Cretaceous petroleum system of the Khasib and Tannuma oil reservoir, East Baghdad oil field, Iraq

Gas chromatography, palynomorph constituents, and maturation are analyzed for oil samples of the Campanian Khasib and Tannuma Formations in the wells of East Baghdad oil field for biomarker studies, while palynomorph constituents and their maturation, Rock Eval pyrolysis, total organic carbon (TOC) analysis are carried on for the Upper Jurassic and the Cretaceous Formations of core samples from the same wells for dating and evaluation of the source rocks. The gas chromatography of these oils have shown biomarkers of abundant ranges of n-alkanes of less than C₂₂(C₁₇–C₂₁) with C₁₉ and C₁₈ peaks to suggest mainly liquid oil constituents of paraffinic hydrocarbons from marine algal source of restricted palaeoenvironments in the reservoir as well as low nonaromatic $ {\hbox{C}}_{15}^{+} $ peaks to indicate their slight degradation and water washing. Oil biomarkers of $ \Pr ./{\hbox{Ph}}{.} = {0}{.85,}{{\hbox{C}}_{31}}/{{\hbox{C}}_{30}} < 1.0 $ , location is in the triangle of C₂₇–C₂₉ sterane, C28/C29 of 0.6 sterane, oleanane of 0.01, and CPI = 1.0, could indicate anoxic marine environment with carbonate deposition of Upper Jurassic–Early Cretaceous source. The recorded palynomorph constituents in this oil and associated water are four miospore, seven dinoflagellates, and one Tasmanite species that could confirm affinity to the Upper most Jurassic–Lower Cretaceous Chia Gara and Ratawi Formations. The recorded palynomorphs from the reservoir oil (Khasib and Tannuma Formations) are of light brown color of $ {\hbox{TAI}} = 2.8 - 3.0 $ and comparable to the mature palynomorphs that belong to Chia Gara and Lower part of Ratawi Formations. Chia Gara Formation had generated and expelled high quantity of oil hydrocarbons according their TOC weight percent of 0.5–8.5 with ${S_2} = 2.5 - 18.5\,{\hbox{mg}}\,{\hbox{Hc/g}}\;{\hbox{rock}} $ , high hydrogen index of the range 150–450 mg Hc/g Rock, good petroleum potential of 4.5–23.5 mg Hc/g rock, mature ( $ {\hbox{TAI}} = 2.8 - 3.0 $ and $ {\hbox{T}}\max = 428 - 443{\hbox{C}} $ ), kerogen type II, and palynofacies parameters of up to 100 amorphous organic matters with algae deposited in dysoxic–anoxic to suboxic–anoxic basin, while the palynomorphs of the rocks of Khasib Formation are of amber yellow color of TAI = 2.0 with low TOC and hence not generated hydrocarbons. But, this last formation could be considered as oil reservoir only according their high porosity (15–23%) and permeability (20–45 mD) carbonate rocks with structural anticline closure trending NW-SE. That oil have generated and expelled during two phases; the first is during Early Palaeogene that accumulated in traps of the Cretaceous structural deformation, while the second is during Late Neogene’s.     

The R{\overline{3}} c \to R{\overline{3}} m transition in nitratine, NaNO3, and implications for calcite, CaCO3

The temperature dependences of the crystal structure and superstructure intensities in sodium nitrate, mineral name nitratine, NaNO₃, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction. Nitratine transforms from $R{\overline{3}} c\;\hbox{to}\;R{\overline{3}} m$ at T _c = 552(1) K. A NO₃ group occupies, statistically, two positions with equal frequency in the disordered $R{\overline{3}} m$ phase, but with unequal frequency in the partially ordered $R{\overline{3}} c$ phase. One position for the NO₃ group is rotated by 60° or 180° with respect to the other. The occupancy of the two orientations in the $R{\overline{3}} c$ phase is obtained from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x ? 1, where S is 0 at T _c and 1 at 0 K. The NO₃ groups rotate in a rapid process from about 541 to T _c, where the a axis contracts. Using a modified Bragg–Williams model, a good fit was obtained for the normalized intensities (that is, normalized, NI^1/2) for the (113) and (211) reflections in $R{\overline{3}} c\hbox {\,NaNO}_{3},$ and indicates a second-order transition. Using the same model, a reasonable fit was obtained for the order parameter, S, and also supports a second-order transition.     

