Interpretation of volcanic gas data from tholeiitic and Alkaline Mafic Lavas

The analyses of approximately 100 high temperature gas samples from erupting lavas of Surtsey, Erta Ale, Ardoukoba, Kilauea, Mount Etna and Nyiragongo exhibit erratic compositions resulting from analytical errors, condensation effects, reactions with sampling devices, and contamination by atmospheric gases, meteoric water and organic material. Computational techniques have been devised to restore reported analyses to compositions representative of the erupted gases. The restored analyses show little evidence of short-term variations. The principal species are H₂O, CO₂, SO₂, H₂, CO, H₂S, S₂, and HCl. The O₂ fugacities range from nickel-nickel oxide to a half order of magnitude below quartz-magnetite-fayalite. There is no evidence for a unique magmatic gas composition; instead, the erupted gases show regular compositional trends characterized by decreasing CO₂ with progressive outgassing. The gases from more alkaline lavas (Etna, Nyiragongo) are distinctly richer in CO₂, while those from less alkaline (Surtsey) or tholeiitic lavas (Erta Ale, Ardoukoba) tend to be richer in H₂O. Kilauean gases range from CO₂-rich to H₂O-rich. The total sulfur contents of the erupted gases show an excellent positive correlation with lava O₂ fugacity. All restored analyses are significantly lower in H₂O and enriched in sulfur and CO₂ compared to the «excess volatiles».     

A simple method for the collection and analysis of volcanic gas samples

Investigations into the chemistry of volcanic gases depend on the availability of complete and accurate analyses of volcanic exhalations. The wide variety of sampling and analysis methods hitherto used, often supplying only partial analyses of low precision, made intercomparison, and thus a systematic study of volcanic gases, difficult. With the method proposed here, complete volcanic gas samples are obtained permitting the accurate determination of all major species by standard analytical methods without the need for highly specialised ancillary equipment. The samples are collected in evacuated 300 ml pyrex flasks through titanium tubes deeply inserted into the gas vent. Two types of flask are used, a single compartment flask allowing the easy determination of the major constituents and containing 50 ml 4 N NaOH, and a double compartment flask for the separate analysis of the sulfur species and containing 25 ml 0.1 N As₂O₃ in 1 N HClO₄ in the first, and 50 ml 4 N NaOH in the second compartment. Non-absorbed gases are determined by gas chromatography, the rest by standard analytical procedures. The determination of H₂O, CO₂, SO₂, SO₂, S₂, H₂S, HCl, HF, H₂, N₂, O₂, CH₄, CO and NH₂ is described.     

The effect of variations in rainfall on the chemical composition of vulcano fumaroles (Italy)

Analytical data for samples collected over a period of 17 months at the crater fumaroles of Vulcano are given. Fluids are both condensed and absorbed in KOH solutions, thus providing a complete analysis of acid and condensable species. Variations in H₂O, CO₂, SO₂, H₂S, HCl, B, F, Br, NH₄ concentrations are taken into account. Rainwater represents an important modifying facor of the basic chemical composition of the investigated discharges, which do not seem to have undergone any other significant change during the above mentioned span of time. While acting essentially as a diluting factor for CO₂ and SO₂, the inflow of meteoric water can introduce substantial modifications in concentrations of other constituents. As a consequence, any correct comparison of fumaroles compositions either for different systems or for different samplings at the same system should take into consideration the influence of meteorological conditions.     

Crystallization temperature and gas phase composition of alkaline effusives as indicated by primary melt inclusions in the phenocrysts

