Studies of the formation process of water-in-oil emulsions

This paper summarizes studies to determine the formation process of water-in-oil emulsions and the stability of such emulsions formed in the laboratory and in a large test tank. These studies have confirmed that water-in-oil mixtures can be grouped into four states: stable emulsions, unstable water-in-oil mixtures, mesostable emulsions, and entrained water. These states are differentiated by rheological properties as well as by differences in visual appearance. The viscosity of a stable emulsion at a shear rate of one reciprocal second is about three orders of magnitude greater than that of the starting oil. An unstable emulsion usually has a viscosity no more than about 20 times greater than that of the starting oil. A stable emulsion has a significant elasticity, whereas an unstable emulsion does not. A mesostable emulsion has properties between stable and unstable, but breaks down within a few days of standing. The usual situation is that emulsions are either obviously stable, mesostable, or unstable. Entrained water, water suspended in oil by viscous forces alone, is also evident. Very few emulsions have questionable stability. Analytical techniques were developed to test these observations.

The type of emulsion produced is determined primarily by the properties of the starting oil. The most important of these properties are the asphaltene and resin content and the viscosity of the oil. The composition and property ranges of the starting oil that would be required to form each of the water-in-oil states are discussed in this paper.     

Oil viscosity limitation on dispersibility of crude oil under simulated at-sea conditions in a large wave tank

This study determined the limiting oil viscosity for chemical dispersion of oil spills under simulated sea conditions in the large outdoor wave tank at the US National Oil Spill Response Test Facility in New Jersey. Dispersant effectiveness tests were completed using crude oils with viscosities ranging from 67 to 40,100 cP at test temperature. Tests produced an effectiveness-viscosity curve with three phases when oil was treated with Corexit 9500 at a dispersant-to-oil ratio of 1:20. The oil viscosity that limited chemical dispersion under simulated at-sea conditions was in the range of 18,690 cP to 33,400 cP. Visual observations and measurements of oil concentrations and droplet size distributions in the water under treated and control slicks correlated well with direct measurements of effectiveness. The dispersant effectiveness versus oil viscosity relationship under simulated at sea conditions at Ohmsett was most similar to those from similar tests made using the Institut Francais du Pétrole and Exxon Dispersant Effectiveness (EXDET) test methods.     

The formation of “chocolate mousse” from Statfjord crude oil and seawater

Physical factors affecting the formation of water-in-oil emulsions (‘chocolate mousse’) from crude Statfjord oil was investigated in the laboratory. Irradiation by visible light and mechanical agitation are shown to be essential. It is suggested that photochemical oxidation of oil components leads to the formation of surface-active, oil-soluble compounds. When these reach a sufficient concentration in the oil, water will be retained within the oil during physical mixing. The plausibility of such a mechanism is investigated further using additions of tetradecanal as an oil-soluble, surface-active agent and β-carotene as an inhibitor of photooxidation. The use of additives to stop ‘mousse’ formation is suggested.     

The relationship between oil droplet size and upper ocean turbulence

Oil spilled at sea often forms oil droplets in stormy conditions. This paper examines possible mechanisms which generate the oil droplets. When droplet Reynolds numbers are large, the dynamic pressure force of turbulent flows is the cause of droplet breakup. Using dimensional analysis, Hinze (1955, A.I.Ch.E. Journal 1, 289–295) obtained a formula for the maximum size of oil droplets that can survive the pressure force. When droplet Reynolds numbers are small, however, viscous shear associated with small turbulent eddies is the cause of breakup. For the shear mechanism, we obtain estimates of droplet size as a function of energy dissipation rate, the ratio of oil-to-water viscosity and the surface tension coefficient.

The two formulae are applied to oil spills in the ocean. At dissipation rates expected in breaking waves, the pressure force is the dominant breakup mechanism and can generate oil droplets with radii of hundreds of microns. However, when chemical dispersants are used to treat an oil slick and significantly reduce the oil-water interfacial tension, viscous shear is the dominant breakup mechanism and oil droplets with radii of tens of microns can be generated. Viscous shear is also the mechanism for disintegrating water-in-oil emulsions and the size of a typical emulsion blob is estimated to be tens of millimeters.     