The origin of mafic rocks in the Naqadeh intrusive complex, Sanandaj-Sirjan Zone, NW Iran

The Naqadeh mafic plutonic rocks are located on a plutonic assemblage and include different granitoid rocks related to ～40 Ma. U-Pb SHRIMP data shows different ages of 96?±?2.3 Ma for mafic rocks. Naqadeh mafic plutonic rocks consist of diorite to diorite-gabbros with relatively high contents of incompatible elements, low Na2O, and $ {\hbox{Mg\# }} = \left[ {{\hbox{molar}}\;{100} \times {\hbox{MgO/}}\left( {{\hbox{MgO}} + {\hbox{FeO}}} \right)} \right] > 44.0 $ . These features suggest that the Naqadeh mafic rocks originate from enriched lithospheric mantle above subducted slab during Neotethys subduction under Iranian plate.     

Carbon dioxide,water vapour and energy fluxes over a semi-evergreen forest in Assam,Northeast India

The eddy covariance method is a powerful technique for quantification of \(\hbox {CO}_{2},\) \(\hbox {H}_{2}\)O and energy fluxes in natural ecosystems. Leaf area index (LAI) and its changes are significant drivers of \(\hbox {CO}_{2}\) and \(\hbox {H}_{2}\)O exchange in a forest ecosystem due to their role in photosynthesis. The present study reports the seasonal variation of \(\hbox {CO}_{2}\) and energy fluxes and their relationship with other meteorological parameters of a semi-evergreen primary forest of Kaziranga National Park, Assam, India during February 2016–January 2017. The diurnal pattern of half hourly average \(\hbox {CO}_{2 }\) fluxes over the forest was found to be mostly dominated by the incident photosynthetically active radiation. During the period of study, diurnal variations of \(\hbox {CO}_{2}\) flux showed a maximum value of \(-9.97\,\upmu \)mol \(\hbox {m}^{-2}\hbox {s}^{-1}\) in the month of June during summer which is also the beginning of the monsoon season. The monthly averaged diurnal \(\hbox {CO}_{2}\) flux and variation in LAI of the forest canopy closely followed each other. The annual net ecosystem exchange of the forest estimated from the \(\hbox {CO}_{2}\) flux data above the canopy is 84.21 g C \(\hbox {m}^{-2}\,\hbox {yr}^{-1}\). Further studies are in progress to confirm these findings. The estimated average annual evapotranspiration of the semi-evergreen forest is 2.8 ± 0.19 mm \(\hbox {day}^{-1}\). The study of partitioning of energy fluxes showed the dominance of latent heat fluxes over sensible heat fluxes. The energy balance closure was found to increase with an increase in instability and the highest closure of around 83% was noted under neutral conditions.     