Minerals formed during magma crystallization trap droplets of melt that are preserved as primary or secondary inclusions. Depending on the rate of cooling, the droplets may solidify as glass, or crystallize. Inclusions may contain one or more bubbles, or none. When inclusions are heated the glass or crystalline material are melted and the inclusion expands, the size of bubbles diminishes, and homogenization of the inclusion occurs. It is possible to observe these transformations by means of high-temperature cameras which permit visual observations to 1600°C and above. The possibility of using the homogenization of inclusions to determine the temperature of formation of the host mineral has been demonstrated experimentally, using inclusions in artificial diopside formed at 1300 ± 10°. Melt inclusions in phenocrysts from nepheline basalt, fergusite porphyry, and tephrite were investigated. In the leucite-bearing rocks leucite crystallized at 1600° or above, and clinopyroxene in the range 1380–1250°. The central part of olivines in nepheline basalt formed at 1290–1270° and the peripheral zones at 1160–1120°; nepheline formed at 1290–1250°; the central part of pyroxenes at 1280–1250° and the peripheral zones at 1160–1120°. These temperatures suggest almost dry magma. Gas from the bubbles of individual inclusions has been analyzed. The predominant gaseous component of the early crystallization stage of the nepheline basalt and fergusite porphry was CO₂, H₂S, SO₂, NH., HCl, HF, and H. comprise less than 5 volume percent except in olivine of olivine basalt in which the total content of these gases was on average 6.22 volume percent, and in leucite of fergusite porphyry in which H₂ was on average 12.7 volume percent. The main gas component in the crystallization of the leucite tephrite were nitrogen and rare gases. Liquid hydrocarbons in the secondary inclusions in pyroxene from nepheline basalt can be accounted for by their assimilation by the magma from enclosing rocks during its rise.     

Petrology of filicudi,aeolian archipelago

Volcanic rocks on the island of Filicudi are typical of the cale-alkaline association of the Aeolian archipelago, and range in composition from basalt to high-K andesite. All specimens contain abundant phenocrystic plagioclase (cores of An_82–97, rims becoming progressively more sodic with increasing Differentiation Index), clinopyroxene, and magnetite; the most basic samples contain olivine, which is replaced by orthopyroxene at around D.I.=44. SiO₂ generally increases with time, and this in conjunction with the continuity in mineralogy suggests that the lavas are the differentiation products of a single batch of magma. Least-squares mixing calculations are consistent with a shallow fractional model, as is the variation in trace element abundances.     

Petrology of tholeiitic lavas from Tanna Island (New Hebrides): Importance of cumulative processes in Island arc magmatism

Tanna, one of the southernmost islands of the New Hebrides volcanic arc, is made of Late Pliocene to Recent island arc tholeiitic basalts and andesites, with SiO₂ contents ranging from 45 to 57%. These lavas are highly porphyritic (30–50% in volume): phenocrysts of plagioclase are the most abundant, together with olivine and clinopyroxene. The groundmass contain plagioclase, augite, olivine, magnetite and glass; pigeonite, tridymite, sanidine and, rarely, biotite may also occur. The olivines and clinopyroxenes show an iron enrichment from the cores of phenocrysts to their rims and the groundmass crystals, but their compositional variations are not correlated with the Mg/Fe ratio of bulk host rocks, the most Fe-rich compositions being found in Mg-rich lavas. Plagioclase compositions range from An₉₅ to An₆₀ in the basalts and An₆₀ to An₅₀ in the andesites, but, within each group, they are not correlated with SiO₂ or Na₂O contents of host lavas. Consequently, the bulk major element compositions of Tanna volcanic rocks cannot be considered as primarily controlled by crystal separation from successive liquids. The oxyde-SiO₂ variations diagrams, and the modal compositions and mineral chemistry show that crystal accumulation is the predominant mechanism accounting for bulk rock compositions. However, this does not exclude fractional crystallization: the variation of the calculated groundmass mineralogy strongly suggest the occurrence of crystal removal mainly clinopyroxene and magnetite.     

Boninite as a possible calc-alkalic primary magma

Boninite is an unusual, plagioclase-free magnesian andesite, occurring as vesicular pillow lavas and hyaloclastites, accompanied by andesites and dacites in Chichi-jima, Bonin Islands. The Bonin Islands belong to the Izu-Mariana arc and consist of dominant volcanic rocks and subordinate sedimentary rocks of late Oligocene-early Miocene age. The chemistry of boninite is characterized by high contents of MgO. Cr and Ni similar to primitive basalts, but apparently in ill accord with its relatively high SiO₂ content of ? 55%. The relation of SiO₂ to total FeO/MgO ratio indicates that boninite belongs to the cale-alkalic rock suite. The mineralogy of boninite consists of olivine (Fo87-90), orthopyroxene (En87-90), clinopyroxene (Wo38-35En37-44Fs25-21), hydrous glass and Cr-spinel, Experimental studies show that the magma of boninite composition could be in equilibrium with upper mantle peridotite at pressures less than 17 kb and temperatures of 1200–1050°C under high P_H2_O. It is suggested that boninite is a sea-floor quenched product (900°C) of a direct partial melt of the upper mantle. Related andesites and dacites are considered to be probably fractional crystallization products from the same magma.     

