Characteristics of intra-annual variations of N2O and CH4 in the middle atmosphere

Intra-annual variations of the N₂O and CH₄ mixing ratios from the SAMS instrument on the Nimbus-7 satellite are analyzed using special amplitude and phase characteristics. Differences of the N₂O and CH₄ evolution in the annual cycle are noted. Essential interhemispheric differences are noted in the species′ intra-annual evolution. Asymmetry of the annual cycle is characterized by an interval of increase and an interval when the N₂O and CH₄ mixing ratios exceed the local annual mean values.     

Stratospheric positive ion composition measurements,ion abundances and related trace gas detection

Positive ion spectra obtained from measurements with a balloon-borne mass spectrometer during three balloon flights are critically investigated and compared with other data. Ion abundances for proton hydrates [H⁺(H₂O)_n ions] at different stratospheric temperatures are compared, as well as the abundances of non proton hydrates H⁺X_itl(H₂O)_m, X being most likely CH₃CN.The detection of trace gases from ion composition measurements is discussed and an upper limit for the number densities of minor constituents such as NH₃ and CH₃OH is estimated at 35 km. Although sodium compounds cannot be responsible for the major positive ions, a closer investigation of high resolution daytime spectra suggests a small contribution of sodium in daytime ion chemistry.     

Electron temperature and electron density in the F-region of the ionosphere. I. Observed relationship

Ionospheric data from three incoherent scatter stations over the height range 225–450 km were studied for all daylight hours over a wide range of solar conditions. The relationship between electron temperature T_e, electron density Nand solar flux at 10.7 cm wavelength S_10.7 was expressed as T_e = A−B·(N−5 × 10¹¹) + C·(S_10.7−750), where N is in units of m⁻³ and S_10.7 in kJy.This provided a very satisfactory expression for all data taken at Malvern and St. Santin between 0800 and 1600 LT. For data taken at Arecibo, however, the linearity broke down at low electron densities. The data from all three stations were therefore divided into two sets according to electron density and reexamined.ForN < 5 × 10¹¹ m⁻³ B increased steadily with height and decreased steadily with latitude.For N > 5 × 10¹¹ m⁻³ B did not appear to vary with height, with season or with latitude. C was approximately constant for all sets of data.The different mechanisms involved in the heat balance of the electron population are discussed and a qualitative explanation for the relationship is proposed.     

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,SW Germany

Highly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (<4.5wt% NaCl + CaCl₂), high‐temperature (≤390°C) H₂O‐NaCl‐(CO₂‐CH₄) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H₂O‐NaCl‐(KCl‐CaCl₂) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl₂, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, >20wt% NaCl + CaCl₂, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios >1000) of similar salinity, resulting in a mixed H₂O‐NaCl‐CaCl₂ brine (50–140°C, 23–26wt% NaCl + CaCl₂, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H₂O‐NaCl‐CaCl₂‐(SO₄‐HCO₃), 70–190°C, 5–25wt% NaCl‐CaCl₂ and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.     

Diffuse hydrothermal methane output and evidence of methanotrophic activity within the soils at Sousaki (Greece)

Methane soil flux measurements have been made in 38 sites at the geothermal system of Sousaki (Greece) with the closed chamber method. Fluxes range from ?47.6 to 29 150 mg m^?2 day^?1, and the diffuse CH₄ output of the system has been estimated at 19 t a^?1. Contemporaneous CO₂ flux measurements showed a moderate positive correlation between CO₂ and CH₄ fluxes. Comparison of the CO₂/CH₄ soil flux ratios with the CO₂/CH₄ ratio of the gases of the main gas manifestations provided evidence for methanotrophic activity within the soil. Laboratory CH₄ consumption experiments confirmed the presence of methanotrophic microorganisms in soil samples collected at Sousaki. Consumption was generally in the range from ?4.9 to ?38.9 pmolCH₄ h^?1 g^?1 but could sometimes reach extremely high values (?33 000 pmolCH₄ h^?1 g^?1). These results are consistent with recent studies on other geothermal systems that revealed the existence of thermoacidophilic bacteria exerting methanotrophic activity in hot, acid soils, thereby reducing methane emissions to the atmosphere.     