Characteristics of surface ozone in Agra,a sub-urban site in Indo-Gangetic Plain

In the present study, measurements of surface ozone (\(\hbox {O}_{3}\)) and its precursors (NO and \(\hbox {NO}_{2}\)) were carried out at a sub-urban site of Agra (\(27{^{\circ }}10'\hbox {N}\), \(78{^{\circ }}05'\hbox {E}\)), India during May 2012–May 2013. During the study period, average concentrations of \(\hbox {O}_{3}\), NO, and \(\hbox {NO}_{2}\) were \(39.6 \pm 25.3\), \(0.8 \pm 0.8\) and \(9.1 \pm 6.6 \, \hbox {ppb}\), respectively. \(\hbox {O}_{3}\) showed distinct seasonal variation in peak value of diurnal variation: summer \({>}\) post-monsoon \({>}\) winter \({>}\) monsoon. However, \(\hbox {NO}_{2}\) showed highest levels in winter and lowest in monsoon. The average positive rate of change of \(\hbox {O}_{3}\) (08:00–11:00 hr) was highest in April (16.3 ppb/hr) and lowest in August (1.1 ppb/hr), while average negative rate of change of \(\hbox {O}_{3}\) (17:00–19:00 hr) was highest in December (–13.2 ppb/hr) and lowest in July (–1.1 ppb/hr). An attempt was made to identify the \(\hbox {VOC--NO}_{\mathrm{x}}\) sensitivity of the site using \(\hbox {O}_{3}/\hbox {HNO}_{3}\) ratio as photochemical indicator. Most of the days this ratio was above the threshold value (12–16), which suggests \(\hbox {NO}_{\mathrm{x}}\) sensitivity of the site. The episodic event of ozone was characterized through meteorological parameters and precursors concentration. Fine particles (\(\hbox {PM}_{2.5}\)) cause loss of ozone through heterogeneous reactions on their surface and reduction in solar radiation. In the study, statistical analyses were used to estimate the amount of ozone loss.     

P wave attenuation structure beneath the Kanto district and surrounding area, Japan

Spectral ratios of teleseismic P waves for 15 deep (>200 km) earthquakes recorded at 146 High-Sensitivity Seismographic Network stations in the Kanto district and its surrounding area, eastern Japan, were inverted for attenuation parameter $ t_P^{ * } $ . The dataset consisted of good-quality vertical-component seismograms, whose P phases were handpicked. The P wave spectral ratios with high signal-to-noise ratios were calculated up to 1 Hz for all the station pairs, linear regressed, and then inverted for $ t_P^{ * } $ using the technique of least squares . The result showed that the active volcanic areas were clearly characterized by high $ t_P^{ * } $ . In contrast, $ t_P^{ * } $ varied in the nonvolcanic areas. The present result on the $ t_P^{ * } $ distribution was roughly consistent with the shallow part (<30 km) of an attenuation structure, which has been previously obtained based on 3-D tomography by using records of high-frequency (around 5 Hz) P waves from local earthquakes. This suggested that the present method of $ t_P^{ * } $ estimation is valid. The advantage and possible application to other areas were also discussed.     

New paleomagnetic results on $$\sim $$2367 Ma Dharwar giant dyke swarm,Dharwar craton,southern India: implications for Paleoproterozoic continental reconstruction

Here we report new paleomagnetic results and precise paleopole position of the extensional study on \(\sim \)2367 Ma mafic giant radiating dyke swarm in the Dharwar craton, southern India. We have sampled 29 sites on 12 dykes from NE–SW Karimnagar–Hyderabad dykes and Dhone–Gooty sector dykes, eastern Dharwar craton to provide unambiguous paleomagnetism evidence on the spectacular radiating dyke swarm and thereby strengthening the presence of single magmatic event at \(\sim \)2367 Ma. A total of 158 samples were subjected to detailed alternating field and thermal demagnetization techniques and the results are presented here along with previously reported data on the same dyke swarm. The remanent magnetic directions are showing two components, viz., seven sites representing four dykes show component (A) with mean declination of \(94{{}^{\circ }}\) and mean inclination of \(-\,70{{}^{\circ }}\) (\(\hbox {k}=87\), \(\upalpha _{95}=10{{}^{\circ }}\)) and corresponding paleopole at \(16{{}^{\circ }}\hbox {N}\), \(41{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=15{{}^{\circ }}\) and \(\hbox {dm}=17{{}^{\circ }}\)) and 22 sites representing 8 dykes yielded a component (B) with mean declination of \(41{{}^{\circ }}\) and mean inclination of \(-\,21{{}^{\circ }}\) (\(\hbox {k}=41\), \(\upalpha _{95}=9{{}^{\circ }}\)) with a paleopole at \(41{{}^{\circ }}\hbox {N}\), \(200{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=5{{}^{\circ }}\) and \(\hbox {dm}=10{{}^{\circ }}\)). Component (A) results are similar to the previously reported directions from the \(\sim \)2367 Ma dyke swarm, which have been confirmed fairly reliably to be of primary origin. The component (B) directions appear to be strongly overprinted by the 2080 Ma event. The grand mean for the primary component (A) combined with earlier reported studies gives mean declination of \(97{{}^{\circ }}\) and mean inclination of \(-\,79{{}^{\circ }}\) (\(\hbox {k}=55\), \(\upalpha _{95}=3{{}^{\circ }}\)) with a paleopole at \(15{{}^{\circ }}\hbox {N}\), \(57{{}^{\circ }}\hbox {E}\) (\(\hbox {dp}=5{{}^{\circ }}\), \(\hbox {dm}=6{{}^{\circ }}\)). Paleogeographical position for the Dharwar craton at \(\sim \)2367 Ma suggests that there may be a chance to possible spatial link between Dharwar dykes of Dharwar craton (India), Widgemooltha and Erayinia dykes of Yilgarn craton (Australia), Sebanga Poort Dykes of Zimbabwe craton (Africa) and Karelian dykes of Kola-Karelia craton (Baltica Shield).     