Melting of Mg2GeO4 under pressure

Melting point of germanate forsterite, Mg₂GeO₄, was raised by compression at the rate of 30°C/GPa. The triple point, at which three phases of olivine- and spinel-type solids and liquid coexisted, was fixed at 1950°C and 3.5GPa. Wen these results are combined with the thermodynamical data of forsterite, Mg₂SiO₄, it is estimated that the triple point of forsterite lies in a region ranging from 2700° to 3000°C in temperature and from 20 to 30GPa in pressure.     

Fractional crystallization trends in the system Mg2SiO4-CaAl2Si2O8-FeO-Fe2O3-SiO2 over the range of oxygen partial pressures of 10−11 to 10−0.7 atm

A brief report is made of current laboratory investigations on phase relations among olivine, pyroxene, anorthite, magnetite, tridymite, liquid and gas in the system Mg₂SiO₄-CaAl₂Si₂O₈-FeO-Fe₂O₂-SiO₂ over a wide range of oxygen partial pressures. Courses of fractional crystallization under various conditions of oxygen partial pressure are depicted using an anorthite saturation diagram. Starting with a basalt-like composition in the system, fractional crystallization at a moderate oxygen partial pressure (10 atm.) results in an andesite-like residual liquid of composition 55 SiO₂, 14 iron oxide, 6 MgO, 9 CaO, 16 Al₂O₃ at a temperature of 1155°C. With fractional crystallization in a closed system, the end liquid approaches the composition of 45 SiO₂, 38 iron oxide, 6 CaO and 11 Al₂O₃, at a temperature of 1050°C and oxygen partial pressure of about 10^?12 atm. The andesitic final liquid in this system would be expected to further differentiate toward dacitic and rhyolitic compositions if alkalies and water were present in the system. On the basis of these studies, the derivation of liquids of andesitic, dacitic or rhyolitic composition from primary basalts by fractional crystallization seems entirely possible if the oxygen partial pressure is maintained at a moderate or high level.     

Some remarks on contact anatexis

The chemical variability of the products of contact-anatexis, completely different from the normal trend of magmatic differentiation, may be explained by the quantitative variation of gaseous transfer, according to the state of the basaltic magma which may be pyromagma or hypomagma at the contact with the surrounding sialic rocks. Therefore, two types of contact-anatexis must be distinguished: 1st.Anatexis at the contact with pyromagma. If the tectonical conditions are favourable, then the basaltic magma rises so high in the sialic crust that the gas tension overcomes the hydrostatic pressure. A gas phase will separate and cause a considerable gas transfer by which pneumatophilic substances (Na, Fe, Ti etc.) are supplied to the overlying anatectic magma. 2nd.Anatexis at the contact with hypomagma. If the rising basaltic magma cannot reach very high levels in the sialic crust, then the gas tension remains lower than the hydrostatic pressure, and the gases are molecularly dispersed within the melt. The gas transfer will be insignificant, and the anatexis is merely due to the supply of heat without any appreciable change of the chemical composition of the anatectic magma.     

Major-element petrochemistry of some extrusive rocks from the volcanically active Mariana Islands

