Nankai Trough, Japan Trench and Kuril Trench: geochemistry of Fluids sampled by submersible “Nautile”

Deep-water samples collected during the Kaiko project are often associated with biological communities located on geological structures favorable to fluid venting. The evidence of fluid venting are the temperature anomalies, the decrease in sulfate concentrations, the content in methane and the lowC₁(C₂ +C₃) ratio of light hydrocarbons. Because of large dilution by ambiant seawater during sampling it is difficult to compute the composition of the advected end-member pore fluid. Part of this fluid should originate in the “petroleum window”, i.e. at temperature about 60°C. Modeling the upward flow of water, taking into account the anomalies of temperature measured on the seafloor and the geochemical anomalies, leads to non-steady-state advection of the pore fluid. The occurrence of a deep component in the fluid has implications for the geological and tectonic models of the subduction zones off Japan.     

Flux and dispersion of gases from the “Drachenschlund” hydrothermal vent at 8°18' S, 13°30' W on the Mid-Atlantic Ridge

Hydrothermal emission of mantle helium appears to be directly related to magma production rate, but other processes can generate methane and hydrogen on mid-ocean ridges. In an on-going effort to characterize these processes in the South Atlantic, the flux and distribution of these gases were investigated in the vicinity of a powerful black smoker recently discovered at 8°17.9' S, 13°30.4' W. The vent lies on the shoulder of an oblique offset in the Mid-Atlantic Ridge and discharges high concentrations of methane and hydrogen. Measurements during expeditions in 2004 and 2006 show that the ratio of CH₄ to ³He in the neutrally buoyant plume is quite high, 4 × 10⁸. The CTD stations were accompanied by velocity measurements with lowered acoustic Doppler current profilers (LADCP), and from these data we estimate the methane transport to have been 0.5 mol s^− 1 in a WSW-trending plume that seems to develop during the ebb tidal phase. This transport is an order of magnitude greater than the source of CH₄ calculated from its concentration in the vent fluid and the rise height of the plume. From this range of methane fluxes, the source of ³He is estimated to be between 0.14 and 1.2 nmol s^− 1. In either case, the ³He source is significantly lower than expected from the spreading rate of the Mid-Atlantic Ridge. From the inventory of methane in the rift valley adjacent to the vent, it appears that the average specific rate of oxidation is 2.6 to 23 yr^− 1, corresponding to a turnover time between 140 and 16 days. Vertical profiles of methane in the surrounding region often exhibited Gaussian-like distributions, and the variances appear to increase with distance from the vent. Using a Gaussian plume model, we obtained a range of vertical eddy diffusivities between 0.009 and 0.08 m²m² s^− 1. These high values may be due to tidally driven internal waves across the promontory on which the vent is located.     

Crustal thickness along the western Galápagos Spreading Center and the compensation of the Galápagos hotspot swell

Wide-angle refraction and multichannel reflection seismic data show that oceanic crust along the Galápagos Spreading Center (GSC) between 97°W and 91°25′W thickens by 2.3 km as the Galápagos plume is approached from the west. This crustal thickening can account for ∼52% of the 700 m amplitude of the Galápagos swell. After correcting for changes in crustal thickness, the residual mantle Bouguer gravity anomaly associated with the Galápagos swell shows a minimum of −25 mGal near 92°15′W, the area where the GSC is intersected by the Wolf-Darwin volcanic lineament (WDL). The remaining depth and gravity anomalies indicate an eastward reduction of mantle density, estimated to be most prominent above a compensation depth of 50-100 km. Melting calculations assuming adiabatic, passive mantle upwelling predict the observed crustal thickening to arise from a small increase in mantle potential temperature of ∼30°C. The associated thermal expansion and increase in melt depletion reduce mantle densities, but to a degree that is insufficient to explain the geophysical observations. The largest density anomalies appear at the intersection of the GSC and the WDL. Our results therefore require the existence of compositionally buoyant mantle beneath the GSC near the Galápagos plume. Possible origins of this excess buoyancy include melt retained in the mantle as well as mantle depleted by melting in the upwelling plume beneath the Galápagos Islands that is later transported to the GSC. Our estimate for the buoyancy flux of the Galápagos plume (700 kg s⁻¹) is lower than previous estimates, while the total crustal production rate of the Galápagos plume (5.5 m³s⁻¹) is comparable to that of the Icelandic and Hawaiian plumes.     