Thermodynamics and phonon dispersion of pyrope and grossular silicate garnets from ab initio simulations

The phonon dispersion and thermodynamic properties of pyrope (\(\hbox {Mg}_3\hbox {Al}_2\hbox {Si}_3\hbox {O}_{12}\)) and grossular (\(\hbox {Ca}_3\hbox {Al}_2\hbox {Si}_3\hbox {O}_{12}\) ) have been computed by using an ab initio quantum mechanical approach, an all-electron variational Gaussian-type basis set and the B3LYP hybrid functional, as implemented in the Crystal program. Dispersion effects in the phonon bands have been simulated by using supercells of increasing size, containing 80, 160, 320, 640, 1280 and 2160 atoms, corresponding to 1, 2, 4, 8, 16 and 27 \(\mathbf {k}\) points in the first Brillouin zone. Phonon band structures, density of states and corresponding inelastic neutron scattering spectra are reported. Full convergence of the various thermodynamic properties, in particular entropy (S) and specific heat at constant volume (\(C_\mathrm{{V}}\)), with the number of \(\mathbf {k}\) points is achieved with 27 \(\mathbf {k}\) points. The very regular behavior of the S(T) and \(C_\mathrm{{V}}(T)\) curves as a function of the number of \(\mathbf {k}\) points, determined by high numerical stability of the code, permits extrapolation to an infinite number of \(\mathbf {k}\) points. The limiting value differs from the 27-\(\mathbf {k}\) case by only 0.40 % at 100 K for S (the difference decreasing to 0.11 % at 1000 K) and by 0.29 % (0.05 % at 1000 K) for \(C_\mathrm{{V}}\). The agreement with the experimental data is rather satisfactory. We also address the problem of the relative entropy of pyrope and grossular, a still debated question. Our lattice dynamical calculations correctly describe the larger entropy of pyrope than grossular by taking into account merely vibrational contributions and without invoking “static disorder” of the Mg ions in dodecahedral sites. However, as the computed entropy difference is found to be larger than the experimental one by a factor of 2–3, present calculations cannot exclude possible thermally induced structural changes, which could lead to further conformational contributions to the entropy.     