Volcanic rocks from six of the currently or recently active volcances of the Mariana Island are show little variation in major element abundances. SiO₂ content averages 51.5 wt.%. The flows are high in Al₂O (mean 17.7 wt.%) and Fe oxides (mean 10.1 wt.% calculated as FeO only), and moderate in MgO content (mean 4.7 wt.%), Na₂O (mean 2.7 wt.%), and K₂O (mean 0.7 wt.%). Only the rocks from Farallon de Pajaros, the northernmost of the Mariana Islands, deviate slightly from the average of the analyses. Three analyses from this island are slightly higher in SiO₂ (about 54 wt.%) and Al₂O₃, and are lower in total Fe oxides and MgO. According to preferred classification, the lavas of the Mariana Islands can be termed mela-andesites, high-alumina basalts, or calc-alkaline (orogenic) basalts. The K₂O values (mean 0.7 wt.%) obtained from lavas of the Mariana Islands are significantly higher than the K₂O values (about 0.33 wt.%) from volcanics of the Izu chain to the north. Inasmuch as the substantial scatter in location of earthquake foci beneath both arcs prevents accurate delineation of the upper boundary of the Benioff zone, it presently cannot be determined whether this discrepancy in K₂O values reflects a difference in depth from the volcanic are to the dipping seismic zone or relates to other phenomena. The older volcanic islands within the Mariana-Bonin island chain apparently defined an island arc system during Eocene to Miocene time. This indicates that the present plane of convergence between the Pacific plate and the Philippine Sea plate has defined the convergence between these plates since Eocene time.     

Calc-alkaline volcanic rocks from NW Sardinia: Evaluation of a fractional crystallization model

The volcanic centre of Monte Seda Oro, N. W. Sardinia, representative of a Cenozoic calc-alkaline andesitic suite of rocks is composed of a variety of rocks ranging from high alumina basalts to dacites. The minerals of basaltic, andesitic and dacitic rocks show only limited variation in chemical composition. The geochemical data suggest that the various rock-types are related by a crystal-liquid fractionation. Least-squate numerical calculations, using major element data, support the derivation of andesites with SiO₃ content ranging from 53.8 to 59.0% from basalts having about 48.7% of SiO₂ by low pressure crystal fractionation of the phenocryst phases present in these rocks. However, the origin of dacites cannot be readily explained by this mechanism.     

A comparison of the recent eruptions of Mt. Pelée,Martinique and Soufrière,St. Vincent

The simultaneous eruption of Mt. Pelée, Martinique and Soufrière, St. Vincent are regarded as the first recognized examples of Pelean-type and St. Vincent-type pyroclastic eruptions. Both produced nuées ardentes, the former usually laterally directed because of the presence of a dome and the latter vertically directed from an open crater. Both volcanoes have subsequently erupted for a second time this century. The 1902–05 and 1929–32 eruptions of Mt. Pelée produced andesite lava of almost identical composition and mineralogy. Both contain two generations of plagioclase, orthopyroxene, Fe-Ti oxide, corroded brown amphibole and olivine rimmed by pyroxene. In contrast, the Soufrière material is more basic in composition varying from basaltic andesite to basalt in 1902–03 and basaltic andesite in 1971–72. The Soufrière material contains two generations of plagioclase (with those of 1971–72 having additional zones of labradorite), clinopyroxene, orthopyroxene, olivine and Fe-Ti oxide. The pyroclastic deposits are strikingly different, those from the Pelean-type eruption are termed «block and ash deposits» being characterised by poorly vesicular lava blocks up to 7 m in diameter, while the St. Vincent-type eruption produced «scoria and ash deposits» containing vesicular ropey blocks or bombs no larger than 1 m in diameter. The differences in styles of eruption are attributed to differences in viscosity and mechanism of eruption of the magmas. Stratigraphic studies of Mt. Pelée reveal that the volcano has produced basaltic andesite scoria and ash deposits from St. Vincent-type eruptions. It is concluded that the recent eruptions of Pelée tapped a deep level magma during both eruptions releasing magma of similar composition, while the 1971 Soufrière magma is thought to be a remnant of the 1903 basaltic magma which remained at a high level within the volcano where it underwent enrichment in plagioclase and loss of olivine and oxide.     

Rapakivi texture from the O’Leary Porphyry,Arizona (U.S.A.)

