Study of the characteristics of earthquake precursory anomalies of He and H2 Beijing No. 2 Cotton Mill well and their relation with earthquakes

This paper systematically summarized the relation of the abnormal change of He and H₂ dissolved gasses in deep hot-water well at Beijing No. 2 Cotton Mill and their relation with seismicity of the region. An empirical formula for the relation of the precursory anomaly of He and H₂ gasses with the magnitude and occurrence time of earthquake has been derived. Two events of magnitude greater than 5 in North China had been successfully predicted by using this formula. The Chinese version of this paper appeared in the Chinese edition ofActa Seismologica Sinica,15, 490–497, 1993.     

Geochemical model of a magmatic–hydrothermal system at the Lastarria volcano, northern Chile

Lastarria volcano (25°10′ S, 68°31′ W; 5,697 m above sea level), located in the Central Andes Volcanic Zone (northern Chile), is characterized by four distinct fumarolic fields with outlet temperatures ranging between 80°C and 408°C as measured between May 2006–March 2008 and April–June 2009. Fumarolic gasses contain significant concentrations of high temperature gas compounds (i.e., SO₂, HCl, HF, H₂, and CO), and isotopic ratios (³He/⁴He, δ¹³C–CO₂, δ¹⁸O–H₂O, and δD–H₂O) diagnostic of magmatic gas sources. Gas equilibria systematics, in both the H₂O-H₂-CO₂-CO-CH₄ and alkane–alkene C₃ system, suggest that Lastarria fumarolic gasses emanate from a superheated vapor that is later cooled and condensed at relatively shallow depths. This two-stage process inhibits the formation of a continuous aquifer (e.g., horizontal liquid layer) at relatively shallow depth. Recent developments in the magmatic gas system may have enhanced the transfer and release of heat causing shallow aquifer vaporization. The consequent pressure increase and aquifer vaporization likely triggered the inflation events beginning in 2003 at the Lastarria volcano.     

Fumarole/plume and diffuse CO2 emission from Sierra Negra caldera, Galapagos archipelago

Measurements of visible and diffuse gas emission were conducted in 2006 at the summit of Sierra Negra volcano, Galapagos, with the aim to better characterize degassing after the 2005 eruption. A total SO₂ emission of 11?±?2?t day^?1 was derived from miniature differential optical absorption spectrometer (mini-DOAS) ground-based measurements of the plume emanating from the Mini Azufral fumarolic area, the most important site of visible degassing at Sierra Negra volcano. Using a portable multigas system, the H₂S/SO₂, CO₂/SO₂, and H₂O/SO₂ molar ratios in the Mina Azufral plume emissions were found to be 0.41, 52.2, and 867.9, respectively. The corresponding H₂O, CO₂, and H₂S emission rates were 562, 394, and 3?t day^?1, respectively. The total output of diffuse CO₂ emissions from the summit of Sierra Negra volcano was 990?±?85?t day^?1, with 605?t day^?1 being released by a deep source. The diffuse-to-plume CO₂ emission ratio was about 1.5. Mina Azufral fumaroles released gasses containing 73.6?mol% of H₂O; the main noncondensable components amounted to 97.4?mol% CO₂, 1.5?mol% SO₂, 0.6?mol% H₂S, and 0.35?mol%?N₂. The higher H₂S/SO₂ ratio values found in 2006 as compared to those reported before the 2005 eruption reveal a significant hydrothermal contribution to the fumarolic emissions. ³He/⁴He ratios measured at Mina Azufral fumarolic discharges showed values of 17.88?±?0.25?R _A , indicating a mid-ocean ridge basalts (MORB) and a Galapagos plume contribution of 53 and 47?%, respectively.     

Anomalous changes of CH4/Ar ratio in subsurface gas bubbles as seismogeochemical precursors at Matsuyama,Japan

The results of seismogeochemical monitoring of subsurface gases associated with ground-waters from deep artesian wells in Matsuyama, Japan, are presented. The weekly collections of bubble-gas samples from the two borehole wells and gas chromatographic determinations of their He/Ar, H₂/Ar, N₂/Ar, and CH₄/Ar ratios for the recent nineteen months have revealed that the bubble-gas CH₄/Ar ratios at the two stations are correlated with the seismic activity in this area. Positive anomalies of the CH₄/Ar ratio were accompanied by five earthquakes with relatively large magnitudes and/or relatively small epicentral distances among thirty earthquakes that occurred during the monitoring period. The anomalous increases in the CH₄/Ar ratio had evidently begun prior to the respective earthquakes.The occurrence of the geochemical anomaly appears to depend strongly upon the earthquake magnitude and distance, because the earthquakes that accompanied the anomalies and those that did not can be reasonably distinguished in the plot of magnitude vs. distance. Similar anomalies can be also seen in the variations of He/Ar and N₂/Ar ratios, but their magnitudes are much smaller than those of the CH₄/Ar ratio. These features have been discussed in relation to the possible mechanism of the seismogeochemical phenomena.     

