Heterogeneous loss of OH on NaCl and NH4 NO 3 at tropospheric temperatures

The uptake coefficients () for OH radicals on some dry salts of tropospheric interest (NaCl and NH₄NO₃) have been investigated as a function of temperature using the flow tube technique combined with an EPR spectrometer as a detection method. The temperature dependence of -values measured over the temperature range 245–340 K can be expressed in Arrhenius form: ^OH_NaCl=(1.2±0.7)×10⁻⁵exp[(1750±200)/T] and ^OH_NH4NO3=(1.4±0.5)×10⁻⁴exp[(1000±100)/T]. These Arrhenius expressions lead to very similar -values (\approx4×10⁻³) for both salts studied at 300 K. It is shown that the heterogeneous OH sinks on solids aerosol play a very minor role in tropospheric chemistry in comparison with the homogeneous sinks.     

Dissolved carbon dioxide in basaltic glasses: concentrations and speciation

Carbon dioxide dissolved in both synthetic Ca±Mg-bearing silicate glasses and natural basaltic glasses has been characterized using infrared spectroscopy. CO₂ is inferred to be dissolved in these glasses as distorted Ca or Mg carbonate ionic complexes that result in unique infrared absorption bands at 1515 cm⁻¹ and 1435 cm⁻¹. This speciation contrasts with the case of CO₂-bearing sodium aluminosilicate glasses, which contain both dissolved molecular CO₂ and dissolved Na-carbonate ionic-complexes. The difference in speciation in Ca±Mg-bearing melts may result in part from a higher activity of oxygens that react with CO₂ molecules to produce carbonate.Dissolved CO₂ contents of natural basaltic glasses can be determined from the intensities of the carbonate absorption bands at 1515 cm⁻¹ and 1435 cm⁻¹. The uncertainty of the method is estimated to be ± 15% of the amount present. The infrared technique is a powerful tool for the measurement of dissolved CO₂ contents in natural basaltic glasses since it is non-destructive, can be aimed at regions of glass a few tens of microns in size, and can discriminate between dissolved carbonate and carbon present as carbonate alteration, contained in fluid inclusions, or adsorbed on the glass.A set of submarine basaltic glasses dredged from a variety of locations contain 0–400 ppm dissolved CO₂, measured using the infrared technique. These concentrations are lower than most previous reports for similar basaltic glasses. No general relationship is observed between dissolved CO₂ content and depth of magmatic eruption, although some correlation might be present in restricted geographic locales.     

Stable isotope compositions and water contents of boninite series volcanic rocks from Chichi-jima, Bonin Islands, Japan

Measurements of stable isotope compositions and water contents of boninite series volcanic rocks from the island of Chichi-jima, Bonin Islands, Japan, confirm that a large amount (1.6–2.4 wt.%) of primary water was present in these unusual magmas. An enrichment of 0.6‰ in¹⁸O during differentiation is explained by crystallization of¹⁸O-depleted mafic phases. Silicic glasses have elevated δ¹⁸O values and relatively low δD values indicating that they were modified by low-temperature alteration and hydration processes. Mafic glasses, on the other hand, have for the most part retained their primary isotopic signatures since Eocene time. Primary δD values of −53 for boninite glasses are higher than those of MORB and suggest that the water was derived from subducted oceanic lithosphere.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

Structure of volcanic glasses from the NMR-EPR perspective: a preliminary application to the Neapolitan Yellow Tuff