A multidisciplinary effort to assign realistic source parameters to models of volcanic ash-cloud transport and dispersion during eruptions

During volcanic eruptions, volcanic ash transport and dispersion models (VATDs) are used to forecast the location and movement of ash clouds over hours to days in order to define hazards to aircraft and to communities downwind. Those models use input parameters, called “eruption source parameters”, such as plume height H, mass eruption rate Ṁ, duration D, and the mass fraction m₆₃ of erupted debris finer than about 4 or 63 μm, which can remain in the cloud for many hours or days. Observational constraints on the value of such parameters are frequently unavailable in the first minutes or hours after an eruption is detected. Moreover, observed plume height may change during an eruption, requiring rapid assignment of new parameters. This paper reports on a group effort to improve the accuracy of source parameters used by VATDs in the early hours of an eruption. We do so by first compiling a list of eruptions for which these parameters are well constrained, and then using these data to review and update previously studied parameter relationships. We find that the existing scatter in plots of H versus Ṁ yields an uncertainty within the 50% confidence interval of plus or minus a factor of four in eruption rate for a given plume height. This scatter is not clearly attributable to biases in measurement techniques or to well-recognized processes such as elutriation from pyroclastic flows. Sparse data on total grain-size distribution suggest that the mass fraction of fine debris m₆₃ could vary by nearly two orders of magnitude between small basaltic eruptions ( 0.01) and large silicic ones (> 0.5). We classify eleven eruption types; four types each for different sizes of silicic and mafic eruptions; submarine eruptions; “brief” or Vulcanian eruptions; and eruptions that generate co-ignimbrite or co-pyroclastic flow plumes. For each eruption type we assign source parameters. We then assign a characteristic eruption type to each of the world's  1500 Holocene volcanoes. These eruption types and associated parameters can be used for ash-cloud modeling in the event of an eruption, when no observational constraints on these parameters are available.     

Chemical reaction rates and entrainment within the Endeavour Ridge hydrothermal plume

The aging of the hydrothermal plume over the Endeavour segment of the Juan de Fuca Ridge was estimated by measuring the²²²Rn³He ratio in the plume as it dispersed. Despite uncertainties in the source function of hydrothermal input, it wa determined that the relative sequence of removal from the plume isH₂ > Δc >²²²Rn>CH₄ Mn, whereΔc is a measure of particle concentration and the mean life of²²²Rn is 5.5 days. H₂ is removed from the plume within hours of input while Mn is not removed within the two-week timescale of the radon-helium clock.Entrainment of bottom water within the buoyant plume may introduce additional chemical signatures into the spreading effluent layer over that which would be introduced by hydrothermal discharge alone. This is particularly significant for those chemical species which are not greatly enriched in the vent fluids relative to bottom water concentration and which display a nutrient-like profile in the deep ocean. Thus we found that significant fractions of the Si and²²⁶Ra anomalies in the plume were not of hydrothermal origin but were derived from entrained bottom water which has a higher concentration of these elements than ambient water at plume height.     

A buoyant plume adjacent to a headland—Observations of the Elwha River plume

Small rivers commonly discharge into coastal settings with topographic complexities - such as headlands and islands - but these settings are underrepresented in river plume studies compared to more simplified, straight coasts. The Elwha River provides a unique opportunity to study the effects of coastal topography on a buoyant plume, because it discharges into the Strait of Juan de Fuca on the western side of its deltaic headland. Here we show that this headland induces flow separation and transient eddies in the tidally dominated currents (O(100 cm/s)), consistent with other headlands in oscillatory flow. These flow conditions are observed to strongly influence the buoyant river plume, as predicted by the “small-scale” or “narrow” dynamical classification using Garvine's (1995) system. Because of the transient eddies and the location of the river mouth on the headland, flow immediately offshore of the river mouth is directed eastward twice as frequently as it is westward. This results in a buoyant plume that is much more frequently “bent over” toward the east than the west. During bent over plume conditions, the plume was attached to the eastern shoreline while having a distinct, cuspate front along its westernmost boundary. The location of the front was found to be related to the magnitude and direction of local flow during the preceding O(1 h), and increases in alongshore flow resulted in deeper freshwater mixing, stronger baroclinic anomalies, and stronger hugging of the coast. During bent over plume conditions, we observed significant convergence of river plume water toward the frontal boundary within 1 km of the river mouth. These results show how coastal topography can strongly influence buoyant plume behavior, and they should assist with understanding of initial coastal sediment dispersal pathways from the Elwha River during a pending dam removal project.     