Multi-scale validation strategy for satellite albedo products and its uncertainty analysis

Coarse-resolution satellite albedo products are important for climate change and energy balance research because of their capability to characterize the spatiotemporal patterns of land surface parameters at both the regional and global scales. The accuracy of coarse-resolution products is usually assessed via comparison with in situ measurements. The key issue in the comparison of remote sensing observations with in situ measurements is scaling and uncertainty. This paper presents a strategy for validating 1-km-resolution remote sensing albedo products using field measurements and high-resolution remote sensing observations. Field measurements were collected to calibrate the high-resolution(30 m) albedo products derived from HJ-1a/b images. Then, the calibrated high-resolution albedo maps were resampled(i.e., upscaled) to assess the accuracy of the coarse-resolution albedo products. The samples of field measurements and high-resolution pixels are based on an uncertainty analysis. Two types of coarse-resolution albedo datasets, from global land surface satellite(GLASS) and moderate-resolution imaging spectroradiometer(MODIS), are validated over the middle reaches of the Heihe River in China. The results indicate that the upscaled HJ(Huan Jing means environment in Chinese and this refers to a satellite constellation designed for environment and disaster monitoring by China) albedo, which was calibrated using field measurements, can provide accurate reference values for validating coarse-resolution satellite albedo products. However, the uncertainties in the upscaled HJ albedo should be estimated, and pixels with large uncertainties should be excluded from the validation process.     

Determining the dispersibility of South Louisiana crude oil by eight oil dispersant products listed on the NCP Product Schedule

We recently conducted a laboratory study to measure the dispersion effectiveness of eight dispersants currently listed on the National Contingency Plan Product Schedule. Results are useful in determining how many commercial dispersant products would have been effective for use on South Louisiana crude oil in the Deepwater Horizon oil spill. The test used was a modification of the Baffled Flask Test (BFT), which is being proposed to replace the current Swirling Flask Test (SFT). The modifications of the BFT in this study included use of one oil rather than two, increasing replication from 4 runs to 6, and testing at two temperatures, 5 °C and 25 °C. Results indicated that temperature was not as critical a variable as the literature suggested, likely because of the low viscosity and light weight of the SLC. Of the eight dispersants tested, only three gave satisfactory results in the laboratory flasks at both temperatures.     

Effects of petrophysical parameters on attenuation and dispersion of seismic waves in the simplified poroelastic theory: Comparison between the Biot's theory and viscosity‐extended theory

The simplified macro‐equations of porous elastic media are presented based on Hickey's theory upon ignoring effects of thermomechanical coupling and fluctuations of porosity and density induced by passing waves. The macro‐equations with definite physical parameters predict two types of compressional waves (P wave) and two types of shear waves (S wave). The first types of P and S waves, similar to the fast P wave and S wave in Biot's theory, propagate with fast velocity and have relatively weak dispersion and attenuation, while the second types of waves behave as diffusive modes due to their distinct dispersion and strong attenuation. The second S wave resulting from the bulk and shear viscous loss within pore fluid is slower than the second P wave but with strong attenuation at lower frequencies. Based on the simplified porous elastic equations, the effects of petrophysical parameters (permeability, porosity, coupling density and fluid viscosity) on the velocity dispersion and attenuation of P and S waves are studied in brine‐saturated sandstone compared with the results of Biot's theory. The results show that the dispersion and attenuation of P waves in simplified theory are stronger than those of Biot's theory and appear at slightly lower frequencies because of the existence of bulk and shear viscous loss within pore fluid. The properties of the first S wave are almost consistent with the S wave in Biot's theory, while the second S wave not included in Biot's theory even dies off around its source due to its extremely strong attenuation. The permeability and porosity have an obvious impact on the velocity dispersion and attenuation of both P and S waves. Higher permeabilities make the peaks of attenuation shift towards lower frequencies. Higher porosities correspond to higher dispersion and attenuation. Moreover, the inertial coupling between fluid and solid induces weak velocity dispersion and attenuation of both P and S waves at higher frequencies, whereas the fluid viscosity dominates the dispersion and attenuation in a macroscopic porous medium. Besides, the heavy oil sand is used to investigate the influence of high viscous fluid on the dispersion and attenuation of both P and S waves. The dispersion and attenuation in heavy oil sand are stronger than those in brine‐saturated sandstone due to the considerable shear viscosity of heavy oil. Seismic properties are strongly influenced by the fluid viscosity; thus, viscosity should be included in fluid properties to explain solid–fluid combination behaviour properly.     