Glass samples from alkali-trachytic pumice of the Lower Member (LM, level LM1) and Upper Member (UM) of the Neapolitan Yellow Tuff at Campi Flegrei Caldera were studied by nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopy. The EPR data show that the relative occupancy of the different iron sites varies in samples from the Lower Member LM1 and Upper Member of the eruptive sequence. The LM1 glasses are characterized by a more homogeneous distribution of the cationic site population of iron compared with UM and by a different Fe³⁺/Al³⁺ substitution in the C_2v symmetrical sites of the silicate framework. ²⁹Si MAS NMR spectra on glasses indicate that LM1 glasses are more depolymerized than UM glasses, indicating the existence of structurally distinct magma batches. ²⁷Al MAS NMR spectra indicate the occurrence in UM glasses of aluminum in both tetrahedral and octahedral coordination; the observed Al^VI is believed to be a primary feature of the glass, since ²⁷Al CP-MAS NMR experiments do not reveal detectable esa-hydrated Al. The Al in sixfold coordination could be ascribed either to the more abundant alkali–OH terminations in UM, in which alkalies would be extracted from their charge-balance role for Al, thus altering its fourfold structural position, or to permanent compaction during fast cooling and decompression of high-pressure melts. ²³Na CP-MAS NMR experiments indicate the existence of Na–OH groups in both LM1 and UM glasses, relatively more abundant in the latter. Although preliminary, the results indicate the possible application of atomic-scale studies to variables that determine the regimes of explosive volcanism. Received: 1 July 1998 / Accepted: 1 October 1998     

Intracrustal origin of Arenal basaltic andesite in the light of solid–melt interactions and related compositional buffering

The origin of Arenal basaltic andesite can be explained in terms of fractional crystallization of a parental high-alumina basalt (HAB), which assimilates crustal rocks during its storage, ascent and evolution. Contamination of this melt by Tertiary calc-alkalic intrusives (quartz–diorite and granite, with ⁸⁷Sr/⁸⁶Sr ratios ranging 0.70381–0.70397, nearly identical with those of the Arenal lavas) occurs at upper crustal levels, following the interaction of ascending basaltic magma masses with gabbroic–anorthositic layers. Fragments of these layers are found as inclusions within Arenal lavas and tephra and may show reaction rims (1–5 mm thick, consisting of augite, hypersthene, bytownitic–anorthitic plagioclase, and granular titanomagnetite) at the gabbro–lava interface. These reaction rims indicate that complete `assimilation' was prevented since the temperature of the host basaltic magma was not high enough to melt the gabbroic materials (whose mineral phases are nearly identical to the early formed liquidus phases in the differentiating HAB). Olivine gabbros crystallized at pressure of about 5–6 kbar and equilibrated with the parental HAB at pressures of 3–6 kbar (both under anhydrous and hydrous conditions), and temperatures ranging 1000–1100°C. In particular, `deeper' interactions between the mafic inclusions and the hydrous basaltic melt (i.e., with about 3.5 wt.% H₂O) are likely to occur at 5.4 (±0.4) kbar and temperatures approaching 1100°C. The olivine gabbros are thus interpreted as cumulates which represent crystallized portions of earlier Arenal-type basalts. Some of the gabbros have been `mildly' tectonized and recrystallized to give mafic granulites that may exhibit a distinct foliation. Below Arenal volcano a zoned magma chamber evolved prior the last eruptive cycle: three distinct andesitic magma layers were produced by simple AFC of a high-alumina basalt (HAB) with assimilation of Tertiary quartz–dioritic and granitic rocks. Early erupted 1968 tephra and 1969 lavas (which represent the first two layers of the upper part of a zoned magma chamber) were produced by simple AFC, with fractionation of plagioclase, pyroxene and magnetite and concomitant assimilation of quartz–dioritic rocks. Assimilation rates were constant (r<sub>1</sub>=0.33) for a relative mass of magma remaining of 0.77–0.80, respectively. Lavas erupted around 1974 are less differentiated and represent the `primitive andesitic magma type' residing within the middle–lower part of the chamber. These lavas were also produced by simple AFC: assimilation rates and the relative mass of magma remaining increased of about 10%, respectively (r₁=0.36, and F=0.89). Ba enrichment of the above lavas is related to selective assimilation of Ba from Tertiary granitic rocks. Lava eruption occurred as a dynamic response to the intrusion of a new magma into the old reservoir. This process caused the instability of the zoned magma column inducing syneruptive mixing between portions of two contiguous magma layers (both within the column itself and at lower levels where the new basalt was intruded into the reservoir). Syneruptive mixing (mingling) within the middle–upper part of the chamber involved fractions of earlier gabbroic cumulitic materials (lavas erupted around 1970). On the contrary, within the lower part of the chamber, mixing between the intruded HAB and the residing andesitic melt was followed by simple fractional crystallization (FC) of the hybrid magma layer (lavas erupted in 1978–1980). By that time the original magma chamber was completely evacuated. Lavas erupted in 1982/1984 were thus modelled by means of `open system' AFCRE (i.e., AFC with continuous recharge of a fractionating magma batch during eruption): in this case assimilation rates were r₁=0.33 and F=0.86. Recharge rates are slightly higher than extrusion rates and may reflect differences in density (between extruded and injected magmas), together with dynamic fluctuations of these parameters during eruption. Ba and LREE (La, Ce) enrichments of these lavas can be related to selective assimilation of Tertiary granitic and quartz–dioritic rocks. Calculated contents for Zr, Y and other REE are in acceptable agreement with the observed values. It is concluded that simple AFC occurs between two distinct eruption cycles and is typical of a period of repose or mild and decreasing volcanic activity. On the contrary, magma mixing, eventually followed by fractional crystallization (FC) of the hybrid magma layer, occurs during an ongoing eruption. Open-system AFCRE is only operative when the original magma chamber has been totally replenished by the new basaltic magma, and seems a prelude to the progressive ceasing of a major eruptive cycle.     

