Volcanic emissions of metals and halogens from White Island (New Zealand) and Erebus volcano (Antarctica) determined with chemical traps

Volcanic emission rates of As, Sb, Pb, Hg, Se, Cl, and F were determined at Erebus volcano, Antarctica and White Island, New Zealand, using chemical traps. The trace metal fluxes were determined by combining the species to S ratios in the solutions with SO₂ emission rates measured by correlation spectrometry at the two volcanoes. At Erebus volcano, fluxes for the metals Pb and Hg were 2.0 × 10^− 4 and 8.1 × 10^− 6 kg s^− 11, respectively. Fluxes for Cl, F, As, Sb and Se (0.35, 0.15, 2.5 × 10^− 4, 1.2 × 10^− 5, and 4.5 × 10^− 6 kg s^− 1, respectively) agreed within error limits for values determined previously by the LiOH impregnated filter method [Zreda-Gostynska, G., Kyle, P., Finnegan, D., Prestbo, K., 1997. Volcanic gas emissions from Mount Erebus and their impact on the Antarctic environment. Journal of Geophysical Research, 102(B7): 15039–15055.], demonstrating the utility of the chemical trap method. A fall in the As/S ratio from 7 × 10^− 4 in 1997/1999 to 3 × 10^− 4 in 2000 at Erebus coincided with a change in the frequency and style of eruptive activity that may have been due to injection of magma into the system. At White Island, chemical trap data indicated fluxes of Cl = 0.90, F = 0.0079, Pb = 2.7 × 10^− 4, Hg = 1.1 × 10^− 5, As = 1.3 × 10^− 4, Sb = 1.9 × 10^− 5 and Se = 1.5 × 10^− 5 kg s^− 1. Samples collected 600 m downwind of the active crater were comparable to samples collected adjacent to the main gas vent, showing that this method can still be used at some distance from a degassing vent.     

Variations in the carbon,sulfur and chlorine contents of volcanic gas discharges from White Island,New Zealand

On six occasions, Irom July 1971 to June 1973, discharge samples from twelve selected fumaroles on White Island in the Bay of Plenty, New Zealand, were collected and analysed. The large variations in the absolute and relative proportions of carbon, sulfur, and chlorine containing species, occurring simultaneously over the entire active area of the volcano, suggest that all fumaroles are essentially supplied with one common type of gas made up of at least three components. During quiet periods, with low fumarolic outlet temperatures (≤300), the component with ratios C:S:Cl of 92:3:5 predominates; during heating up periods the relative carbon contents decrease, considered to be due to admixture of a component with C:S:Cl ratios of 44:26:30. Coinciding with maximum outlet temperatures (≈ 800°), however, the component with C:S:Cl ratios of 70:29:1 predominates, causing a rapid and marked rise in the ratio S:Cl from unity to above ten. The latter component with low ratios of C:S of around 2.5 and ratios of S:Cl of above ten is considered to be most closely related to the primary magmatic gas phase.     

Seismicity at White Island volcano, New Zealand: a revised classification and inferences about source mechanism

The classification of earthquakes at White Island volcano, New Zealand, has been revised to address problems in existing classification schemes, to better reflect new data and to try to focus more on source processes. Seismicity generated by the direct involvement of magmatic or hydrothermal fluids are referred to as volcanic, and that generated by fault movement in response to stresses caused by those fluids, regional stresses, thermal effects and so on are referred to as volcano-tectonic. Spasmodic bursts form a separate category, as we have insufficient information to classify them as volcanic or volcano-tectonic. Volcanic seismicity is divided into short-duration, long-period volcanic earthquakes, long-duration volcanic earthquakes, and harmonic- and non-harmonic volcanic tremor, while volcano-tectonic seismicity is divided into shallow and deep volcano-tectonic earthquakes. Harmonic volcanic tremor is related to sub-surface intrusive processes, while non-harmonic volcanic tremor originates close to active craters at shallow depth, and usually occurs during eruptive activity. Short-duration, long-period volcanic earthquakes come from a single source close to the active craters, but originate deeper than non-harmonic volcanic tremor, and are not related to eruptive activity. Long-duration volcanic earthquakes often accompany larger discrete eruptions. The waveform of these events consists of an initial low-frequency part from a deep source, and a later cigar-shaped part of mixed frequencies from a shallow crater source.     