Discharge of H2 from the Atotsugawa and Ushikubi Faults,Japan, and its relation to earthquakes

The concentration of H₂ in soil gases has been measured weekly at five stations on the Atotsugawa and Ushikubi faults in northern central Main Island, Japan, since 1981 in search of possible relationship with earthquakes. The observed H₂ concentration varies from lower than 1 ppm to 7.8% in time and place. When a large earthquake (M: 7.7, epicenter distance: 486 km) occurred on 26 May 1983, an outstanding discharge of H₂ was observed at all five stations, preseismically at three of them, and coseismically at the other two. Simultaneous H₂ emission was also observed at some stations in seven other occasions. These periods of unusual H₂ discharge nearly coincided with occurrences of major earthquakes in Japan, but not of local minor earthquakes along the Atotsugawa fault. This fault, being a deep fracture zone, may be sensitive to large-scale crustal stress changes which incidentally cause the major earthquakes. Increased H₂ may be produced by rock fracture caused by the increased stresses on the fault and by the earthquakes themselves. Local minor earthquakes along Atotsugawa fault with magnitude lower than 3 may be unable to cause sufficient rock fracture to produce significant H₂.     

N<Subscript>2</Subscript>, Ar,and He as a tool for discriminating sources of volcanic fluids with application to Vulcano,Italy

A detailed analysis of published data on the N₂, Ar, and He content and Ar and He isotopic composition of fumarolic fluids from Vulcano crater (south Italy) supports a model with two endmembers comprising magmatic and hydrothermal fluids with correspondingly low and high H₂O content. The magmatic component with the highest ³He/⁴He and highest absolute concentrations of N₂, Ar, and He also has the lowest N₂/Ar and N₂/He ratios (∼300 and ∼500, respectively). In contrast, the hydrothermal endmember, with the lower ³He/⁴He and lower absolute N₂, Ar, and He abundances, has high N₂/Ar (∼1,000) and high N₂/He (>3,000) ratios. The hydrothermal component is also characterized by the highest ⁴⁰Ar/³⁶Ar ratios (>1,000) and is proposed to be the main carrier of metamorphic gases from the arc crust.     

Gas hazard assessment in a densely inhabited area of Colli Albani Volcano (Cava dei Selci, Roma)

The northwestern flank of the Colli Albani, a Quaternary volcanic complex near Rome, is characterised by high pCO₂ values and Rn activities in the groundwater and by the presence of zones with strong emission of gas from the soil. The most significant of these zones is Cava dei Selci where many houses are located very near to the gas emission site. The emitted gas consists mainly of CO₂ (up to 98 vol%) with an appreciable content of H₂S (0.8–2%). The He and C isotopic composition indicates, as for all fluids associated with the Quaternary Roman and Tuscany volcanic provinces, the presence of an upper mantle component contaminated by crustal fluids associated with subducted sediments and carbonates. An advective CO₂ flux of 37 tons/day has been estimated from the gas bubbles rising to the surface in a small drainage ditch and through a stagnant water pool, present in the rainy season in a topographically low central part of the area. A CO₂ soil flux survey with an accumulation chamber, carried out in February–March 2000 over a 12 000 m² surface with 242 measurement points, gave a total (mostly conductive) flux of 61 tons/day. CO₂ soil flux values vary by four orders of magnitude over a 160-m distance and by one order of magnitude over several metres. A fixed network of 114 points over 6350 m² has been installed in order to investigate temporal flux variations. Six surveys carried out from May 2000 to June 2001 have shown large variations of the total CO₂ soil flux (8–25 tons/day). The strong emission of CO₂ and H₂S, which are gases denser than air, produces dangerous accumulations in low areas which have caused a series of lethal accidents to animals and one to a man. The gas hazard near the houses has been assessed by continuously monitoring the CO₂ and H₂S concentration in the air at 75 cm from the ground by means of two automatic stations. Certain environmental parameters (wind direction and speed; atm P, T, humidity and rainfall) were also continuously recorded. At both stations, H₂S and CO₂ exceeded by several times the recommended concentration thresholds. The highest CO₂ and H₂S values were recorded always with wind speeds less than 1.5 m/s, mostly in the night hours. Our results indicate that there is a severe gas hazard for people living near the gas emission site of Cava dei Selci, and appropriate precautionary and prevention measures have been recommended both to residents and local authorities.     