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.     

Experimental evidence for the role of accessory phases in magma genesis

Recent experimental studies have established petrogenetic models based on melting processes involving major phases. The possible residual character of trace-element-enriched accessory phases is not considered for temperatures well above the solidus in these models. In contrast, geochemists, applying trace element data to independently test the experimentally-based models, have concluded that residual (or fractionating) accessory phases may have an essential role in controlling the trace element (especially REE) distributions in magmas.Some recent experimental work provides data on the stability of potentially significant accessories such as sphene, rutile, apatite, zoisite and mica in basaltic compositions at elevated P and T. Sphene is stable to 1000°C with 60% melting of a hydrous tholeiite at 15 kbar. At higher pressure, rutile is the only Ti-rich accessory phase, and is present to at least 1000°C and high degrees of melting. Published REE data on sphene and rutile suggest that these phases may be important in controlling REE distribution in some magmas. For example, island are high-Mg, low-Ca-Ti tholeiites with low REE abundances and U-shaped patterns (Hickey and Frey, 1979) may reflect the role of sphene. In addition to rutile, similar close-packed Ti-rich accessory phases such as priderite, perovskite, crichtonite and loveringite may occur in mantle-derived magmas. These phases readily accommodate the REE but their possible role needs experimental confirmation.Apatite is recorded in hawaiite (1.16% P₂O_s) with 2% H₂O added at 5–6 kbar and 1050°C within 30°C of the liquidus, but at present no other experimental data are available on its high P, T stability, although thermodynamic calculations indicate that F may increase its stability markedly. Apatite is well known in high-pressure inclusions and as a phenocryst phase in rocks of the alkaline and calc-alkaline series.Ilmenite is known as a near-liquidus phase in some mafic magmas at 5–10 kbar, but its stability decreases to near-solidus at 25–30 kbar. Zoisite occurs in hydrous mafic compositions at mantle pressures, but it is confined to temperatures < 780°C. Finally, mica has a wide temperature range of stability at mantle pressures, especially in potassic magmas, and phlogopitic mica is stable to 1040°C at 20–25 kbar in a hydrous, K-rich “tholeiite” (1.6% K₂O).     