Patos Lagoon outflow within the Río de la Plata plume using an airborne salinity mapper: Observing an embedded plume

Major river systems discharging into continental shelf waters frequently form buoyant coastal currents that propagate along the continental shelf in the direction of coastal trapped wave propagation (with the coast on the right/left, in the northern/southern hemisphere). The combined flow of the Uruguay and Paraná Rivers, which discharges freshwater into the Río de la Plata estuary (Lat. ∼36°S), often gives rise to a buoyant coastal current (the ‘Plata plume’) that extends northward along the continental shelf off Uruguay and Southern Brazil. Depending upon the prevailing rainfall, wind and tidal conditions, the Patos/Mirim Lagoon complex (Lat. ∼32°S) may also produce a freshwater outflow plume that expands across the inner continental shelf. Under these circumstances the Patos outflow plume can be embedded in temperature, salinity and current fields that are strongly influenced by the larger Plata plume. The purpose of this paper is to present observations of such an embedded plume structure and to determine the dynamical characteristics of the ambient and embedded plumes.     

IDOAS: A new monitoring technique to study the 2D distribution of volcanic gas emissions

Imaging Differential Optical Absorption Spectroscopy (IDOAS) is an optical remote-sensing method using scattered sunlight as light source. It combines a “pushbroom” imaging spectrometer with the DOAS technique and thus allows imaging two-dimensional trace gas distributions, e.g., in volcanic plumes. The highly sensitive and specific detection of many trace gases simultaneously (specific molecules, not just elements, e.g. SO₂, BrO, NO₂, O₃, HCHO, etc.) is possible, and the temporal and spatial variation of these gases can be measured. The IDOAS system presented here enables the taking of two-dimensional images of trace gas distributions in a volcanic plume with a spatial resolution of 100 pixels horizontally × 64 pixels vertically, each with a field of view of 0.087° in horizontal and 0.208° in vertical directions. Therefore, IDOAS provides useful information about the chemical composition and chemical variability in a volcanic plume and allows studying plume dispersal and chemical transformations. The technique was applied to map the SO₂ distribution in the plume of Mt. Etna volcano for the first time in October 2003.     

Nutrient processes and chlorophyll in the estuaries and plume of the Gulf of Papua

This paper investigates the waters of the Gulf of Papua during three cruises of the TROPICS (Tropical River Ocean Processes In Coastal Settings) programme. Plume characteristics were investigated during Leg 1 (May 1997), and estuarine properties during Leg 5a (September 1997) and Leg 7 (January 1999). During Leg 1 the plume was apparent as a well mixed layer up to 30 m deep extending offshore to a distance of 150 km off the Fly River. Lowest salinities were found off the Taruma Delta. Highest chlorophyll concentrations were found at the inner plume close to the river mouth. Dissolved phosphate and nitrate are removed in this zone, whereas silicate behaves conservatively. Primary productivity within the plume appears to rely upon recycled nutrients, with organic fractions representing the majority of the nutrient pool. In the estuaries nutrients were found to behave differently during the monsoon than during the low flow of the extremely dry conditions associated with the 1997 El Niño event. Normally the Fly is characterised by remineralisation of organic nitrogen in the upper estuary, but during drought conditions DON production and NH₄⁺ uptake suggest that bacterial activity is more prevalent. Ocean Colour and Temperature Scanner imagery shows a number of features of the plume, but generally overestimates chlorophyll concentrations due to the effects of high suspended sediment concentrations and, to a lesser extent, coloured dissolved organic matter.     

Thermal-image-derived dynamics of vertical ash plumes at Santiaguito volcano,Guatemala

Vertical ash plumes were imaged at Santiaguito (Guatemala) using a thermal camera to capture plume ascent dynamics. The plumes comprised a convecting plume front fed by a steady feeder plume. Of the 25 plumes imaged, 24 had a gas thrust region within which ascent velocities were 15–50 m s⁻¹. A transition to buoyant ascent occurred 20 to 50 m above the vent, where ascent velocities declined to 4–15 m s⁻¹. Plumes that attained greater heights had higher heat contents, wider feeder plumes and higher buoyant ascent velocities.     