FT-IR measurements of petroleum fluid inclusions: methane, n-alkanes and carbon dioxide quantitative analysis

A recent advancement in petroleum geochemistry is to model fossil oil composition using microthermometric and volumetric data acquired from individual fluid inclusion analysis. Fourier transform infrared (FT‐IR) microspectroscopy can record compositional information related to gas (CH₄ and CO₂) and alkane contents of petroleum inclusions. In this study, a quantitative procedure for FT‐IR microspectrometry has been developed to obtain, from individual fluid inclusions, mol percentage concentrations of methane, alkanes and carbon dioxide as constraints to thermodynamic modelling. A petroleum inclusion in a sample from the Québec City Promontory nappe area was used as standard to record a reference spectrum of methane. The analytical procedure is based on the measurement of CH₄/alkane and CH₄/CO₂ band area ratios. CH₄/alkane infrared band area ratio is obtained after spectral subtraction of the reference methane spectrum. This area ratio, affected by absolute absorption intensities of methane, methyl and methylene, provides a molar CH₄/alkane ratio. Methyl/methylene ratio (CH₂/CH₃) ratio is obtained following procedures established in previous work. CO₂/CH₄ concentration ratio is estimated from relative absolute absorption intensities. Application to natural inclusions from different environments shows good correlation between FT‐IR quantification and PIT (petroleum inclusion thermodynamic) modelling.     

Constraining the rate and extent of mantle serpentinization from seismic and petrological data: implications for chemosynthesis and tectonic processes

We used seismic velocity as a proxy for serpentinization of the mantle, which occurred beneath thinned but laterally continuous continental crust during continental break up, prior to opening of the Atlantic Ocean. The serpentinized sub‐continental mantle is now exhumed, beneath the Iberia Abyssal Plain and was accessed by scientific drilling on Ocean Drilling Program legs 149 and 173. Chromatographic modelling of kinetically limited transport of the serpentinization front yields a front displacement of 2197 ± 89 m, a time‐integrated fluid flux of 1098 ± 45 m³ m^?2 and a Damköhler number of 6.0 ± 0.2. Whether either surface reaction or chemical transport limit the rate of reaction, we calculate timescales for serpentinization of approximately 10⁵–10⁶ years. This yields time‐average fluid flux rates for H₂O, entering and reacting with the mantle, of 60–600 mol m^?2 a^?1 and for CH₄, produced as a by‐product of oxidation of Fe⁺⁺ to magnetite and exiting the mantle, of 0.55–5.5 mol m^?2 a^?1. This equates to a CH₄‐flux of 0.18–1.8 Tg a^?1 for coeval serpentinization of the mantle that was exhumed west of Iberia. This represents 0.03–0.3% of the present‐day annual CH₄‐flux from all sources and a higher fraction of pre‐anthropogenic (lower) CH₄ levels. CH₄ released by serpentinization at or beneath the seafloor could provide substrate for biological chemosynthesis and/or promote gas‐hydrate formation. Finally, noting its volumetric extent and rapidity (<10⁶ years), we interpret serpentinization to be a reckonable component of tectonic processes, contributing both diapiric and expansional forces and helping to ‘lubricate’ extensional processes. Given its anisotropic permeability, actively deforming serpentinite might impede melt migration which may be of interest, given the apparent lack of melt in some rifted margins.     

Temporal variations of POGO equatorial electrojet parameters

An analysis of the POGO satellites observations of the magnetic field of the equatorial electroject for the September equinoctial months of the years 1967, 1968 and 1969, provided about 500 values each of the electrojet half-width w, its peak current intensity J₀, its total eastward current I₊ at 11, 12, 13, 14 and 15 h LT. The all-sector daytime average values of the parameters for the three years are 232 ± 47 A km⁻¹ for J₀, 234 ± 6 km for w and (55± 8)×10³ A for I₊.This first coverage of all sectors of the globe gives the first study of the diurnal variation of the total current and shows that all the three parameters vary substantially with local time; that w has minimal values around local noon; that J₀ has a pronounced peak around local noon as may be expected from the diurnal variation of H; and that I₊ has a broad maximum around 11 h and 12 h LT.     