Al andBe production in iron meteorites

We have measured by accelerator mass spectrometry the²⁶Al contents of 20 and the¹⁰Be contents of 14 iron meteorites. The²⁶Al contents are typically 30% or more lower than values obtained by counting techniques; the¹⁰Be contents are 10–15% lower. The production rates (P) of these nuclides decrease by more than a factor of two as the⁴He/²¹Ne ratio increases with increasing shielding from 200 to 400. For the lighter shielding conditions expected in stony meteorites we estimateP₂₆(Fe) as 3–4 dpm/kg andP₁₀(Fe) as 4–5 dpm/kg. The average P/₁₀P₂₆ activity ratio is close to 1.5. Exposure ages calculated from²¹Ne/²⁶Al ratios cannot be calibrated so as to agree with both⁴⁰KK/ ages and ages based on the shorter-lived nuclides³⁹Ar and³⁶Cl. If agreement with the latter is forced, then the disagreement with⁴⁰KK/ ages may signal a 35% increase in the cosmic-ray intensity during the last 10⁷ a.     

Water-saturated oceanic lavas from the Manus Basin: volatile behaviour during assimilation–fractional crystallisation–degassing (AFCD)

We have analysed volatiles (H₂O, He, Ar, CO₂) in differentiated (basaltic andesite, dacite) volcanic glasses dredged at a depth of ca. 2000 m in the eastern part of the Manus Basin between 151°20′ and 152°10′ E. These samples have Sr–O–B isotopic ratios that show that they most likely represent lavas evolved from a common magma source. Since these glasses are very fresh, they provide a unique opportunity to study the behaviour of magmatic volatiles during assimilation–fractional crystallisation–degassing (AFCD). The samples are highly vesicular (up to 18%) and the volatiles trapped in vesicles consist predominantly of H₂O with minor amounts of CO₂, and the concentration of water in the glasses indicates that H₂O saturation was attained. Rare gases except helium are atmospheric in origin, and the ³He/⁴He ratios and the CO₂/³He ratios are respectively lower and higher than those typical of Mid-Ocean Ridge Basalt (MORB), and appear to correlate with the degree of differentiation. AFCD allows efficient degassing of mantle-derived volatiles and contribution of crust-derived and atmosphere-derived volatiles. Given the widespread occurrence of differentiated magmatism at arcs, we suggest that AFCD is responsible for large-scale occurrence of ³He-rich crustal fluids and of atmospheric-like rare gases in arc emanations, and that most of the volatiles are lost continuously during fractional crystallisation, rather than catastrophically during eruptions.     

Apatite/liquid partition coefficients for the rare earth elements and strontium

Sixteen sets of apatite/liquid partition coefficients (D^ap/liq) for the rare earth elements (REE; La, Sm, Dy, Lu) and six values for Sr were experimentally determined in natural systems ranging from basanite to granite. The apatite + melt (glass) assemblages were obtained from starting glasses artificially enriched in REE, Sr and fluorapatite components; these were run under dry and hydrous conditions of 7.5–20 kbar and 950–1120°C in a solid-media, piston-cylinder apparatus. An SEM-equipped electron microprobe was used for subsequent measurement of REE and Sr concentrations in coexisting apatites and quenched glasses. The resulting partition coefficient patterns resemble previously determined apatite phenocryst/groundmass concentration ratios in the following respects: (1) the rare earth patterns are uniformly concave downward (i.e., the middle REE are more compatible in apatite than the light and heavy REE); (2) D_REE^ap/liq is much higher for silicic melts than for basic ones; and (3) strontium (and therefore Eu²⁺) is less concentrated by apatite than are the trivalent REE. The effects of both temperature and melt composition on D_REE^ap/liq are systematic and pronounced. At 950°C, for example, a change in melt SiO₂ content from 50 to 68 wt.% causes the average REE partition coefficient to increase from ～7 to ～30. A 130°C increase in temperature, on the other hand, results in a two-fold decrease in D_REE^ap/liq. Partitioning of Sr is insenstitive to changes in melt composition and temperature, and neither the Sr nor the REE partition coefficients appear to be affected by variations in pressure or H₂O content of the melt.The experimentally determined partition coefficients can be used not only in trace element modelling, but also to distinguish apatite phenocrysts from xenocrysts in rocks. Reported apatite megacryst/host basalt REE concentration ratios [12], for example, are considerably higher than the equilibrium partition coefficients, which suggest that in this particular case the apatite is actually xenocrystic.A reversal experiment incorporated in our study yielded diffusion profiles of REE in apatite, from which we extracted a REEαCa interdiffusion coefficient of 2–4×10^?14 cm²/s at 1120°C. Extrapolated downward to crustal temperatures, this low value suggests that complete REE equilibrium between felsic partial melts and residual apatite is rarely established.     