Hydrothermal activity on the southern Mid-Atlantic Ridge: Tectonically- and volcanically-controlled venting at 4–5°S

We report results from an investigation of the geologic processes controlling hydrothermal activity along the previously-unstudied southern Mid-Atlantic Ridge (3–7°S). Our study employed the NOC (UK) deep-tow sidescan sonar instrument, TOBI, in concert with the WHOI (USA) autonomous underwater vehicle, ABE, to collect information concerning hydrothermal plume distributions in the water column co-registered with geologic investigations of the underlying seafloor. Two areas of high-temperature hydrothermal venting were identified. The first was situated in a non-transform discontinuity (NTD) between two adjacent second-order ridge-segments near 4°02′S, distant from any neovolcanic activity. This geologic setting is very similar to that of the ultramafic-hosted and tectonically-controlled Rainbow vent-site on the northern Mid-Atlantic Ridge. The second site was located at 4°48′S at the axial-summit centre of a second-order ridge-segment. There, high-temperature venting is hosted in an  18 km² area of young lava flows which in some cases are observed to have flowed over and engulfed pre-existing chemosynthetic vent-fauna. In both appearance and extent, these lava flows are directly reminiscent of those emplaced in Winter 2005−06 at the East Pacific Rise, 9°50′N and reference to global seismic catalogues reveals that a swarm of large (M 4.6−5.6) seismic events was centred on the 5°S segment over a  24 h period in late June 2002, perhaps indicating the precise timing of this volcanic eruptive episode. Temperature measurements at one of the vents found directly adjacent to the fresh lava flows at 5°S MAR (Turtle Pits) have subsequently revealed vent-fluids that are actively phase separating under conditions very close to the Critical Point for seawater, at  3000 m depth and 407 °C: the hottest vent-fluids yet reported from anywhere along the global ridge crest.     

Characteristics of hydrothermal plumes from two vent fields on the Juan de Fuca Ridge, northeast Pacific Ocean

Deep CTD/transmissometer tows and water bottle sampling were used during 1985 to map the regional distribution of the neutrally-buoyant plumes emanating from each of two major vent fields on the Southern Symmetrical Segment (SSS) and Endeavour Segment (ES) of the Juan de Fuca Ridge. At both vent fields, emissions from point and diffuse hydrothermal sources coalesced into a single 200-m-thick plume elongated in the direction of current flow and with characteristic temperature anomalies of 0.02–0.05°C and light-attenuation anomalies of 0.01–0.08 m⁻¹ (10–80 μg/l above background). Temperature anomalies in the core of each plume were uniform as far downcurrent as the plumes were mapped (10–15 km). Downcurrent light-attenuation trends were non-uniform and differed between plumes, apparently because different vent fluid chemistries at each field cause significant differences in the settling characteristics of the hydrothermal precipitates. Vent fluids from the SSS are metal-dominated and mostly precipitate very fine-grained hydrous Fe-oxides that remain suspended in the plume. Vent fluids from the ES are sulfur-dominated and precipitate a high proportion of coarser-grained Fe-sulfides that rapidly settle from the plume. The integrated flux of each vent field was estimated from measurements of the advective transport of each plume. Heat flux was 1700 ± 1100 MW from the ES and 580 ± 351 MW from the SSS. Particle flux varied from 546 ± 312 g/s to 204 ± 116 g/s at the ES depending on distance from the vent field, and was 92 ± 48 g/s from the SSS.     

Dynamical geochemistry of the Hawaiian plume

This paper presents a simple dynamical model for melting and trace element distribution in the Hawaiian mantle plume. I model the plume as a partially molten stagnation point flow against the oceanic lithosphere, and obtain solutions for the temperature, melt migration rate, and trace element concentration within it. Trace element concentrations in the melt exceed simple batch melting predictions by up to 70%. The magnitude of this effect depends strongly on the solid-melt partition coefficientK. Trace elements with differentK therefore experience a “dynamical fractionation” within the plume, and incompatible trace element ratios such asLa/Ce always exceed the batch melting predictions. I suggest a simple model for plume-lithosphere interaction in which melts from these two sources mix in proportions determined by thermodynamic constraints. The model can explain the composition of basalts from Haleakala if the degree of melting of the lithosphereF₁ decreases with time from roughly 10% for tholeiites to 2% for alkalic basalts. These values are considerably higher than previous estimates ofF₁ < 1%, and imply correspondingly smaller and more realistic values ( 10 km) for the thickness of the melted part of the lithosphere. Partial melting of additional depleted sources such as the asthenosphere is therefore not required by the Haleakala data. Estimates ofF₁ are highly sensitive to the values chosen for the partition coefficients, however, and should therefore be interpreted with caution.     