High-frequency earthquakes at White Island volcano, New Zealand: insights into the shallow structure of a volcano-hydrothermal system

Volcano-tectonic earthquakes at White Island are concentrated in a single seismically active zone, southeast of the active vents and at depths of less than 1 km. A few deeper earthquakes also occur beneath the active vents. A composite focal mechanism indicates that the stress regime in the shallow seismic zone is N-S extensional. Shallow seismicity occurs within the main volume of the volcano-hydrothermal system that underlies the Main Crater floor, and we interpret this as a region where the rocks have been weakened by past magmatic intrusions, elevated pore fluid pressure and physico-chemical effects of acid volcanic fluids, thereby allowing preferential seismic failure. Brittle seismic failure within this region requires a temperature less than about 400 °C, and implies high horizontal temperature gradients close to the active craters and fumaroles. Spasmodic bursts events are also a result of brittle failure, but occur close to zones of significant permeability in response to changes in local fluid pressure.     

Stable isotope ratios of volcanic steam from White Island,New Zealand

The D/H and¹⁸O/¹⁶O ratios of fumarole condensates from White Island, an andesite volcano in the Bay of Plenty, have been measured during the period 1965 to 1969 to determine the origin of the water and the changes which occur as the volcanic activity changes. The D/H and¹⁸O/¹⁶O ratios of all of the samples were correlated with a slope of ?2. The δ¹⁸O values were proportional to the logarithm of the chloride concentration but with distinctly different relationships between the period from 1965 to 1967, and the period of tephra eruptions in 1968. In the latter period the chloride contents were close to that of sea water while in the former quieter period the contents were lower. The δD values follow a similar pattern but with a poorer correlation, indicating that a more variable process is controlling the deuterium results. Possible hydrothermal models are: mixing of near surface water and magmatic water; progressive leaching of chloride from underground rocks and exchange of isotopes (Craig, 1966); and lastly, equilibrium evaporation at about 255°C of either sea water or local surface water. The first of these models is considered most unlikely because of the incompatible logarithmic relationship between the chloride content and the oxygen isotope results. The second model has some merit, but the available evidence favours the last of the three models in which the 1965–67 samples derive from surface water or vapour from a boiling chloride water aquifer of sea water origin and the 1968 samples derive from the boiling chloride water, because of disturbance of the system during the tephra eruptions.     

Evolution of a Quaternary peralkaline volcano: Mayor Island, New Zealand

Mayor Island is a Holocene pantelleritic volcano showing a wide range of dispersive power and eruptive intensity despite a very limited range in magma composition of only 2% SiO₂. The primary controls on this range appear to have been the magmatic gas content on eruption and a varying involvement of basaltic magma, rather than major-element chemistry of the rhyolites. The ca. 130 ka subaerial history of the volcano contains portions of three geochemical cycles with abrupt changes in trace-element chemistry following episodes of caldera collapse. The uniform major-element chemistry of the magma may relate to a fine balance between rates of eruption and supply and the higher density of the more evolved (Ferich) magmas which could be tapped only after caldera-forming events had removed significant volumes of less evolved but lighter magma.     