Comparison of incoherent scatter observations of electron density,and electron and ion temperature at Millstone Hill with the International Reference Ionosphere

Millstone Hill incoherent scatter (IS) observations of electron density (N_e, electron temperature (T_e) and ion temperature (T_i) are compared with the International Reference Ionosphere (IRI-86) for both noon and midnight, for summer, equinox and winter, at both solar maximum (1979–1980) and solar minimum (1985–1986). The largest difference inN_e is found in the topside, where values of N_e given by IRI-86 are generally larger than those obtained from IS measurements, by a factor which increases with increasing height, and which has a mean value near two at 600 km. Apart from the bottom of the profile, which is tied to the CIRA neutral temperature, the IRI-86 T_e model has no solar cycle variation. However, the IS measurements during the summer reveal larger T_e at solar maximum than at solar minimum. At other seasons higher T_e at solar maximum occurs only during the daytime at the greater heights. Nighttime T_e is shown by the IS radar to be generally larger in winter than in summer, an effect not included in the IRI. This is apparently due to photoelectron heating during winter from the sunlit ionosphere conjugate to Millstone Hill. The day-night difference in T_i given by IRI-86 above 600km is not as large in the IS measurements.     

Mobilization of ore fluids during Alpine metamorphism: evidence from hydrothermal veins in the Variscan basement of Western Carpathians,Slovakia

Hydrothermal polymetallic veins of the Gemeric unit of the Western Carpathians are oriented coherently with the foliation of their low‐grade Variscan basement host. Early siderite precipitated from homogeneous NaCl‐KCl‐CaCl₂‐H₂O brines with minor CO₂, while immiscible gas–brine mixtures are indicative of the superimposed barite, quartz–tourmaline and quartz–sulphide stages. The high‐salinity aqueous fluid (18–35 wt%) found in all mineralization stages corresponds to formation water modified by interaction with crystalline basement rocks at temperatures between 140 and 300°C. High brominity (around 1000 ppm in average) resulted from evaporation and anhydrite precipitation in a Permo‐Triassic marine basin, and from secondary enrichment by dissolution of organic matter in the marine sediments at diagenetic temperatures. Sulphate depletion reflects thermogenic reduction during infiltration of the formation waters into the Variscan crystalline basement. Crystallization temperatures of the siderite fill (140–300°C) and oxygen isotope ratios of the parental fluids (4–10‰) increase towards the centre of the Gemeric cleavage fan, probably as a consequence of decreasing water/rock ratios in rock‐buffered hydrothermal systems operating during the initial stages of vein evolution. In contrast, buoyant gas–water mixtures, variable salinities and strongly fluctuating P–T parameters in the successive mineralization stages reflect transition from a closed to an open hydrothermal system and mixing of fluids from various sources. Depths of burial were 6–14 km (1.7–4.4 kbar, in a predominantly lithostatic fluid regime) during the siderite and barite sub‐stages of the north‐Gemeric veins, and up to 16 km (1.6–4.5 kbar, in a hydrostatic to lithostatic fluid regime) in the quartz–tourmaline stage of the south‐Gemeric veins. The fluid pressure decreased down to approximately 0.6 kbar during crystallization of sulphides. U‐Pb‐Th, ⁴⁰Ar/³⁹Ar and K/Ar geochronology applied to hydrothermal muscovite–phengite and monazite, as well as cleavage phyllosilicates in the adjacent basement rocks and deformed Permian conglomerates corroborated the opening of hydrothermal veins during Lower Cretaceous thrusting and their rejuvenation during Late Cretaceous sinistral transpressive shearing and extension.     