Characterization and source of oil contamination on the beaches and seabird corpses, Sable Island, Nova Scotia, 1996-2005

During April 1996-May 2005, 2343 oiled seabird corpses were recorded in beach surveys conducted on Sable Island, Nova Scotia. One hundred eighty-three samples of oil were collected from the beaches and from the feathers of bird corpses. Gas chromatographic (GC/FID) analysis was used to identify generic oil type and likely marine source. During this period, at least 74 marine oil discharge events were probably responsible for beached pelagic tar and contamination of seabird corpses found on Sable Island, of which 77.0% were crude oils, 14.9% were fuel oils, and 8.1% were bilge oil mixtures. While fuel and bilge oils may be discharged by all vessel and platform types, crude oil discharges are associated with tanker operations. This study demonstrates that oiling of the sea from tankers remains a serious wildlife issue in the Northwest Atlantic.     

Viscosity of a Teide phonolite in the welding interval

The viscosity of a natural phonolitic composition with variable amounts of H₂O has been experimentally determined. The starting materials were crystal-free phonolitic glasses from Montaña Blanca, situated within the Las Cañadas caldera of Teide. Dry phonolitic melt viscosities were determined using concentric cylinder viscometry in the low viscosity range. The glassy quench products of these runs were then hydrated by high pressure synthesis in a piston–cylinder apparatus to generate a suite of samples with water contents ranging from 0.02 to 3.75 wt%. Samples thus hydrated were quenched rapidly and prepared (cut and polished) for the determination of water contents by infrared spectroscopy before and after experimental viscometry. The viscosities of the melts (dry and hydrated) were determined at 1 bar using a micropenetration technique. Samples were stable under the measurement conditions up to 3.75 wt% H₂O. Homogeneity of water content was confirmed by infrared spectroscopy and total water contents were calculated using absorptivity coefficients for compositions extremely close to that investigated here. The variation of viscosity as a function of water content and temperature can be described in the high viscosity interval of relevance to many welding processes by the non-Arrhenian expression:

(1)

log₁₀ η=−5.900−0.286 ln (H₂O)+(10775.4−394.8(H₂O))/(T−148.7+21.65 ln (H₂O))

whereas the high viscosity range alone is adequately described by the Arrhenian expression

(2)

log₁₀ η=−10.622−0.738 ln (H₂O)+(17114.3−590.4(H₂O))×1/T

where η is the viscosity in Pa s, H₂O is the water content in wt% and T is the temperature in K.These results are particularly useful for the scaling of conditions extant during the welding of phonolitic products of Montaña Blanca. The welding of glassy phonolitic rocks is enhanced by the lower viscosity of these melts with respect to calcalkaline rhyolites. The ratio of viscosities of phonolitic to calcalkaline rhyolitic melts is a complex function of temperature and water content and reaches up to 10^4.5 at 0.1 wt% H₂O and 500°C. Abundant evidence of welding and remobilisation of pyroclastic and spatter products of Teide system volcanism are consistent with these experimental observations.     

The pollution of groundwater and unsaturated zone rocks by oil products and PAH in urban areas

An approach to assessing the hazard of unsaturated zone rocks as a source of subsoil-water secondary pollution by oil products and PAH is considered based on environmental-geochemical studies of soils and rocks of the unsaturated zone, groundwater, and snow, which were carried out during the rehabilitation of the water environment of Lefortovskii Park (Moscow). The impact of the primary pollution sources is analyzed, and the formation of groundwater and rock pollution by oil products and PAH is considered. To assess the role of the unsaturated zone as a secondary source of pollution of surface and subsurface waters under the conditions of possible elimination of the primary sources, the transport of oil products (benzol and toluene) and PAH (pyrene) in unsaturated zone was simulated using WHI UnSat Suite Plus software package.     