Sulfur dioxide emissions and degassing behavior of Erebus volcano,Antarctica

Emission rates of sulfur dioxide (SO₂) were measured at Erebus volcano, Antarctica in December between 1992 and 2005. Since 1992 SO₂ emissions rates are normally distributed with a mean of 61 ± 27 Mg d^− 1 (0.7 ± 0.3 kg s^− 1) (n = 8064). The emission rates vary over minutes, hours, days and years. Hourly and daily variations often show systematic and cyclic trends. Long-wavelength, large amplitude trends appear related to lava lake area and both are likely controlled by processes occurring at depth. Time series analysis of continuous sequences of measurements obtained over periods of several hours reveals periodicity in SO₂ output ranging from 10 to 360 min, with a 10 min cycle being the most dominant. Closed and open-system degassing models are considered to explain observed variable degassing rates. Closed-system degassing is possible as rheological stiffening and stick/slip may occur within the system. However, the timescales represented in these models do not fit observations made on Erebus. Open-system degassing and convection fits the observations collected as the presented models were developed for a system similar to Erebus in terms of degassing, eruptive activity and process repose time. We show that with the observed emission rate (0.71 kg s^− 1) and a crystal content of 30%, magma will cool 65 °C to match observed heat fluxes; this cooling is sufficient enough to drive convection.     

Rates and patterns of erosion on inter-tidal shore platforms,Kaikoura Peninsula,South Island,New Zealand

This paper presents measured rates of erosion on shore platforms at Kaikoura Peninsula, South Island, New Zealand. Surface lowering rates were measured with a micro-erosion meter and traversing micro-erosion meter. The mean lowering rate for all shore platforms was 1·130 mm a⁻¹. Differences in lowering rates were found between different platform types and lithologies. The rate of surface lowering on Type A (sloping) mudstone platforms was 1·983 mm a⁻¹, and 0·733 mm a⁻¹ on Type B mudstone platforms (subhorizontal). On limestone platforms the lowering rate was 0·875 mm a⁻¹. A previously reported cross-shore pattern of surface lowering rates from Kaikoura was not found. Rates were generally higher on the landward margins and decreased in a seaward direction. Season is shown statistically to influence erosion rates, with higher rates during summer than winter. The interpretation given to this is that the erosive process is subaerial weathering in the form of wetting and drying and salt weathering. This is contrary to views of shore platform development that have favoured marine processes over subaerial weathering. Copyright © 1998 John Wiley & Sons, Ltd.     

Magma mingling in an andesite pyroclastic flow of the Pourahu Member, Ruapehu volcano, New Zealand

We describe a magma mingling episode from Ruapehu volcano between two andesite magmas, one very much minor in volume relative to the other. The event acted to trigger eruption of the andesitic Pourahu pyroclastic flow which is preserved in a thick sequence of tephras and laharic deposits in the southeastern ring plain of the volcano. The predominant andesite is pale brown coloured and porphyritic containing phenocrysts of plagioclase-clinopyroxene-orthopyroxene-Fe-Ti oxides. Rare clasts of a darker andesite are different texturally, less vesicular, and contain distinctive microphenocrysts of plagioclase and quench olivine. Equally rare clasts, of streaky pumice consisting of interbanded ‘dark’ and ‘light’ andesite attest to mingling between these two andesite components.Chemical analyses of discrete clasts demonstrate that the Pourahu pyroclastic flow andesites span much of the compositional spectrum of Ruapehu andesites. This observation demonstrates heterogeneity in the products of a relatively small eruption. The darker clast analyses and those from associated distal fall deposits lie within the fields defined by the dominant light coloured clasts. Phenocryst and microphenocryst geothermometry suggest slightly higher temperatures in the dark component. However, glasses from groundmass and phenocryst inclusions in the same specimen may differ considerably, leading us to conclude that many phenocrysts are in fact xenocrystic and were incorporated in the melts as they migrated towards the surface.We prefer a model in which a small volume of hot andesite magma injects a vent-feeding magma chamber, triggering vesiculation and eruption. We infer that the process of magma withdrawal extended downward into the magma body causing the dark component to intermingle with the lighter (dominant) component, ‘sucking’ more dark magma into the chamber. Our observations are entirely consistent with the existence of a plexus of small, possibly interlinked magma chambers beneath Ruapehu.     