Volatile emissions and gas geochemistry of Hot Spring Basin,Yellowstone National Park,USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H₂, and mildly enriched in CH₄ and H₂S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water–rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or ^40?Ar/^4?He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 °C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO₂ flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO₂ fluxes across all the thermal/altered area suggests that 410 ± 140 t d^− 1 CO₂ are emitted at HSB (vent emissions not included). Diffuse fluxes of H₂S were measured in Yellowstone for the first time and likely exceed 2.4 t d^− 1 at HSB. Comparing estimates of the total estimated diffuse H₂S emission to the amount of sulfur as SO₄²⁻ in streams indicates ~ 50% of the original H₂S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140–370 MW using CO₂ as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1–3% for CO₂, 2–8% for heat) of that estimated for the entire Yellowstone system.     

Research on characteristics of magnitude structure of earthquake sequences

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Peridotite-CO2-H2O and the low-velocity zone

The properties of the seismic low-velocity zone are consistent with incipient melting of mantle peridotite. Vapor-absent melting of amphibole-peridotite has been used to model the low-velocity zone, but evidence that CO₂ exists in the upper mantle indicates that peridotite-CO₂-H₂O would be a better model. The divariant solidus surface for peridodite-CO₂-H₂O is traversed by a series of univariant lines marking the intersections of divariant subsolidus reactions involving dolomite or magnesite, amphibole, or phlogopite (other hydrous minerals are neglected in this treatment), or combinations of these. The vapor phase compositions are buffered to specific values, which limits the range of vapor compositions that can coexist with peridotite at various pressures. Below about 30 kbar, the vapor phase is buffered by the melting of amphibole-peridotite, with composition ranging from H₂O to high CO₂/H₂O. Above about 25 kbar, the vapor phase is buffered by the melting of dolomite-peridotite, with composition ranging from CO₂ to high H₂O/CO₂ at pressures above 30 kbar. The buffered curve for phlogopite-peridotite intersects the dolomite-peridotite curve, generating another line for phlogopite-dolomite-peridotite; the strong buffering capacity of dolomite forces the vapor on this line to high H₂O/CO₂. Near the buffered curve for the solidus of partly carbonated peridotite there is a temperature maximum on the peridotite-vapor solidus surface. On the CO₂ side of the maximum, above 26 kbar, CO₂/H₂O is greater in liquid than in vapor; on the H₂O side of this maximum, and at all pressures below 26 kbar, CO₂/H₂O is greater in vapor than in liquid. The suboccanic low-velocity zone is caused by incipient melting of amphibole-peridotite in the presence of vapor with high CO₂/H₂O, with generation of forsterite-normative liquid. The subcontinental low-velocity zone, where present, is probably caused by incipient melting of dolomite-peridotite, or phlogopite-dolomite-peridotite, either with H₂O-rich vapor or without vapor, with the generation of CO₂-rich, alkalic, SiO₂-poor liquid (larnite-normative) that in extreme conditions may be carbonatitic.     

尾波持续时间比τH/τV 在强震短临预报中的应用

本文根据Aki等人提出的尾波理论,导出了地方震尾波水平分量与垂直分量的持续时间比的具体表达式: τ_H/τ_V=I_H/I_V(Q_H/Q_V)~(1/4)·B_H/B_V。该式表明,τ_H/τ_V的变化主要反映了震源体一定范围内,由于介质的各向异性而引起的尾波在不同方向上的激发及衰减能力的差异。本文还讨论了地震前τ_H/τ_V短临异常的物理机制,认为异常的产生与孕震期间介质内裂隙的出现和闭合有关。1986年门源6.4级地震和1975年海城7.3级地震前,τ_H/τ_V都有不同程度的短期低值异常及临震高值突跳。门源地震前后门源台记录的直达S波的最大振幅比A_(mH)/A_(mv)也有与尾波持续时间比类似的异常。最后通过对一些震例的分析,初步得到震级与异常时间的关系为M=0.657lnT+3.44。     

Kinetics of Methyldiethanolamine Mineralization by Using UV/H2O2 Process

The UV/H₂O₂ is one of the popular techniques in the advanced oxidation processes (AOPs) and has been applied in the wastewater treatment during recent two decades. UV exposure on the H₂O₂ generate highly reactive hydroxyl radicals (OH^?), which are used to degrade organic contaminants through oxidation processes in wastewater. This present study involves the estimation of hydroxyl radical rate constants of methyldiethanolamine (MDEA) mineralization at different temperatures by using UV/H₂O₂ in aqueous solution. Laboratory experiments have been conducted and the profile of MDEA mineralization has been established. The hydroxyl radical rate constants and the activation energy of mineralization process have been calculated. The estimated hydroxyl rate constants and the activation energy are in good agreement with those reported in the literature.     