The feasibility of isolation and detection of fullerenes and carbon nanotubes using the benzene polycarboxylic acid method

The incorporation of fullerenes and carbon nanotubes into electronic, optical and consumer products will inevitably lead to the presence of these anthropogenic compounds in the environment. To date, there have been few studies isolating these materials from environmental matrices. Here we report a method commonly used to quantify black carbon (BC) in soils, the benzene polycarboxylic acid (BPCA) method, for measurement of two types of single walled carbon nanotubes (SWCNTs), two types of fullerenes and two forms of soot. The distribution of BC products (BPCAs) from the high pressure and high temperature oxidation illustrates the condensed nature of these compounds because they form predominantly fully substituted mellitic acid (B6CA). The conversion of carbon nanoparticles to BPCAs was highest for fullerenes (average of 23.2 ± 4.0% C recovered for both C₆₀ and C₇₀) and lowest for non-functionalized SWCNTs (0.5 ± 0.1% C). The recovery of SWCNTs was 10 times higher when processed through a cation-exchange column, indicating the presence of metals in SWCNTs compromises the oxidation chemistry. While mixtures of SWCNTs, soot and sediment revealed small losses of black carbon during sample processing, the method is suitable for quantifying total BC. The BPCA distribution of mixtures did not agree with theoretical mixtures using model polyaromatic hydrocarbons, suggesting the presence of a matrix effect. Future work is required to quantify different types of black carbon within the same sample.     

A hierarchical approach measures the aerial extent and concentration levels of PAH-contaminated shoreline sediments at historic industrial sites in Prince William Sound, Alaska

A field study was conducted in 2003 to estimate the areal distribution and concentrations of polycyclic aromatic hydrocarbons (PAH) in intertidal sediments at sites of past human and industrial activity (HA sites) in Prince William Sound (PWS), Alaska, the site of the 1989 Exxon Valdez oil spill. More than 50 HA sites, primarily in western PWS, were identified through analysis of historic records and prior field studies, and nine sites were selected for detailed surveys. The areal assessment process consisted of seven steps: (1) identify site from historic records and field surveys; (2) locate visual evidence of surface oil/tar at a site; (3) prepare a site map and lay out a sampling grid over the entire site with 10-m grid spacing; (4) excavate pits to 50 cm depth on the grid; (5) perform a field colorimetric test to estimate total PAH (TPAH) in sediments from the wall of each pit and record the results in the ranges <1 ppm; 1-10 ppm; >10 ppm TPAH; (6) expand grid size if necessary if elevated PAH levels are detected colorimetrically; (7) select 20 samples from each site for same-day shipboard PAH analysis by immunoassay (SDI RaPID PAH) and, based on these results, select sediment samples from each site for full PAH analysis in the laboratory to identify PAH sources. A total of 416 pits were dug at the nine sites. Nine acres of sediments with TPAH >2500 ppb dry wt. were mapped at the nine sites. TPAH concentrations obtained by immunochemical analysis of 181 samples from the nine sites ranged from 20 to 1,320,000 ppb (wet wt.). The contaminants are mixtures of petroleum products (2-3 ring PAH) and combustion products (4-6 ring PAH) unrelated to the 1989 Exxon Valdez oil spill. Mussels and clams collected at these sites have elevated levels of PAH that are compositionally similar to the PAH in the sediments. These findings indicate that at least a portion of the sediment PAH is bioavailable. The PAH sources at these historic industrial sites are chronic. They include relict fuel oil tanks and works located above and within the intertidal zone, with contamination at some locations extending into nearshore sub-tidal sediments. This study shows how a hierarchical approach can be used to quickly and successfully map, quantify, and subsequently, identify sources of PAH in shoreline sediments.     

Monitoring viscosity changes from time‐lapse seismic attenuation: case study from a heavy oil reservoir

Heating heavy oil reservoirs is a common method for reducing the high viscosity of heavy oil and thus increasing the recovery factor. Monitoring of these viscosity changes in the reservoir is essential for delineating the heated region and controlling production. In this study, we present an approach for estimating viscosity changes in a heavy oil reservoir. The approach consists of three steps: measuring seismic wave attenuation between reflections from above and below the reservoir, constructing time‐lapse Q and Q^?1 factor maps, and interpreting these maps using Kelvin–Voigt and Maxwell viscoelastic models. We use a 4D relative spectrum method to measure changes in attenuation. The method is tested with synthetic seismic data that are noise free and data with additive Gaussian noise to show the robustness and the accuracy of the estimates of the Q‐factor. The results of the application of the method to a field data set exhibit alignment of high attenuation zones along the steam‐injection wells, and indicate that temperature dependent viscosity changes in the heavy oil reservoir can be explained by the Kelvin–Voigt model.     