Investigations of the winter anomaly in ionospheric absorption in January 1981

Ground-based and rocket-borne investigations were carried out in January 1981 in the Volgograd region to study space-time peculiarities of the winter anomaly in ionospheric radio wave absorption (WA). Electron-density altitude profiles N_e(h) were measured with rockets, by the coherent frequency method and by using electrostatic probes; temperature profiles T(h) were measured by a resistance thermometer: wind velocity and direction were measured by radio-observations of a chaff cloud and of the payload parachute drift. At the same time, ionospheric radio wave absorption was measured in Volgograd at two frequencies, 2.2 and 2.7 MHz, by the A1 method. The condition of the lower ionosphere could be determined from absorption data and from f min parameter data obtained from vertical sounding ionograms. “Salvo” launchings of the rockets were performed on 14 January, when absorption was anomalously large, and on 21 and 28 January, which were days of normal winter absorption.Data analysis has shown that N_e values on the day with excessive absorption exceeded the same values on a normal day at altitudes from 72 to 95 km; on 21 January N_c values exceeded those of 29 February 1980 (without WA) at all altitudes below ~ 90 km. The absorption at Volgograd on 28 January was somewhat higher than on 21 January and than at stations at higher latitude, which may be due to a stable local increase of N_e values in the altitude range 80–90 km. The temperature in the region of the N_e-enhanced values (up to the limit altitude of measurements, about 80 km) was below the standard temperature (COSPAR, 72), both on 14 January and on the normal days. Measurements carried out at night have shown that winter N_c values considerably exceeded those during the autumn. The zonal and meridional wind profiles (up to about 80 km) at Volgograd exhibit a stable eastward flux, both in the stratsophere and in the mesosphere. The value of the wind velocity meridional component on 21 January is close to zero at all altitudes. On 14 and 28 January the wind profiles show an irregular structure with large velocity gradients at all altitudes above about 50–60 km.The absorption data and f min data from a number of stations, viz. from Juliusruh to Yakutsk (in longitude) and from Arkhangel'sk to Rostov-on-Don (in latitude), show that anomalously excessive absorption occurred over a vast distance exceeding 100° of longitude at ~ 55° latitude and that, based on the dates of absorption maxima (f min), one may conclude that the source of the disturbance was moving from west to east. Data on the motion of the air as shown by rocket and radiometeoric observations, indicate the same wind direction in the stratosphere as in the mesosphere. These data and the constant pressure charts point to the conclusion that the enhanced radio absorption values at mid-latitudes may be explained by a transport of dry air rich in nitric oxide from the auroral zone towards lower latitudes. The transport is provided by a stable circumpolar vortex existing in winter time. This mechanism may explain both the normal and anomalous winter absorption, as well as the post-storm effect.     

The middle atmospheric response to short and long term solar UV variations: analysis of observations and 2D model results

We have investigated the middle atmospheric response to the 27-day and 11-yr solar UV flux variations at low to middle latitudes using a two-dimensional photochemical model. The model reproduced most features of the observed 27-day sensitivity and phase lag of the profile ozone response in the upper stratosphere and lower mesosphere, with a maximum sensitivity of +0.51% per 1% change in 205 nm flux. The model also reproduced the observed transition to a negative phase lag above 2 mb, reflecting the increasing importance with height of the solar modulated HO_x chemistry on the ozone response above 45 km. The rnodel revealed the general anti-correlation of ozone and solar UV at 65–75 km, and simulated strong UV responses of water vapor and HO_x species in the mesosphere. Consistent with previous 1D model studies, the observed upper mesospheric positive ozone response averaged over ±40° was simulated only when the model water vapor concentrations above 75 km were significantly reduced relative to current observations. Including the observed temperature-UV response in the model to account for temperature-chemistry feedback improved the model agreement with observations in the middle mesosphere, but did not improve the overall agreement above 75 km or in the stratosphere for all time periods considered. Consistent with the short photochemical time scales in the upper stratosphere, the model computed ozone-UV sensitivity was similar for the 27-day and 11-yr variations in this region. However, unlike the 27-day variation, the model simulation of the 11-yr solar cycle revealed a positive ozone-UV response throughout the mesosphere due to the large depletion of water vapor and reduced HO_x-UV sensitivity. A small negative ozone response at 65–75 km was obtained in the 11-yr simulation when temperature-chemistry feedback was included,In agreement with observations, the model computed a low to middle latitude total ozone phase lag of +3 days and a sensitivity of +0.077% per 1% change in 205 nm flux for the 27-day solar variation, and a total ozone sensitivity of +0.27% for the 11-yr solar cycle. This factor of 3 sensitivity difference is indicative of the photochemical time constant for ozone in the lower stratosphere which is comparable to the 27-day solar rotation period but is much shorter than the 11-yr solar cycle.     