The rhyodactic O’Leary Porphyry which forms the Pleistocene (0.233±0.37 m.y.) volcanic domes of O’Leary Peak and Darton Dome in the San Francisco Volcanic Field (northern Arizona, U.S.A.) contains sanidine phenocrysts with oligoclase mantles (rapakivi texture). Rapakivi texture occurs worldwide in silicic rocks of many ages and has been attributed to various igneous and metamorphic processes. The O’Leary Porphyry contains both mantled and unmantled sanidine (both are Or_63–69 Ab_30–36An₁), oligoclase and quartz phenocrysts, labradorite (An₅₃Ab₄₅Or₂) and kaersutite xenocrysts and andesite xenoliths. The compositional range of oligoclase is the same (An_11–26Ab_70–80Or_r–10) for the rapakivi mantles, the oligoclase phenocrysts, and the oligoclase crystals poikilitic within sanidines. Most mantles are discontinuous. The sanidine appears to have been resorbed prior to mantling. Experimental melting studies on the O’Leary Prophyry show that, for a 15 wgt.% water system, plagioclase crystallized prior to sanidine and quartz crystallized last. The O’Leary Porphyry, although inhomogeneous, plots on a Q-Or-Ab-An diagram well within the plagioclase stability field. Poikilitic plagioclases within sanidines further support crystallization of plagioclase prior to sanidine in the O’Leary Porphyry. Exsolution of a ternary feldspar to form a plagioclase mantle is the most commonly accepted igneous theory of rapakivi texture formation but has been eliminated as the origin of the O’Leary Porphyry rapakivi. Petrologic models by Tuttle and Bowen and by Stewart are rejected for the O’Leary rapakivi because of inconsistencies with the O’Leary occurrences. Two theories are viable for the O’Leary rapakivi texture. First, is a decrease in water vapor pressure which would enlarge the plagioclase stability field possibility causing mantling of metastable sanidines. The second and preferred theory is that of an addition of sodium and calcium by basification (chemical assimilation without melting) of the xenoliths within the O’Leary Porphyry. This would move the bulk composition of the melt into the plagioclase field possibly resulting in crystallization of plagioclase on sanidine crystals. Diffusion of sodium and calcium from the xenoliths to sanidine would result in mantling only those crystals near to the xenoliths. Later, convection would result in distribution throughout the melt of rapakivi, unmantled sanidines, and xenolithic kaersutite as is seen in the porphyry. Basic xenoliths are extremely common in rapakivi-bearing rocks. Those within the O’Leary Porphyry are andesitic and show resorption, and in some areas of O’Leary Peak itself, have been drawn out into schlieren.     

Voluminous acid volcanism in the Busheveld Complex: A review of the Rooiberg Felsite

The 2.1 b.y. old Rooiberg Felsite roofs and is intruded by the mafic layered rocks and granites of the Bushveld Complex. The felsite unit, which locally exceeds 5 km in thickness and may represent an originally erupted volume of more than 300,000 km³, is dominated by rhyolitic to dacitic lavas with minor pyroclastic and sedimentary rock types. Volcanic rocks of more mafic composition occur towards the base of the sequence. The Rooiberg episode essentially terminated the volcanic activity in the Transvaal basin and heralded the emplacement of the Bushveld Complex. Despite the close spatial and temporal relationships between the Rooiberg Felsite and the Bushveld Complex, the precise nature of the petrogenetic link is obscure. Chemical analyses of felsite have been variously interpreted to suggest cyclic differentiation along a comagmatic trend or to demonstrate anomalous enrichment in SiO₂. Several characteristics delineate the Rooiberg Felsite as a possibly unique occurrence of rhyolitic magmatism, notably the immense volume of the unit, the marked preponderance of lavas over pyroclastic types, and the unusually great thickness and lateral extent of the flows. The thesis that the Rooiberg Felsite represents a shock-produced, meteorite-impact melt cannot be supported on the available evidence.     

Eruption of Piip Crater (Kamchatka)

In autumn of 1966 on the northern slope of Kliuchevskoy volcano a chain of new adventive craters broke out at the height of about 2200 m. Eighty-four hours before the beginning of the eruption a swarm of preliminary volcanic earthquakes had appeared. The number of preliminary shocks was 457 with total energy of 4 × 10¹⁷ erg. With the beginning of the lava flow the earthquakes stopped and a continuous volcanic tremor appeared. The total energy of volcanic tremor amounts to 10¹⁶ erg. During the eruption numerous explosive earthquakes with the energy of 10¹⁵–10¹⁶ erg were recorded and besides the microbarograph of the Volcanostation recorded 393 explosions with an energy more than 10¹³ erg and their total energy was equal to 10¹⁷ erg. All together it has been formed 8 explosive craters and the lowest 9th crater was effusive. The slag cone was formed round this effusive crater, the lava effusion of basaltic-andesite composition (52,5% SiO₂) tooke place from the lava boccas at the cone base and from the crater. The lava flow covered a distance of 10 km along the valley of the Sopochnoy river and descended to a height of about 800 m. The lava flow velocity at the outflow reached 800 m/hr, the lava temperature was 1050°C. The effused lava volume amounts to 0.1 km³. The eruption stopped on December 25–26, 1966.     