The crystal structure of waylandite from Wheal Remfry, Cornwall, United Kingdom

Sr- and Ca-rich waylandite, $ {\left( {{\hbox{B}}{{\hbox{i}}_{0.{54}}}{\hbox{S}}{{\hbox{r}}_{0.{31}}}{\hbox{C}}{{\hbox{a}}_{0.{25}}}{{\hbox{K}}_{0.0{1}}}{\hbox{B}}{{\hbox{a}}_{0.0{1}}}} \right)_{\Sigma 1.12}}{{\hbox{H}}_{0.{18}}}{\left( {{\hbox{A}}{{\hbox{l}}_{{2}.{96}}}{\hbox{C}}{{\hbox{u}}_{0.0{2}}}} \right)_{\Sigma 2.98}}{\left[ {{{\left( {{{\hbox{P}}_{0.{97}}}{{\hbox{S}}_{0.0{3}}}{\hbox{S}}{{\hbox{i}}_{0.0{1}}}} \right)}_{\Sigma 1.00}}{{\hbox{O}}_4}} \right]_2}{\left( {\hbox{OH}} \right)_6} $ , from Wheal Remfry, Cornwall, United Kingdom has been investigated by single-crystal X-ray diffraction and electron microprobe analyses. Waylandite crystallises in space group R $ \overline 3 $ ? m, with the cell parameters: a?=?7.0059(7) Å, c?=?16.3431(12) Å and V?=?694.69(11) ų. The crystal structure has been refined to R ₁?=?3.76%. Waylandite has an alunite-type structure comprised of a rhombohedral stacking of (001) composite layers of corner-shared AlO₆ octahedra and PO₄ tetrahedra, with (Bi,Sr,Ca) atoms occupying icosahedrally coordinated sites between the layers.     

Phase diagram and thermodynamic properties of AIPO<Subscript>4</Subscript> based on first-principles calculations and the quasiharmonic approximation

We calculated the phase diagram of \(\hbox {AlPO}_{4}\) up to 15 GPa and 2,000 K and investigated the thermodynamic properties of the high-pressure phases. The investigated phases include the berlinite, moganite-like, \(\hbox {AlVO}_{4},\, P2_1/c\), and \(\hbox {CrVO}_{4}\) phases. The computational methods used include density functional theory, density functional perturbation theory, and the quasiharmonic approximation. The investigated thermodynamic properties include the thermal equation of state, isothermal bulk modulus, thermal expansivity, and heat capacity. With increasing pressure, the ambient phase berlinite transforms to the moganite-like phase, and then to the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases, and further to the \(\hbox {CrVO}_{4}\) phase. The stability fields of the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases are similar in pressure but different in temperature, as the \(\hbox {AlVO}_{4}\) phase is stable at low temperatures, whereas the \(P2_1/c\) phase is stable at high temperatures. All of the phase relationships agree well with those obtained by quench experiments, and they support the stabilities of the moganite-like, \(\hbox {AlVO}_{4}\), and \(P2_1/c\) phases, which were not observed in room-temperature compression experiments.     

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.     

Petrological cannibalism: the chemical and textural consequences of incremental magma body growth

The textures of minerals in volcanic and plutonic rocks testify to a complexity of processes in their formation that is at odds with simple geochemical models of igneous differentiation. Zoning in plagioclase feldspar is a case in point. Very slow diffusion of the major components in plagioclase means that textural evidence for complex magmatic evolution is preserved, almost without modification. Consequently, plagioclase affords considerable insight into the processes by which magmas accumulate in the crust prior to their eventual eruption or solidification. Here, we use the example of the 1980–1986 eruptions of Mount St. Helens to explore the causes of textural complexity in plagioclase and associated trapped melt inclusions. Textures of individual crystals are consistent with multiple heating and cooling events; changes in total pressure (P) or volatile pressure ( $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O ) are less easy to assess from textures alone. We show that by allying textural and chemical analyses of plagioclase and melt inclusions, including volatiles (H₂O, CO₂) and slow-diffusing trace elements (Sr, Ba), to published experimental studies of Mount St. Helens magmas, it is possible to disambiguate the roles of pressure and temperature to reconstruct magmatic evolutionary pathways through temperature–pressure–melt fraction (T– $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O –F) space. Our modeled crystals indicate that (1) crystallization starts at $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  > 300 MPa, consistent with prior estimates from melt inclusion volatile contents, (2) crystal cores grow at $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  = 200–280 MPa at F = 0.65–0.7, (3) crystals are transferred to $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  = 100–130 MPa (often accompanied by 10–20 °C of heating), where they grow albitic rims of varying thicknesses, and (4) the last stage of crystallization occurs after minor heating at $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O  ~ 100 MPa to produce characteristic rim compositions of An₅₀. We hypothesize that modeled $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O decreases in excess of ~50 MPa most likely represent upward transport through the magmatic system. Small variations in modeled $P_{{{\text{H}}_{ 2} {\text{O}}}}$ P H 2 O , in contrast, can be effected by fluxing the reservoir with CO₂-rich vapors that are either released from deeper in the system or transported with the recharge magma. Temperature fluctuations of 20–40 °C, on the other hand, are an inevitable consequence of incremental, or pulsed, assembly of crustal magma bodies wherein each pulse interacts with ancestral, stored magmas. We venture that this “petrological cannibalism” accounts for much of the plagioclase zoning and textural complexity seen not only at Mount St. Helens but also at arc magmas generally. More broadly we suggest that the magma reservoir below Mount St. Helens is dominated by crystal mush and fed by frequent inputs of hotter, but compositionally similar, magma, coupled with episodes of magma ascent from one storage region to another. This view both accords with other independent constraints on the subvolcanic system at Mount St. Helens and supports an emerging view of many active magmatic systems as dominantly super-solidus, rather than subliquidus, bodies.     