Temporal variations of gas compositions of fumaroles in the Tatun Volcano Group,northern Taiwan

Hydrothermal activity is common in the Tatun Volcano Group of northern Taiwan. Helium isotopic compositions of fumarolic samples show that mantle component occupies more than 60% in the previous study. Along with recent seismic results, a magma reservoir is inferred to have existed beneath the area of Da-you-keng, where fumarolic venting is the most active in Tatun Volcano Group. Progressive increases of HCl concentrations and SO₂/H₂S ratio in fumaroles from Da-you-keng have been observed since August 2004. The HCl concentration changed from almost the detection limit to thousands of ppm, even up to 30,000 ppm. SO₂/H₂S ratios varied from almost 0 to 3; hence SO₂ became the dominated S species in this area. These variations were accompanied by rising temperature of fumaroles in the Tatun Volcano Group, especially in the area of Da-you-keng (from boiling point to 131 °C). Meanwhile, ³He/⁴He ratios showed a decreasing trend but returned to normal values shortly thereafter. We propose two possible processes, 1) new magma supply and 2) recent opening of fractures in local area, to explain these observations. Based on the change of ³He/⁴He ratio and lack of ground deformation, we consider the latter might be more plausible.     

Gas geochemistry of the Valles caldera region, New Mexico and comparisons with gases at Yellowstone, Long Valley and other geothermal systems

Noncondensible gases from hot springs, fumaroles, and deep wells within the Valles caldera geothermal system (210–300°C) consist of roughly 98.5 mol% CO₂, 0.5 mol% H₂S, and 1 mol% other components. ³He/⁴He ratios indicate a deep magmatic source (R/R_a up to 6) whereas δ¹³C–CO₂ values (−3 to −5‰) do not discriminate between a mantle/magmatic source and a source from subjacent, hydrothermally altered Paleozoic carbonate rocks. Regional gases from sites within a 50-km radius beyond Valles caldera are relatively enriched in CO₂ and He, but depleted in H₂S compared to Valles gases. Regional gases have R/R_a values ≤1.2 due to more interaction with the crust and/or less contribution from the mantle. Carbon sources for regional CO₂ are varied. During 1982–1998, repeat analyses of gases from intracaldera sites at Sulphur Springs showed relatively constant CH₄, H₂, and H₂S contents. The only exception was gas from Footbath Spring (1987–1993), which experienced increases in these three components during drilling and testing of scientific wells VC-2a and VC-2b. Present-day Valles gases contain substantially less N₂ than fluid inclusion gases trapped in deep, early-stage, post-caldera vein minerals. This suggests that the long-lived Valles hydrothermal system (ca. 1 Myr) has depleted subsurface Paleozoic sedimentary rocks of nitrogen. When compared with gases from many other geothermal systems, Valles caldera gases are relatively enriched in He but depleted in CH₄, N₂ and Ar. In this respect, Valles gases resemble end-member hydrothermal and magmatic gases discharged at hot spots (Galapagos, Kilauea, and Yellowstone).     

Performance of A Combination Process of UV/H2O2/Micro‐Aeration for Oxidation of Dichloroacetic Acid in Drinking Water

The decomposition of dichloroacetic acid (DCAA) in water using a UV/H₂O₂/micro‐aeration process was investigated in this paper. DCAA cannot be removed by UV radiation, H₂O₂ oxidation or micro‐aeration alone, while UV/H₂O₂/micro‐aeration combination processes have proved effective and can degrade this compound completely. With initial concentrations of about 110 μg/L, more than 95.1% of DCAA can be removed in 180 min under UV intensity of 1048.7 μW/cm², H₂O₂ dosage of 30 mg/L and micro‐aeration flow rate of 2 L/min. However, more than 30 μg/L of DCAA was left after 180 min by UV/H₂O₂ combination process without micro‐aeration with the same UV intensity and H₂O₂ dosage. The effects of applied UV radiation intensity, H₂O₂ dose, initial DCAA concentration and pH on the degradation of DCAA have been examined in this study. Degradation mechanisms of DCAA with hydroxyl radical oxidation have been discussed. The removal rate of DCAA was sensitive to operational parameters. There was a linear relationship between rate constant k and UV intensity and initial H₂O₂ concentration, which indicated that a higher removal capacity can be achieved by improvement of both factors. A newly found nitrogenous disinfection by‐product (N‐DBP)‐DCAcAm, which has the potential to form DCAA, was easier to remove than DCAA by UV/H₂O₂ and UV/H₂O₂/micro‐aeration processes. Finally, a preliminary cost comparison revealed that the UV/H₂O₂/micro‐aeration process was more cost‐effective than the UV/H₂O₂ process in the removal of DCAA from drinking water.     