Upscaling of CO2 vertical migration through a periodic layered porous medium: The capillary-free and capillary-dominant cases

We present an upscaled model for the vertical migration of a CO₂ plume through a vertical column filled with a periodic layered porous medium. This model may describe the vertical migration of a CO₂ plume in a perfectly layered horizontal aquifer. Capillarity and buoyancy are taken into account and semi-explicit upscaled flux functions are proposed in the two following cases: (i) capillarity is the main driving force and (ii) buoyancy is the only driving force. In both cases, we show that the upscaled buoyant flux is a bell-shaped function of the saturation, as in the case of a homogeneous porous medium. In the capillary-dominant case, we show that the upscaled buoyant flux is the harmonic mean of the buoyant fluxes in each layer. The upscaled saturation is governed by the continuity of the capillary pressure at the interface between layers. In the capillary-free case, the upscaled buoyant flux and upscaled saturation are determined by the flux continuity condition at the interface. As the flux is not continuous over the entire range of saturation, the upscaled saturation is only defined where continuity is verified, i.e. in two saturation domains. As a consequence, the upscaled buoyant flux is described by a piecewise continuous function. Two analytical approximations of this flux are proposed and this capillary-free upscaled model is validated for two cases of heterogeneity. Upscaled and cell averaged saturations are in good agreement. Furthermore, the proposed analytical upscaled fluxes provide satisfactory approximations as long as the saturation set at the inlet of the column is in a range where analytical and numerical upscaled fluxes are close.     

Metropolitan-scale Transport and Dispersion from the New York World Trade Center Following September 11, 2001. Part II: An Application of the CALPUFF Plume Model

Following the collapse of the New York World Trade Center (WTC) towers on September 11, 2001, Local, State, and Federal agencies initiated numerous air monitoring activities to better understand the ongoing impacts of emissions from the disaster. The collapse of the World Trade Center towers and associated fires that lasted for several weeks resulted at times in a noticeable plume of material that was dispersed around the Metropolitan New York City (NYC) area. In general, the plume was only noticeable for a short period of time following September 11, and only apparent close to the World Trade Center site. A study of the estimated pathway which the plume of WTC material would likely follow was completed to support the United States Environmental Protection Agency’s 2002 initial exposure assessments. In this study, the WTC emissions were simulated using the CALMET-CALPUFF model in order to examine the general spatial and temporal dispersion patterns over NYC. This paper presents the results of the CALPUFF plume model in terms of plume dilution and location, since the exact source strength remains unknown. Independent observations of PM_2.5 are used to support the general dispersion features calculated by the model. Results indicate that the simulated plume matched well with an abnormal increase (600–1000% of normal) in PM_2.5 two nights after the WTC collapse as the plume rotated north to southeast, towards parts of NYC. Very little if any evidence of the plume signature was noted during a similar flow scenario a week after September 11. This leads to the conclusion that other than areas within a few kilometers from the WTC site, the PM_2.5 plume was not observable over NYC’s background concentration after the first few days.     

Magmatismes basiques dits “orogeniques” et “anorogeniques” et teneurs entro2: Les associations “Isotitanees” et “anisotitanfes”

The patterns of variation of TiO₂ conent during magmatic evolution are different in the so called “orogenic” and “anorogenie” basic associations; these last terms, which are the cause of much misunderstanding, can be replaced by the terms “isotitaniferous” and “anisotitaniferous”.     