Application of Binary Permeability Fields for the Study of $${\hbox {CO}_{2}}$$ Leakage from Geological Carbon Storage in Saline Aquifers of the Michigan Basin

The feasibility of geological carbon storage (GCS) sites depends on their capacity to retain safely \({\hbox {CO}_{2}}\). While deep saline formations and depleted gas/oil reservoirs are good candidates to sequester \({\hbox {CO}_{2}}\), gas/oil reservoirs typically have a limited storage capacity compared to ideal targets (\(\sim \) 1 Mt/year) considered for \({\hbox {CO}_{2}}\) disposal (Celia et al. in Water Resour Res 51(9):6846–6892, 2015. doi: 10.1002/2015WR017609). In this respect, deep saline aquifers are considered more appropriate formations for GCS, but present the disadvantage of having limited characterization data. In particular, information about the continuity of the overlying sealing formations (caprock) is often sparse if it exists at all. In this work, a study of \({\hbox {CO}_{2}}\) leakage is conducted for a candidate GCS site located in the Michigan Basin, whose sealing properties of the caprock are practically unknown. Quantification of uncertainty on \({\hbox {CO}_{2}}\) leakage from the storage formation is achieved through a Monte Carlo simulation approach, relying on the use of a computationally efficient semi-analytical leakage model based upon the solution derived by Nordbotten et al. (Environ Sci Technol 43(3):743–749, 2009), which assumes leakage occurs across “passive” wells intersecting caprock layers. A categorical indicator Kriging simulator is developed and implemented to represent the caprock sealing properties and model the permeability uncertainty. Binary fields of caprock permeability are generated and exhibit mostly low permeability, with sparsely-occurring local high permeability areas where brine and \({\hbox {CO}_{2}}\) may leak out of the storage formation. In addition, the feasibility of extending the use of the semi-analytical model to large-area leakage pathways is studied. This work advances a methodology for preliminary uncertainty quantification of \({\hbox {CO}_{2}}\) leakage at sites of GCS with little or no information on the sealing properties of the caprock. The implemented analysis shows that, for the considered site, \({\hbox {CO}_{2}}\) leakage may not be negligible even for relatively low (\(\sim \) 1%) probabilities of finding permeable inclusions in the caprock and highlights the importance of being able to characterize caprock sealing properties over large areas.     