Evaluation of precipitation products over complex mountainous terrain: A water resources perspective

The availability of in situ measurements of precipitation in remote locations is limited. As a result, the use of satellite measurements of precipitation is attractive for water resources management. Combined precipitation products that rely partially or entirely on satellite measurements are becoming increasingly available. However, these products have several weaknesses, for example their failure to capture certain types of precipitation, limited accuracy and limited spatial and temporal resolution. This paper evaluates the usefulness of several commonly used precipitation products over data scarce, complex mountainous terrain from a water resources perspective. Spatially averaged precipitation time series were generated or obtained for 16 sub-basins of the Paute river basin in the Ecuadorian Andes and 13 sub-basins of the Baker river basin in Chilean Patagonia. Precipitation time series were generated using the European Centre for Medium Weather Range Forecasting (ECMWF) 40 year reanalysis (ERA-40) and the subsequent ERA-interim products, and the National Centers for Environmental Prediction/National Center for Atmospheric Research reanalysis dataset 1 (NCEP R1) hindcast products, as well as precipitation estimation from Remotely Sensed Information using Artificial Neural Networks (PERSIANN). The Tropical Rainfall Measurement Mission (TRMM) 3B42 is also used for the Ecuadorian Andes. These datasets were compared to both spatially averaged gauged precipitation and river discharge. In general, the time series of the remotely sensed and hindcast products show a low correlation with locally observed precipitation data. Large biases are also observed between the different products. Hydrological verification based on river flows reveals that water balance errors can be extremely high for all evaluated products, including interpolated local data, in basins smaller than 1000 km². The observations are consistent over the two study regions despite very different climatic settings and hydrological processes, which is encouraging for extrapolation to other mountainous regions.     

Oil spill treatment products approval: the UK approach and potential application to the Gulf region

The environmental threat from oil spills remains significant across the globe and particularly in regions of high oil production and transport such as the Gulf. The ultimate damage caused can be limited by mitigation actions that responders deploy. The responsible and appropriate use of oil spill treatment products (e.g. dispersants, sorbents etc.) can offer response options that can result in substantial net environmental benefit. However, the approval and choice of what products to use needs careful consideration. The United Kingdom has had in place a statutory approval scheme for oil spill treatment products for 30 years. It is based on measures of efficiency and environmental acceptability. Two toxicity tests form an integral part of the assessment, the Sea test and the Rocky Shore test, and work on the premise that approved products will not make the situation significantly worse when added to spilled oil. This paper outlines the UK approach and how its rationale might be applied to the approval of products specific for the Gulf region. Issues such as species choice, higher temperatures and salinity and regional environmental conditions are considered.     

Migration of Petroleum Products Through Sandy Hydrogeologic Systems

Laboratory column experiments were carried out to study the migration of petroleum products through a sandy porous medium. It was found that the oil pressure needed to displace water from the pores of the sand medium increased with depth below the top of the column. While oil under negative pressure displaced water through the variably unsaturated zone, a significant vertical column of oil was needed to displace water from the pores at the water table. These results indicate that oil penetration to and below the water table will occur only if the porous medium is highly conductive and the rate of oil leak is high. For small to moderate leak rates and hydraulic conductivities, oil would preferentially spread laterally through the zones above the water table. This process of spreading could serve as a natural barrier to severe aquifer contamination by petroleum products.
A simplified procedure was developed to give an order-of-magnitude estimate of the preferred subsurface migration pathways of leaked petroleum products. This procedure utilizes the main drainage and wetting curves for oil and water and the interfacial pressure between these two fluids. This approach could be useful in guiding exploratory investigations, reducing both the risk for further spreading of the contaminants and the investigative cost.     