Taupo Volcanic Zone calc-alkaline tephras on the peralkaline Mayor Island volcano, New Zealand: identification and uses as marker horizons

Mayor Island is a peralkaline rhyolitic caldera volcano characterised by numerous, sector-confined pyroclastic deposits, together with lavas forming at least five composite shields. Correlation of sequences between sectors is difficult because of the scarcity of island-wide marker beds. However, eight distal calc-alkaline fall tephras (ca. 7.3 ¹⁴C ka to 64 ka) from Okataina and Taupo volcanic centres in the nearby Taupo Volcanic Zone (TVZ) have been identified on the island. These “foreign” TVZ tephras provide marker planes to correlate activity in different sectors of Mayor Island volcano, and refine an eruptive chronology. At least seventeen pyroclastic eruptions and fourteen lava-producing events (including multiple, shield-forming events) have occurred in the past ca. 64 ka. Age controls provided by the calc-alkaline tephras confirm the extremely local dispersal characteristics of many of the Mayor Island eruptives and show that K/Ar ages as young as 25–33 ka on obsidians with 4.2–4.4% K₂O are reliable.     

Earthquakes at depth beneath volcanoes,forerunners of their activities. Application to White Island,New Zealand

The concept of a time-depth correlation between tectonic earthquakes at depth beneath some volcanoes, and their eruptions, developed by the author since 1962, has been confirmed by new observations and successful prediction of renewed volcanic activity in New Zealand.Regular earthquake migrations are observed along the Benioff zone, and volcanic eruptions are found to be related to these seismic migrations beneath the volcanoes, as follows:

Therefore, in island arcs and continental margins, volcanic activity is the result of two processes occurring beneath the volcanoes: (1) a “tectonic process”, a migration of strain release along the downgoing lithosphere, of which the earthquakes are the manifestation; (2) a “magmatic process”, a relatively fast vertical ascent of magmatic material from the deep root of the volcano, where the observed shocks may be the starting signal from this level.The rate of migration of tectonic earthquakes increases with depth in the upper mantle.An empirical time relationship between the earthquakes occurring at depth beneath a volcano and its eruptions, has been successfully tested for renewed activity at White Island in New Zealand, over the period 1977–1978.     

Sulfur dioxide emissions from Popocatépetl volcano (Mexico): case study of a high-emission rate, passively degassing erupting volcano

Popocatépetl volcano in central Mexico has been erupting explosively and effusively for almost 4 years. SO₂ emission rates from this volcano have been the largest ever measured using a COSPEC. Pre-eruptive average SO₂ emission rates (2–3 kt/d) were similar to the emission rates measured during the first part of the eruption (up to August 1995) in contrast with the effusive–explosive periods (March 1996–January 1998) during which SO₂ emission rates were higher by a factor of four (9–13 kt/d). Based on a chronology of the eruption and the average SO₂ emission rates per period, the total SO₂ emissions (up to 1 January 1998) are estimated to be about 9 Mt, roughly half as much as the SO₂ emissions from Mount Pinatubo in a shorter period. Popocatépetl volcano is thus considered as a high-emission rate, passively degassing eruptive volcano. SO₂ emission rates and SO₂ emissions are used here to make a mass balance of the erupted magma and related gases. Identified excess SO₂ is explained in terms of continuous degassing of unerupted magma and magma mixing. Fluctuations in SO₂ emission rate may be a result of convection and crystallization in the chamber or the conduits, cleaning and sealing of the plumbing system, and/or SO₂ scrubbing by the hydrothermal system.     