地方震尾波震级的初步研究

地方震尾波由地壳横向不均匀性而产生的反向散射波组成。从这一观点出发,根据尾波随掠过时间的衰减特性,结合地震矩对数和地方震里克特地震级的线性关系,导出利用任一掠过时间的震尾来计算的尾波震级Mc公式。它的简化形式可以和持续时间震级的表达式近似一致。尾波震级可作为持续时间震级的一种广义形式,它是直接从震源地震矩导出的震级标度,从而为解释持续时间震级物理基础提供了可能的途径。应用于丹江地震台的资料,得到丹江口及邻区的尾波品质因子和介质函数以及地震矩对数和震级的期望关系,同时得到实用于该台的持续时间震级和简化尾波震级公式。     

Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

The concentration of molecular H2 and CH4 in the stratosphere

Stratospheric profiles of CH₄ and H₂ over eastern Texas have been derived up to 31 km altitude from air samples collected aboard a balloon and analyzed by gas chromatography. For H₂, contamination during flight and measurement presented a problem which has been resolved only recently. The earlier profiles require corrections which are rather large for the highest altitudes.The three profiles indicate an increase of the H₂ concentration in the lower stratosphere from about 0.5 p.p.m. per volume at the tropopause to about 0.8 p.p.m. at around 27 km altitude. Above that altitude the H₂ concentration decreases again. An air sample collected between 44 and 62 km by a rocket-borne cryogenic sampler had an H₂ concentration of 0.4 p.p.m.The five CH₄ profiles showed a decrease in CH₄ concentration with altitude generally with a steeper gradient directly above the tropopause and a weaker gradient at higher altitudes reaching 0.9 p.p.m. at 30 km altitude. The CH₄ concentration in the rocket sample was 0.25 p.p.m., in good agreement with the gradient obtained from the balloon samples.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

Biodegradability and Toxicity of Anionic Surfactants

Alkyl sulphates of the general formula CH_{2n + 1}-O-SO₃Na and alkyl sulphonates of the general formula C_nH_{2n + 1}-SO₃Na, where n = 8, 10, 12, 14 in each series have been tested for biodegradability with the modified OECD screening test No. 301 E, and for toxicity with Daphnia magna and with Photobacterium phosphoreum (the Microtox^TM test). The results show that both alkyl sulphates and alkyl sulphonates are biodegraded with the alkyl sulphates degrading more rapidly under the test conditions. The alkyl sulphates also have higher toxicity to both test species and for both alkyl sulphates and sulphonates the toxicity increases linearly with increasing molecular weight of the surfactant.     

Geochemical evidence for mixing of magmatic fluids with seawater,Nisyros hydrothermal system,Greece

The chemical and isotopic compositions (δD_H2O, δ¹⁸O_H2O, δ¹⁸O_CO2, δ¹³C_CO2, δ³⁴S, and He/N₂ and He/Ar ratios) of fumarolic gases from Nisyros, Greece, indicate that both arc-type magmatic water and local seawater feed the hydrothermal system. Isotopic composition of the deep fluid is estimated to be +4.9±0.5‰ for δ¹⁸O and ?11±5‰ for δD corresponding to a magmatic water fraction of 0.7. Interpretation of the stable water isotopes was based on liquid–vapor separation conditions obtained through gas geothermometry. The H₂–Ar, H₂–N₂, and H₂–H₂O geothermometers suggest reservoir temperatures of 345±15 °C, in agreement with temperatures measured in deep geothermal wells, whereas a vapor/liquid separation temperature of 260±30 °C is indicated by gas equilibria in the H₂O–H₂–CO₂–CO–CH₄ system. The largest magmatic inputs seem to occur below the Stephanos–Polybotes Micros crater, whereas the marginal fumarolic areas of Phlegeton–Polybotes Megalos craters receive a smaller contribution of magmatic gases.