Effect of oil composition on fluid substitution in heavy oil reservoirs

Unlike light oils, heavy oils do not have a well‐established scheme for modelling elastic moduli from dynamic reservoir properties. One of the main challenges in the fluid substitution of heavy oils is their viscoelastic nature, which is controlled by temperature, pressure, and fluid composition. Here, we develop a framework for fluid substitution modelling that is reliable yet practical for a wide range of cold and thermal recovery scenarios in producing heavy oils and that takes into account the reservoir fluid composition, grounded on the effective‐medium theories for estimating elastic moduli of an oil–rock system. We investigate the effect of fluid composition variations on oil–rock elastic moduli with temperature changes. The fluid compositional behaviour is determined by flash calculations. Elastic moduli are then determined using the double‐porosity coherent potential approximation method and the calculated viscosity based on the fluid composition. An increase in temperature imposes two opposing mechanisms on the viscosity behaviour of a heavy‐oil sample: gas liberation, which tends to increase the viscosity, and melting, which decreases the viscosity. We demonstrate that melting dominates gas liberation, and as a result, the viscosity and, consequently, the shear modulus of the heavy oils always decrease with increasing temperature. Furthermore, it turns out that one can disregard the effects of gas in the solution when modelling the elastic moduli of heavy oils. Here, we compare oil–rock elastic moduli when the rock is saturated with fluids that have different viscosity levels. The objective is to characterize a unique relation between the temperature, the frequency, and the elastic moduli of an oil–rock system. We have proposed an approach that takes advantage of this relation to find the temperature and, consequently, the viscosity in different regions of the reservoir.     

Bio‐based Ester Oils for Use as Lubricants in Metal Working

The potential application of bio‐based ester oils for use as lubricants in metal working has been investigated for sustainable production processes in the future. When waste edible and animal fats came into focus as starting materials, it was already proven, that ester oils produced from plant fats performed very well as cooling lubricants. Waste fats were first characterized by analyzing and monitoring samples for one complete year. Inorganic and organic contaminations were found to be low and without seasonal variations. Fatty acid methyl esters (FAME) were produced by transesterification of the waste fats and they were separated into fractions with saturated FAME or unsaturated FAME by fractional crystallisation (winterisation). Further transesterification with 2‐ethylhexanol led to products that could be successfully tested as lubricants. The development of an extraction process aimed at the recycling of oil containing grinding mud by enabling the recirculation of lubricating oil and reutilization of oil‐free metal chips.     

Correlation of dispersant effectiveness and toxicity of oil dispersants towards the alga Chlamydomonas reinhardti

Using synchronous cultures of the unicellular green alga Chlamydomonas reinhardti, the toxicities of mixtures of Ekofisk crude oil and oil dispersants were measured. Sixteen so-called concentrates and 10 solvent-based dispersants were tested. The dispersing effectiveness of these compounds with respect to the Ekofisk crude oil was also measured. The concentrates were tested undiluted as well as diluted using algal growth medium (2‰ salinity) and artificial sea water (33‰ salinity) as dispersing liquid. The solvent-based compounds were tested in algal medium. For all compounds we found significant correlations between their toxicity and their effectiveness in dispersing the Ekofisk oil, such that the more effective the compound, the more toxic it was.     

Miocene lamproite volcanoes in south-eastern Spain—an association of phreatomagmatic and magmatic products

A series of small Miocene (8.3–6.7 Ma) lamproite rock occurrences (as monogenetic volcanoes and/or dykes) cover a large area in southeastern Spain. These rocks are associated with extensional basins filled by Neogene deposits in the Betic and Subbetic structural units. At Cancarix (Sierra de las Cabras), Calasparra, Barqueros, Cerro de Monagrillo, Jumilla, and Vera, eruptions occurred, whereas at Fortuna, Mula and Zeneta there were only small-scale intrusions (mainly dykes). This paper describes volcanic centers at Cancarix, Calasparra and Barqueros, which show initial phreatomagmatic eruptions driven by interaction of rising lamproite magma with groundwater. Tuff ring formed during this volcanic activity. Subsequent activity consisted of dome extrusion in the vent areas of Cancarix and Calasparra and by explosive to effusive magmatic activity accompanied by extensive lava flows at Barqueros.Calasparra and Cancarix are relatively symmetric monogenetic tuff rings filled by late stage massive vertical plug, extruded as degassed crystalline high-viscosity magma along the volcanic conduit. Barqueros was initially a tuff ring, whose late stage Hawaiian-style fountaining generated spatter and clastogenic lavas that built the intra-tuff ring cone of Cabezo del Morron. Finally, extensive lava flows spread from the base of the cone toward the northern part of the edifice. Variations in the tectonic (extensional regime) and local hydrogeologic conditions (shallow aquifers) influenced the occurrence of these lamproite volcanoes. Late stage magma rise was dependent on the magmatic volatile regime, being already degassed at Calasparra and Cancarix, by showing higher viscosity (high crystallization rate) of intra-tuff ring dome extrusions, or still rich in volatiles at Barqueros, displaying lower viscosity lava fountaining and then lava flows.