Polar thermospheric Joule heating,and redistribution of recombination energy in the upper mesosphere

Kellogg, W. W. (1961, J. Met. 18, 373) suggested that transport of atomic oxygen from the summer into the winter hemisphere and subsequent release of energy by three body recombination, O + O + N₂→O₂ + N₂ + E, may contribute significantly to the so-called mesopause temperature anomaly (increase in temperature from summer to winter). Earlier model calculations have shown that Kellogg's mechanism produces about a 10% increase in the temperature from summer to winter at 90 km. This process, however, is partly compensated by differential heating from absorption of UV radiation associated with dissociation of O₂. In the auroral region of the thermosphere, there is a steady (component of) energy dissipation by Joule heating (with a peak near 130 km) causing a redistribution and depletion of atomic oxygen due to wind-induced diffusion. With the removal of O. latent chemical energy normally released by three body recombination is also removed, and the result is that the temperature decreases by almost 2% near 90 km. Through dynamic feedback, this process reduces the depletion of atomic oxygen by about 25% and the temperature perturbation in the exosphere from 10% to 7% at polar latitudes. Under the influence of the internal dynamo interaction, the prevailing zonal circulation in the upper thermosphere (small in magnitude) changes direction when the redistribution of recombination energy is considered. The above described effects are very sensitive to the adopted rates of eddy diffusion. They are also strongly time dependent and are significantly reduced for disturbances associated with magnetic storms.     

On the geochemistry of gases and noble gas isotopes (including 222Rn) in deep crustal fluids: the 4000 m KTB-pilot hole fluid production test 2002–03

The concentrations of H₂, O₂, CO₂, and concentrations and isotopic composition of the noble gases (including ²²²Rn), N₂, CH₄, and higher hydrocarbons dissolved in 4000 m deep‐seated fluids from a 12‐month fluid production test in the KTB pilot hole were analyzed. This determination of the gas geochemistry during the test in combination with the knowledge of the hydraulic data provides relevant information about the fluid hydraulics of the deep system. All gas concentrations and isotopic signatures, except for ²²²Rn, showed constancy during the course of the test. This, in combination with large fluid flow rates at a moderate water table drawdown, imply an almost infinite fluid reservoir in 4000 m depth. From the change in ²²²Rn‐activity as a function of pump rate, the contribution of smaller and wider pores to the overall fluid flow in an aquifer can be deduced. This ²²²Rn‐activity monitoring proved therefore to be a valuable instrument for the qualitative observation of the scavenging of pore and fracture surfaces, a hydraulic feature invisible to standard hydraulic testing tools. The observance of this scavenging effect is due to (i) the continuous on‐line geochemical monitoring, (ii) the durability of the test, (iii) a change in pump rate during the course of the test, and (iv) due to the short half‐life of ²²²Rn. The fluids have a 5.9% mantle He component, and a δ²¹Ne excess of 14%, and a noble gas model age of about (5.5–6.2) ± 2.0 Myr. The mean N₂/Ar‐ratio of 516 and δ¹⁵N‐data of about +1.5‰ indicates sedimentary or metamorphic origin of N₂. The hydrocarbons, amounting to 33 vol.% in the gas phase, are derived from thermal decomposition of marine organic matter of low maturity. But a key question, the identification of the potential source region of the fluids and the migration pathway, is still unidentified.     

Study of coal gas wettability for CO2 storage and CH4 recovery

To quantify and rank gas wettability of coal as a key parameter affecting the extent of CO₂ sequestration in coal and CH₄ recovery from coal, we developed a contact angle measuring system based on a captive gas bubble technique. We used this system to study the gas wetting properties of an Australian coal from the Sydney Basin. Gas bubbles were generated and captivated beneath a coal sample within a distilled water‐filled (pH 5.7) pressurised cell. Because of the use of distilled water, and the continuous dissolution and shrinkage of the gas bubble in water during measurement, the contact angles measured correspond to a ‘transient receding’ contact angle. To take into account the mixed‐gas nature (CO₂, CH₄, and to a lesser extent N₂) of coal seam gas in the basin, we evaluated the relative wettability of coal by CH₄, CO₂ and N₂ gases in the presence of water. Measurements were taken at various pressures of up to 15 MPa for CH₄ and N₂, and up to 6 MPa for CO₂ at a constant temperature of 22°C. Overall, our results show that CO₂ wets coal more extensively than CH₄, which in turn wets coal slightly more than N₂. Moreover, the contact angle reduces as the pressure increases, and becomes < 90° at various pressures depending on the gas type. In other words, all three gases wet coal better than water under sufficiently high pressure.     