Thermal equation of state of synthetic orthoferrosilite at lunar pressures and temperatures

Iron-rich orthopyroxene plays an important role in models of the thermal and magmatic evolution of the Moon, but its density at high pressure and high temperature is not well-constrained. We present in situ measurements of the unit-cell volume of a synthetic polycrystalline end-member orthoferrosilite (FeSiO₃, fs) at simultaneous high pressures (3.4–4.8 GPa) and high temperatures (1,148–1,448 K), to improve constraints on the density of orthopyroxene in the lunar interior. Unit-cell volumes were determined through in situ energy-dispersive synchrotron X-ray diffraction in a multi-anvil press, using MgO as a pressure marker. Our volume data were fitted to a high-temperature Birch–Murnaghan equation of state (EoS). Experimental data are reproduced accurately, with a  $\varDelta P$ Δ P  standard deviation of 0.20 GPa. The resulting thermoelastic parameters of fs are: V ₀ = 875.8 ± 1.4 Å³, K ₀ = 74.4 ± 5.3 GPa, and $\frac{{\text d}K}{{\text d}T} = -0.032 \pm 0.005\,\hbox{GPa K}^{-1}$ d K d T = - 0.032 ± 0.005 GPa K - 1 , assuming ${K}^{\prime}_{0} = 10 $ K 0 ′ = 10 . We also determined the thermal equation of state of a natural Fe-rich orthopyroxene from Hidra (Norway) to assess the effect of magnesium on the EoS of iron-rich orthopyroxene. Comparison between our two data sets and literature studies shows good agreement for room-temperature, room-pressure unit-cell volumes. Preliminary thermodynamic analyses of orthoferrosilite, FeSiO₃, and orthopyroxene solid solutions, (Mg_1?x Fe _x ) SiO₃, using vibrational models show that our volume measurements in pressure–temperature space are consistent with previous heat capacity and one-bar volume–temperature measurements. The isothermal bulk modulus at ambient conditions derived from our measurements is smaller than values presented in the literature. This new simultaneous high-pressure, high-temperature data are specifically useful for calculations of the orthopyroxene density in the Moon.     

Application of environmental isotopes and hydrochemistry in the identification of source of seepage and likely connection with lake water in Lesser Himalaya,Uttarakhand, India

Oxygen (\({\updelta }^{18}\hbox {O}\)) and hydrogen (\({\updelta }^{2}\hbox {H}\) and \(^{3}\hbox {H}\)) isotopes of water, along with their hydrochemistry, were used to identify the source of a newly emerged seepage water in the downstream of Lake Nainital, located in the Lesser Himalayan region of Uttarakhand, India. A total of 57 samples of water from 19 different sites, in and around the seepage site, were collected. Samples were analysed for chemical tracers like \(\hbox {Ca}^{++}\), \(\hbox {Mg}^{++}\), \(\hbox {Na}^{+}\), \(\hbox {K}^{+}\), \({\hbox {SO}_{4}}^{--}\) and \(\hbox {Cl}^{-}\) using an Ion Chromatograph (Dionex IC-5000). A Dual Inlet Isotope Ratio Mass Spectrometer (DIIRMS) and an Ultra-Low Level Liquid Scintillation Counter (ULLSC), were used in measurements of stable isotopes (\({\updelta }^{2}\hbox {H}\) and \({\updelta }^{18}\hbox {O}\)) and a radioisotope (\(^{3}\hbox {H}\)), respectively. Results obtained in this study repudiate the possibility of any likely connection between seepage water and the lake water, and indicate that the source of seepage water is mainly due to locally recharged groundwater. The study suggests that environmental isotopes (\({\updelta }^{2}\hbox {H}\), \({\updelta }^{18}\hbox {O}\) and \(^{3}\hbox {H}\)) can effectively be used as ‘tracers’ in the detection of the source of seepage water in conjunction with other hydrochemical tracers, and can help in water resource management and planning.     