Sourcing and identifying andesitic tephras using major oxide titanomagnetite and hornblende chemistry,Egmont volcano and Tongariro Volcanic Centre,New Zealand

 Canonical discriminant function analysis was employed to discriminate between electron microprobe-determined titanomagnetite and hornblende analyses from Egmont volcano and Tongariro Volcanic Centre. Data sets of 436 titanomagnetite and 206 hornblende analyses from the two sources were used for the study. Titanomagnetite chemistry provided the best discrimination between these two sources with classification efficiencies of 99% for sample averages and 95% for individual analyses. The difference between sources for hornblende chemistry was less marked, but classification efficiencies of 100% for sample averages and 87% for individual analyses were achieved. Using the same methods a preliminary discrimination of individual Egmont volcano-sourced tephras was attempted. Titanomagnetite chemistry enabled the discrimination of several individual tephras or at least pairs of tephra units, but hornblende chemistry provided little discrimination. This technique provides an improvement on previous methods for chemically distinguishing distal tephra from the two sources as well as potentially identifying individual tephras from a particular source. A major advantage over previous discrimination techniques is that individual analyses can be classified with a known probability of group membership (with groups such as volcano source or an individual tephra unit). Tephras in a depositional environment where mixing is common such as within soil, loess and marine sequences, can be sourced or identified more easily with classification of individual grains. Received: 19 July 1995 / Accepted: 13 February 1996     

A monogenetic,Surtla-type,Surtseyan volcano from the Eocene-Oligocene Waiareka-Deborah volcanics,Otago, New Zealand: A model

The relics of a small, monogenetic, continental-shelf, Surtseyan volcano are preserved on the North Otago coast, South Island, New Zealand, in the late Eocene-early Oligocene Waiareka-Deborah volcanics. The succession consists of two parts, i. e. a lower interval of bedded lapilli tuffs and lapillistones, representing the eruptive, aggradational-cone-building phase, and an upper epiclastic sequence, representing the post-eruptive degradational phase. All of the preserved succession appears to have been deposited below storm wave base. The lapilli tuffs and lappillistones are subaqueous fall deposits, modified contemporaneously by downslope grain flow and turbidity current redeposition, and perhaps by local reworking caused by turbulent thermal eddies. The absence of major discordances in the lapilli tuffs suggests that the active eruptive period was very short-lived, perhaps lasting only a few days. The epiclastic succession consists of redeposited volcanic, skeletal, lime mud and glauconitic detritus, transported by debris flows and other mass flows. The initial epiclastic unit, a debris flow, appears to represent the sector collapse of a significant part of the cone. The appearance of fossils and rounded clasts low in the epiclastic succession coincides with stabilisation of the top of the submarine volcanic edifice, development of a wave-planed top, and its colonisation by a diverse fauna. Periodic storm activity swept material off the platform, redepositing it as marginal talus ramps. Surtla, a wholly submarine satellite volcanic centre of the 1963–1967 eruptive activity of Surtsey, is an excellent modern analogue for both the eruptive and post-eruptive phases of the Bridge Point-Aorere Point volcanic centre. By analogy with Surtla, the 120 metres of lapilli tuffs and lapillistones exposed on Bridge Point and Aorere Point accumulated in only several days. The 25 metres of reworked, glauconitic and fossiliferous volcaniclastics, represent thousands of years based on the time required for glauconite to form.     

Transport and emplacement mechanisms of channelised long-runout debris avalanches,Ruapehu volcano,New Zealand

The steep flanks of composite volcanoes are prone to collapse, producing debris avalanches that completely reshape the landscape. This study describes new insights into the runout of large debris avalanches enhanced by topography, using the example of six debris avalanche deposits from Mount Ruapehu, New Zealand. Individual large flank collapses (>1 km³) produced all of these units, with four not previously recognised. Five major valleys within the highly dissected landscape surrounding Mount Ruapehu channelled the debris avalanches into deep gorges (≥15 m) and resulted in extremely long debris avalanche runouts of up to 80 km from source. Classical sedimentary features of debris avalanche deposits preserved in these units include the following: very poor sorting with a clay-sand matrix hosting large subrounded boulders up to 5 m in diameter, jigsaw-fractured clasts, deformed clasts and numerous rip-up clasts of late-Pliocene marine sediments. The unusually long runouts led to unique features in distal deposits, including a pervasive and consolidated interclast matrix, and common rip-up clasts of Tertiary mudstone, as well as fluvial gravels and boulders. The great travel distances can be explained by the debris avalanches entering deep confined channels (≥15 m), where friction was minimised by a reduced basal contact area along with loading of water-saturated substrates which formed a basal lubrication zone for the overlying flowing mass. Extremely long-runout debris avalanches are most likely to occur in settings where initially partly saturated collapsing masses move down deep valleys and become thoroughly liquified at their base. This happens when pore water is available within the base of the flowing mass or in the sediments immediately below it. Based on their H/L ratio, confined volcanic debris avalanches are two to three times longer than unconfined, spreading flows of similar volume. The hybrid qualities of the deposits, which have some similarities to those of debris flows, are important to recognise when evaluating mass flow hazards at stratovolcanoes.     

