upward flow through the marine sediments, as end members of the discharge process. In this study, chemical and isotopic analysis results of marine subsurface waters are reported. These were obtained from deep boreholes of an undersea liquefied petroleum gas (LPG) storage cavern, located about 8 km off the western coast of Korea. The cavern is about 130–150 m below the sea bottom, which is covered by a 4.8–19.5 m silty clay stratum. An isotopic composition (δ²H and δ¹⁸O) of the marine subsurface waters falls on a mixing line between terrestrial groundwater and seawater. Vertical EC profiling at the cavern boreholes revealed the existence of a fresh water zone. An increase in the contents of ferrous iron and manganese and a decrease in levels of nitrate, bicarbonate and cavern seepage were recorded in August 2006, indicating a decreased submarine groundwater flux originating from land, mainly caused by an elevated cavern gas pressure. It is suggested in this study that the main source of fresh waters in the man-made undersea cavern is the submarine groundwater discharge mainly originating from the land.     

Hydrogeochemical outline of thermal waters and geothermometry applications in Anatolia (Turkey)

The chemical compositions of a total of 120 thermal water samples from four different tectonically distinct regions (Central, North, East and West Anatolia) of Turkey are presented and assessed in terms of geothermal energy potential of each region through the use of chemical geothermometers. Na–Ca–HCO₃ type waters are the dominant water types in all the regions except that Na–Cl type waters are typical for the coastal areas of West Anatolia and for a few inland areas of West and Central Anatolia where deep water circulation exists. The discharge temperature of the springs ranges up to 100°C, and the bottom-hole temperatures in drilled wells up to 232°C. Geothermometry applications yield reservoir temperatures of about 125°C for Central Anatolia, 110°C for North Anatolia, 136°C for East Anatolia and 251°C for West Anatolia, the latter agreeing with some of the bottom hole temperatures measured in drilled wells. The results reveal that the highest geothermal energy potential in Turkey is associated with the West Anatolian extensional tectonics which provides a regional, deep-seated heat source and a widespread graben system allowing deep circulation of waters. The North Anatolian region, bounded to the south by the dextral North Anatolian Fault along which most of the geothermal sites are located, has the lowest energy potential, probably due to the restriction of the heat source to local magmatic activities confined to pull-apart basins. The East Anatolian region (undergoing contemporary compression) and the Central Anatolian region (where the compressional regime in the east is converted to the extensional regime in the west) have moderate energy potential. Although the recently active volcanoes suggest the presence, at depth, of still cooling magma chambers that are potential heat sources, the lack of well-developed fault systems is probably responsible for the comparatively low energy potential of these regions. Almost all the thermal waters of Turkey are saturated with respect to calcite and, hence, have a significant calcite scaling potential which is particularly high for West Anatolian waters.     

Charge distribution on the atmospheric aerosol over the North Atlantic and the Indian Ocean

The distribution of electric charge on the marine aerosol was determined near the sea surface of the Indian Ocean and the North Atlantic during the final stage of the Snellius II-expedition. Mean values for small ion concentrationsn ⁺=455 cm^–3 andn ^–=340 cm^–3 were found over the Atlantic, whilen ⁺=310 andn ^–=250 cm^–3 were the mean values over the Indian Ocean. The ration ⁺/n^– increased from 1.2 to 2.0 with decreasing wind velocity. At wind velocities below 5 m/s 75% of the net space charge near the ocean surface was found to be carried by small ions.