Diurnal propagating tides in the low-latitude middle atmosphere

Using an equivalent gravity wave f-plane model it is shown that longitude variations in diurnal insolation absorption by tropospheric H₂O can account for longitudinal variations of at least ± 12–15% about zonal mean values in the diurnal wind amplitude at low latitudes (0–20°) between 80 and 100 km, by virtue of the non-migrating propagating tidal modes which are excited. Phase variations of about ± 0.75 h also occur. These percentage variations are conservative estimates, since the background migrating (1,1,1) mode appears to be slightly (20–25%) overestimated in amplitude. In addition, the assumed eddy dissipation values, which appear necessary to model the breaking (1,1,1) mode, are larger than generally considered ‘reasonable’ by photochemical modellers. For a photochemically more reasonable eddy diffusion profile, estimates of longitude differences in diurnal wind amplitude are quite similar to the above values below 87 km, but increase to ± 17–25% near 100 km, with accompanying phase variations of ± 1–2 h about zonal mean values. In addition, it is shown that radiative damping by CO₂ parameterized by a scale-dependent Newtonian cooling coefficient accounts for no more than a 20% reduction in the amplitudes of diurnal propagating tides above 80 km.     

EISCAT incoherent scatter radar observations and model studies of day to twilight variations in the D-region during the PCA event of August 1989

An intense solar proton event causing enhanced ionization in the ionospheric D-region occurred on 12 August 1989. The event was partially observed during three successive nights by the EISCAT UHF incoherent scatter radar at Ramfjordmoen near Tromsa, Norway. Ion production rates calculated from GOES-7 satellite measurements of proton flux and a detailed ion chemistry model of the D-region are used together with the radar data to deduce electron concentration, negative ion to electron concentration ratio, mean ion mass and neutral temperature in the height region from 70 to 90 km, at selected times which correspond to the maximum and minimum solar elevations occurring during the radar observations. The quantitative interpretation of EISCAT data as physical parameters is discussed. The obtained temperature values are compared with nearly simultaneous temperature measurements at Andøya based on lidar technique.     

Geothermal fluids circulation at Caldas do Moledo area, Northern Portugal: geochemical and isotopic signatures

A hydrogeological conceptual model of the Caldas do Moledo geothermal site is proposed that shows mixing between geothermal waters and local shallow groundwaters. Stable isotope values of Caldas do Moledo geothermal waters indicate recharge areas located at relatively high altitudes (850–1250 m a.s.l.). The NW–SE Vigo–Régua shear zone plays an important role in fluid recharge and circulation towards the NNE–SSW Régua–Verin fault system, forming a path for ascent of geothermal fluids. The apparent ¹⁴C age of geothermal fluids (15.66 ± 2.86 ka BP) was estimated in the total dissolved inorganic carbon (TDIC). Geothermometer calculations indicate that, assuming a conductive temperature gradient of 32°C per kilometer for northern Portugal, the maximum depth of circulation is roughly 1.8 ± 0.4 km. The K, Ca and SO₄ concentrations found in some Caldas do Moledo geothermal spring waters show mixing between deep geothermal and shallow groundwater systems. Local shallow groundwaters showing the highest SO₄ concentrations were found at low elevation areas, originating from fertilisers and pesticides applied to the Port wine vineyards in the Douro River valley. Geothermal waters from boreholes AC1 and AC2 do not show evidences of direct pollution from the spreading of such agrochemicals.     

Measurements of odd oxygen in the polar region on 10 February 1984 during MAP/WINE

Abundances of atomic oxygen and ozone have been measured by various techniques over northern Scandinavia during the MAP/WINE campaign in the winter 1983–1984. On 10 February at Kiruna, Sweden, rocket experiments used resonance fluorescence and twin path absorption at 130 nm to measure [O]between 70 and 178 km. Rocket-borne measurements of nightglow at 557.7, 761.9 and 551.1 nm and at 1.27 μm have also been obtained and [O]values derived from the atmospheric band intensities. Ozone abundances between 50 and 90 km have been determined from rocket-borne measurements of the ν₃ 9.6 μm nightglow intensity from Andøya, Norway, and Kiruna. These have been compared with [O₃] measured on the same day from the Solar Mesospheric Explorer satellite, using measurements of dayglow at 1.27 μm, and with results from other rocket launchings in MAP/WINE. The results show evidence of low, perhaps exceedingly low, [O] and below normal [O₃] above the mesopause. Below 75 km at night [O₃] exceeded earlier and subsequent observations in the campaign. The measurements were made during a minor stratospheric warming, characterised by an offset polar vortex centred near the measurement zone.