Geochemical mapping of magmatic gas–water–rock interactions in the aquifer of Mount Etna volcano

Systematic analysis of major and minor elements in groundwaters from springs and wells on the slopes of Mt. Etna in 1995–1998 provides a detailed geochemical mapping of the aquifer of the volcano and of the interactions between magmatic gas, water bodies and their host rocks. Strong spatial correlations between the largest anomalies in pCO₂ (pH and alkalinity) K, Rb, Mg, Ca and Sr suggest a dominating control by magmatic gas (CO₂) and consequent basalt leaching by acidified waters of the shallow (meteoric) Etnean aquifer. Most groundwaters displaying this magmatic-type interaction discharge within active faulted zones on the S–SW and E lower flanks of the volcanic pile, but also in a newly recognised area on the northern flank, possibly tracking a main N–S volcano-tectonic structure. In the same time, the spatial distribution of T°C, TDS, Na, Li, Cl and B allows us to identify the existence of a deeper thermal brine with high salinity, high content of B, Cl and gases (CO₂, H₂S, CH₄) and low K/Na ratio, which is likely hosted in the sedimentary basement. This hot brine reaches the surface only at the periphery of the volcano near the Village of Paternò, where it gives rise to mud volcanoes called “Salinelle di Paternò”. However, the contribution of similar brines to shallower groundwaters is also detected in other sectors to the W (Bronte, Maletto), SW (Adrano) and SE (Acireale), suggesting its possible widespread occurrence beneath Etna. This thermal brine is also closely associated with hydrocarbon fields all around the volcano and its rise, generally masked by the high outflow of the shallow aquifer, may be driven by the ascent of mixed sedimentary–magmatic gases through the main faults cutting the sedimentary basement.     

On the dynamics of 3-D single thermal plumes at various Prandtl numbers and Rayleigh numbers

Three-dimensional (3-D) numerical simulations of single turbulent thermal plumes in the Boussinesq approximation are used to understand more deeply the interaction of a plume with itself and its environment. In order to do so, we varied the Rayleigh and Prandtl numbers from Ra?～?10⁵ to Ra?～?10⁸ and from Pr?～?0.025 to Pr?～?70. We found that thermal dissipation takes place mostly on the border of the plume. Moreover, the rate of energy dissipation per unit mass ε _T has a critical point around Pr?～?0.7. The reason is that at Pr greater than ～0.7, buoyancy dominates inertia and thermal advection dominates wave formation whereas this trend is reversed at Pr less than ～0.7. We also found that for large enough Prandtl number (Pr?～?70), the velocity field is mostly poloidal although this result was known for Rayleigh–Bénard convection (see Schmalzl et al. [On the validity of two-dimensional numerical approaches to time-dependent thermal convection. Europhys. Lett. 2004, 67, 390--396]). On the other hand, at small Prandtl numbers, the plume has a large helicity at large scale and a non-negligible toroidal part. Finally, as observed recently in details in weakly compressible turbulent thermal plume at Pr?=?0.7 (see Plourde et al. [Direct numerical simulations of a rapidly expanding thermal plume: structure and entrainment interaction. J. Fluid Mech. 2008, 604, 99--123]), we also noticed a two-time cycle in which there is entrainment of some of the external fluid to the plume, this process being most pronounced at the base of the plume. We explain this as a consequence of calculated Richardson number being unity at Pr?=?0.7 when buoyancy balance inertia.     

The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

Water contents, temperatures and diversity of the magmas of the catastrophic eruption of Nevado del Ruiz, Colombia, November 13, 1985

The petrology of the highly phyric two-pyroxene andesitic to dacitic pyroclastic rocks of the November 13, 1985 eruption of Nevado del Ruiz, Colombia, reveals evidence of: (1) increasingly fractionated bulk compositions with time; (2) tapping of a small magma chamber marginally zoned in regard to H₂O contents (1 to 4%), temperature (960–1090°C), and amount of residual melt (35 to 65%); (3) partial melting and assimilation of degassed zones in the hotter less dense interior of the magma chamber; (4) probable heating, thermal disruption and mineralogic and compositional contamination of the magma body by basaltic magma “underplating”; and (5) crustal contamination of the magmas during ascent and within the magma chamber. Near-crater fall-back or “spill-over” emitted in the middle of the eruptive sequence produced a small pyroclastic flow that became welded in its central and basal portions because of ponding and thus heat conservation on the flat glaciated summit near the Arenas crater. The heterogeneity of Ruiz magmas may be related to the comparatively small volume (0.03 km³) of the eruption, nearly ten times less than the 0.2 km³ of the Plinian phase of Mount St. Helens, and probable steep thermal and P_H2O gradients of a small source magma chamber, estimated at 300 m long and 100 m wide for an assumed ellipsoidal shape.