Magmatic gases extracted and analysed from ocean floor volcanics

Magmatic gases extracted and analysed from basaltic rocks collected in the FAMOUS area near 36°50′ N in the Atlantic ocean show that the total amount of gas included in the samples varies between about 500 ppm to 1600 ppm. The main gaseous phases included in the various types of basalts consist of CO₂ (270–700 ppm), CO (150–800 ppm), HCl (100–1000 ppm), H₂ (0–50 ppm), SO₂ (up to 175 ppm), N₂ (up to about 213 ppm) and traces of hydrocarbons (up to about 24 ppm). The relative amount of CO, CO₂ and SO₂ varies with both the degree of crystallinity of the rock and with fractional crystallization and/or fractional melting. The glassy margin of pillow lavas have a higher CO/CO₂ ratio than the more crystalline interior. The most fractionated rocks of the series rich in clinopyroxene are depleted in the CO/CO₂ ratio and have a higher SO₂ content than do the most mafic end members rich in olivine. Early-formed olivine was crystallized in a reducing environment rich in CO and H₂ with respect to later formed mineral associations. It is likely that the carbon and sulfur oxidation is taking place at a relatively shallow depth during magmatic ascent or during volcanism. The ocean floor volcanics when compared to subaerial basalts are depleted in SO₂ and have on the average ten times more H₂.     

Geochemical surveillance of active volcanoes: data on the fumaroles of Vulcano (Aeolian Islands,Italy)

Temperature and chemical composition of condensates of higher temperature fumaroles, located on the rim of the crater of Vulcano, were studied over a period of one year. Maximum temperature changed from 216°C (June 1977) to 291°C (May 1978). HCl is the main constituent of condensates which, in comparison with data from fumaroles of other volcanoes, contain also noteworthy quantities of boron and bromine. Since these chemical characteristics suggested the possible inflow of water of marine origin into the volcanic conduit, experimental data on seawater-rock reactions at high temperatures and pressures were taken into account. A model is drafted for the volcanic system, in which the occurrence of an aquifer interposed between the magma chamber and the surface is considered. The vaporization of this aquifer would feed the fumaroles giving rise, through different mixing processes with surface waters, to the observed differences in temperature and chemical composition. However, data available at present are not sufficient to support the proposed model, which must be mainly considered as a working hypothesis.     

Volcan ceboruco: A major composite volcano of the mexican volcanic belt

Ceboruco is a major composite volcano at the western end of the Mexican Volcanic Belt, near the junction between the North American and Pacific plates. The volcano is built from successive eruptions of andesite lavas and pyroclastic rocks, and major eruptions during its history have resulted in the formation of two concentric calderas. The youngest volcanic activity has included the extrusion of dacites within the inner caldera and a voluminous flank eruption of andesite during 1870–72. Fumarolic activity persists to the present day. Chemical analyses show that the lavas are of cale-alkaline type and rangs from andesite (SiO₂=58–61%) to acid dacite (SiO₂=68%) in composition. The rate of increase of K₂O relative to SiO is greater than that in volcanic rocks from the Mexican Volcanic Belt as a whole. This indicates that simple models based on the application of such relationships may not be adequate to explain the petrogenesis of calc-alkaline lavas.     

Ground deformations on Mt. Vesuvius from 1977 to 1981

The results of a ground deformation study (1) of Vesuvius are reported. The study is a part of the geophysical program for the surveillance of this extremely dangerous active volcano. The results obtained in the period 1977–1981 show no significant changes in the dynamic state of the volcano. Corresponding to the southern Aapennines Nov. 23, 1980 earthquake a modification of the zenithal distance between the rim and bottom of the Vesuvius crater was observed which was likely connected with fairly shallow effects.