Ozone and airglow in the mesosphere region

The paper presents the results of a photometric study of the hydroxyl bands (7–2) and (8–3) in the night airglow spectrum at Mt. Abu in the winter and spring of 1966–1972. The observed nocturnal variation differs from the variation expected from the theoretical studies of Hesstvedt, Hunt, Shimazaki and others. Instead of a gradual fall in intensity after sunset to shortly before sunrise, a peak in intensity is found at a time which changes from month to month and roughly coincides with the transit times of the X-ray star TAU (XR-1)-Crab Nebula. Anexplanation of the observed phenomenon is offered in terms of the increased energy output into the D and E regions of the atmospheres, increased eddy diffusion, and production, of additional O(³P) and O₃ in the region 80–95 km. O₃ reacting with H gives rise to OH^*.     

Silicic magma entering a basaltic magma chamber: eruptive dynamics and magma mixing — an example from Salina (Aeolian islands,Southern Tyrrhenian Sea)

The Pollara tuff-ring resulted from two explosive eruptions whose deposits are separated by a paleosol 13 Ka old. The oldest deposits (LPP, about 0.2 km³) consist of three main fall units (A, B, C) deposited from a subplinian column whose height (7–14 km) increased with time from A to C, as a consequence of the increased magma discharge rate during the eruption (1–8x10⁶ kg/s). A highly variable juvenile population characterizes the eruption. Black, dense, highly porphyritic, mafic ejecta (SiO₂=50–55%) almost exclusively form A deposits, whereas grey, mildly vesiculated, mildly porphyritic pumice (SiO₂=56–67%) and white, highly vesiculated, nearly aphyric pumice (SiO₂=66–71%) predominate in B and C respectively. Mafic cumulates are abundant in A, while crystalline lithic ejecta first appear in B and increase upward. The LPP result from the emptying of an unusual and unstable, compositionally zoned, shallow magma chamber in which high density mafic melts capped low density salic ones. Evidence of the existence of a short crystal fractionation series is found in the mafic rocks; the andesitic pumice results from complete blending between rhyolitic and variously fractionated mafic melts (salic component up to 60 wt%), whereas bulk dacitic compositions mainly result from the presence of mafic xenocrysts within rhyolitic glasses. Viscosity and composition-mixing diagrams show that blended liquids formed when the visosities of the two end members had close values. The following model is suggested: 1. A rhyolitic magma rising through the metamorphic basement enterrd a mafic magma chamber whose souter portions were occupied by a highly viscous, mafic crystal mush. 2. Under the pressure of the rhyolitic body the nearly rigid mush was pushed upwards and mafic melts were squeezed against the walls of the chamber, beginning roof fracturing and mingling with silicic melts. 3. When the equilibrium temperature was reached between mafic and silicic melts, blended liquids rapidly formed. 4. When fractures reached the surface, the eruption began by the ejection of the mafic melts and crystal mush (A), followed by the emission of variously mingled and blended magmas (B) and ended by the ejection of nearly unmixed rhyolitic magma (C).     