Environmental hazards of fluoride in volcanic ash: a case study from Ruapehu volcano, New Zealand

The vent-hosted hydrothermal system of Ruapehu volcano is normally covered by a c. 10 million m³ acidic crater lake where volcanic gases accumulate. Through analysis of eruption observations, granulometry, mineralogy and chemistry of volcanic ash from the 1995–1996 Ruapehu eruptions we report on the varying influences on environmental hazards associated with the deposits. All measured parameters are more dependent on the eruptive style than on distance from the vent. Early phreatic and phreatomagmatic eruption phases from crater lakes similar to that on Ruapehu are likely to contain the greatest concentrations of environmentally significant elements, especially sulphur and fluoride. These elements are contained within altered xenolithic material extracted from the hydrothermal system by steam explosions, as well as in residue hydrothermal fluids adsorbed on to particle surfaces. In particular, total F in the ash may be enriched by a factor of 6 relative to original magmatic contents, although immediately soluble F does not show such dramatic increases. Highly soluble NaF and CaSiF₆ phases, demonstrated to be the carriers of ‘available’ F in purely magmatic eruptive systems, are probably not dominant in the products of phreatomagmatic eruptions through hydrothermal systems. Instead, slowly soluble compounds such as CaF₂, AlF₃ and Ca₅(PO₄)₃F dominate. Fluoride in these phases is released over longer periods, where only one third is leached in a single 24-h water extraction. This implies that estimation of soluble F in such ashes based on a single leach leads to underestimation of the F impact, especially of a potential longer-term environmental hazard. In addition, a large proportion of the total F in the ash is apparently soluble in the digestive system of grazing animals. In the Ruapehu case this led to several thousand sheep deaths from fluorosis.     

Monitoring and mapping of hydrogen sulphide emissions across an active geothermal field: Rotorua,New Zealand

Hydrogen sulphide (H₂S) is one of a number of gaseous species associated with geothermal activity in the Taupo Volcanic Zone (TVZ), New Zealand. The city of Rotorua is located within Rotorua Caldera in the TVZ and is one of the few urban areas in the world where a large population (>60,000 people) is frequently exposed to geothermal emissions. In order to evaluate the health hazard from long-term exposure to H₂S being emitted from the Rotorua geothermal field, a passive sampler has been developed to measure concentrations of H₂S at many locations across the city simultaneously. In contrast to other passive or pump-based samplers, the sampler is inexpensive, easily mass-manufactured, and involves the reaction of H₂S with silver halide contained in treated photographic paper. H₂S-exposed paper shows a distinct colour change from white to dark brown as H₂S concentrations increase and is sensitive to concentrations between ≪30 and around 1000 ppb. Rotorua city can be divided into three regions—an area of low H₂S concentration in the west, a ‘corridor’ of high concentrations running north–south through the city centre where H₂S is being emitted, and an area of medium concentration to the east which is influenced by the prevailing wind direction, creating a plume from the central corridor. The data give new insight into the subsurface routes of degassing in the Rotorua geothermal field, by showing the surface expression of the main upflow zone and the direction of the conjectured faulting below.