Dredged basalts from the western Nazca plate and the evolution of the East Pacific Rise

Ocean-floor basalts and glasses were recovered from three stations along the western Nazca plate, from a sublinear topographic feature believed to represent the proto-East Pacific Rise (EPR), and include abyssal tholeiites, FeTi-basalts and glasses, as well as transitional and little fractionated compositions. When compared with their coexisting fresh glasses, the FeTi-basalts have higher total alkalies, TiO₂ and MgO, and lower FeO^*, suggesting that they have also been affected by non-oxidative post-magmatic alteration processes. The FeTi-glasses form a remarkably uniform compositional group through space and time. A little fractionated composition having anMg-number= 73, similar to those reported from the Mathematician Ridge, has higher Na₂O and TiO₂, and slightly lower CaO than similar compositions from the slowly accreting Mid-Atlantic Ridge. The basalts and glasses reported here exhibit the compositional diversity expected for propagating rifts and probably represent more than one volcanic episode.Both geochemical and geophysical interpretations support the inference that the EPR grew from Miocene times by the progressive growth and propagation of mantle perturbations, leaving a remnant sublinear zone of rough topography characteristic of slower accretion as the trace of the proto-EPR. Continuing translations and rotations of axial segments are occurring along the EPR, probably in response to self-reorganizations of mantle flow patterns arising from rapid melting and depletion of the source regions. The data allow the inference that the youthful rift systems of the eastern Pacific are far from thermodynamic equilibrium as might be expected if such systems were to drive fundamental life processes.     

Geochemistry of basalts from the Dumisseau Formation, southern Haiti: implications for the origin of the Caribbean Sea crust

Basalt and diabase from the Cretaceous Dumisseau Formation, southern Haiti have Mg-numbers of 43–63, TiO₂ contents of 1.6–3.9% and La abundances of 3.6–15.3 ppm.La/Ta ratios average 10, and indicate that the basalts are oceanic in character, distinct from the arc associations forming the northern part of Haiti. Oldest lavas have low TiO₂ (1.6%) and are LREE-depleted, similar to N-MORBs, whereas overlying lavas have higher TiO₂ (2–3.9%) and are LREE-enriched, similar to E-MORBs or hotspot basalts.⁸⁷Sr⁸⁶Sr ratios vary from 0.70280 to 0.70316,¹⁴³Nd¹⁴⁴Nd from 0.512929 to 0.513121, and²⁰⁶Pb²⁰⁴Pb from 19.00 to 19.27. LREE-depleted lavas have high¹⁴³Nd¹⁴⁴Nd (0.51309–0.51310) typical of MORBs, whereas¹⁴³Nd¹⁴⁴Nd in the LREE-enriched lavas varies widely (0.512929–0.513121).Chemical features of the Dumisseau basalts are equivalent to those of Caribbean seafloor basalts recovered on DSDP Leg 15, and support the contention that the Dumisseau is an uplifted section of Caribbean Sea crust. Oldest lavas are analogous to MORB-like basalts cored at Leg 15 Sites 146, 150, 152 and 153, and the overlying lavas are analogous to incompatible-element-enriched basalts cored at Site 151 on the Beata Ridge. Isotopic compositions of the Dumisseau basalts overlap with those of the eastern Pacific Galapagos and Easter Island hotspots. However, the presence of N-MORB basalts in the lower part of the Dumisseau and at the majority of Leg 15 Sites indicates that the anomalously thick Caribbean crust probably did not originate as a hotspot-related basaltic plateau, but may have been generated by on-ridge or near-ridge hotspot magmatism.     

Experimental determination of the solubility of carbon dioxide in molten basalt at low pressure

We report the first measurements of CO₂ solubility in molten basalt at pressures comparable to those at which submarine basalts erupt. A basalt from the Juan de Fuca ridge was equilibrated with CO₂-rich vapor at 1200°C, 100–1500 bar for up to four hours. After quenching, the glass was analyzed for dissolved carbonate ions by infrared spectroscopy. No forms of dissolved CO₂ other than carbonate were detected. CO₂ solubility is roughly a linear function of pressure at these low pressures. The experimentally determined solubility differs from previous estimates based on CO₂ concentrations of submarine glasses, on CO₂ solubilities in basaltic liquids at significantly higher pressures, and on CO₂ concentrations of glasses equilibrated with H₂OCO₂ vapor. Our results are compatible with those obtained previously at higher pressures on a molten Kilauea tholeiite only if there is a significant positive dependence of carbonate solubility on temperature.CO₂ contents of mid-ocean ridge glasses measured by infrared spectroscopy are generally higher than would be expected based on solubilities at the hydrostatic pressures for the water depths from which the glasses were recovered, but the lowest dissolved CO₂ contents agree with the experimentally determined solubilities. We propose that submarine glasses with low CO₂ contents were quenched from magmas that were able to degas because they rose slowly from depth. The common occurrence of glasses with dissolved CO₂ contents in excess of the experimentally determined solubility suggests they were quenched from magmas that ascended too rapidly to degas fully. In conjunction with our solubility data, the highest CO₂ contents allow minimum estimates of depths to magma chambers. Depths of 2.3 km beneath the ridge are indicated for the East Pacific Rise at 21°N, in agreement with geophysical constraints.     

Scattering and anelastic attenuation of seismic energy in northern Greece

The relative contribution of scattering (Q _s ^–1 ) and intrinsic (Q _i ^–1 ) attenuation to the totalS-wave attenuation for the frequencies of 1.5, 3.0, 6.0 and 12.0 Hz has been studied by applying the radiative energy transfer theory, Data of local earthquakes which occurred in northern Greece and were recorded by the permanent telementered network of the Geophysical Laboratory of the University of Thessaloniki have been used. The results show that in this area the scattering attenuation is dominant over all frequencies while intrinsic attenuation is significantly lower. The estimatedQ _s ^–1 andQ _i ^–1 values have frequency dependences off ^–0.72 andf ^–0.45, respectively. The frequency dependence ofQ _s ^–1 is the same as that of the codaQ _c ^–1 , obtained by applying the single scattering model, which probably implies that the frequency dependence of the coda wave attenuation is attributed to the frequency dependence of the scattering attenuation.Q _c ^–1 values are very close to scattering attenuation for short lapse times, (10–20 sec), and intermediate between scattering and intrinsic attenuation for the longer lapse times, (50–100 sec). This difference is explained as the result of the depth-dependent attenuation properties and the multiple scattering effects.     

Gas geochemistry of the Valles caldera region, New Mexico and comparisons with gases at Yellowstone, Long Valley and other geothermal systems

Noncondensible gases from hot springs, fumaroles, and deep wells within the Valles caldera geothermal system (210–300°C) consist of roughly 98.5 mol% CO₂, 0.5 mol% H₂S, and 1 mol% other components. ³He/⁴He ratios indicate a deep magmatic source (R/R_a up to 6) whereas δ¹³C–CO₂ values (−3 to −5‰) do not discriminate between a mantle/magmatic source and a source from subjacent, hydrothermally altered Paleozoic carbonate rocks. Regional gases from sites within a 50-km radius beyond Valles caldera are relatively enriched in CO₂ and He, but depleted in H₂S compared to Valles gases. Regional gases have R/R_a values ≤1.2 due to more interaction with the crust and/or less contribution from the mantle. Carbon sources for regional CO₂ are varied. During 1982–1998, repeat analyses of gases from intracaldera sites at Sulphur Springs showed relatively constant CH₄, H₂, and H₂S contents. The only exception was gas from Footbath Spring (1987–1993), which experienced increases in these three components during drilling and testing of scientific wells VC-2a and VC-2b. Present-day Valles gases contain substantially less N₂ than fluid inclusion gases trapped in deep, early-stage, post-caldera vein minerals. This suggests that the long-lived Valles hydrothermal system (ca. 1 Myr) has depleted subsurface Paleozoic sedimentary rocks of nitrogen. When compared with gases from many other geothermal systems, Valles caldera gases are relatively enriched in He but depleted in CH₄, N₂ and Ar. In this respect, Valles gases resemble end-member hydrothermal and magmatic gases discharged at hot spots (Galapagos, Kilauea, and Yellowstone).     

Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.