Fission-track evidence of tectonic evolution in the northwestern Qaidam Basin,China

Fission-track dating was conducted on zircons and apatites from 11 cores of the upper Xiaganchaigou Formation and lower Shangganchaigou Formation (northwestern Qaidam Basin). The obtained apatite fission-track age is 3.1–61.9 Ma, and the zircon fission-track age is 49.2–123.5 Ma. Although the average apatite age is consistent with ages predicted from the stratigraphy, nine of the 11 apatite fission-track ages have \(\hbox {P}(\upchi ^{2}) < 5\%\), indicating that the grains experienced heterogeneous annealing after sedimentation. The average zircon age is greater than that indicated by stratigraphy, and all eight zircon fission ages have \(\hbox {P}(\upchi ^{2})>5\%\), exhibiting consistent characteristics and indicating that zircons retain provenance age information after burial. From the zircon and apatite ages, the fission-track length distribution, and the geological setting, the northwestern Qaidam Basin has experienced two tectonothermal events since the Late Mesozoic, at \(39.1 \pm 9.3\) to \(133.7\,\pm \,6.6\,\hbox {Ma}\) and \(1.2 \pm 0.6\) to \(32.0\,\pm \,3.0\,\hbox {Ma}\). The earlier (39.1–133.7 Ma) tectonothermal event resulted from the initial collision of the Indian and Eurasian plates. As a consequence of the collision, the Altyn Tagh fault, which forms the northwestern boundary of the Qaidam Basin, began to develop. Subsequently, uplift of the Altyn Tagh mountains began and the northwestern depression of the Qaidam Basin started to form. The later (1.2–32.0 Ma) tectonothermal event resulted from further collision of the Indian and Eurasian plates along the Yarlung Tsangpo suture zone. Strata in the Qaidam Basin were further deformed by transpression in this period and this period played a crucial role in petroleum accumulation.     

Fluvial geochemistry of Subarnarekha River basin,India

The fluvial geochemistry of the Subarnarekha River and its major tributaries has been studied on a seasonal basis in order to assess the geochemical processes that explain the water composition and estimate solute fluxes. The analytical results show the mildly acidic to alkaline nature of the Subarnarekha River water and the dominance of \(\hbox {Ca}^{2+}\) and \(\hbox {Na}^{+}\) in cationic and \(\hbox {HCO}_{3}^{-}\) and \({\hbox {Cl}}^{-}\) in anionic composition. Minimum ionic concentration during the monsoon and maximum concentration in the pre-monsoon seasons reflect concentrating effects due to decrease in the river discharge and increase in the base flow contribution during the pre-monsoon and dilution effects of atmospheric precipitation in the monsoon season. The solute acquisition processes are mainly controlled by weathering of rocks, with minor contribution from marine and anthropogenic sources. Higher contribution of alkaline earth \((\hbox {Ca}^{2+}{+}\,\hbox {Mg}^{2+})\) to the total cations \((\hbox {TZ}^{+})\) and high \((\hbox {Na}^{+}+\hbox {K}^{+})/\hbox {Cl}^{-}\), \((\hbox {Na}^{+}+\hbox {K}^{+})/\hbox {TZ}^{+}\), \(\hbox {HCO}_{3}^{-}/(\hbox {SO}_{4}^{2-}+\hbox {Cl}^{-})\) and low \((\hbox {Ca}^{2+}+\hbox {Mg}^{2+})/(\hbox {Na}^{+}+\hbox {K}^{+})\) equivalent ratios suggest that the Subarnarekha River water is under the combined influence of carbonate and silicate weathering. The river water is undersaturated with respect to dolomite and calcite during the post-monsoon and monsoon seasons and oversaturated in the pre-monsoon season. The pH–log \(\hbox {H}_{4}\hbox {SiO}_{4}\) stability diagram demonstrates that the water chemistry is in equilibrium with the kaolinite. The Subarnarekha River annually delivered \(1.477\times 10^{6}\) ton of dissolved loads to the Bay of Bengal, with an estimated chemical denudation rate of \(77\hbox { ton km}^{-2}\hbox { yr}^{-1}\). Sodium adsorption ratio, residual sodium carbonate and per cent sodium values placed the studied river water in the ‘excellent to good quality’ category and it can be safely used for irrigation.     

Assessing climate change impacts on river hydrology – A case study in the Western Ghats of India

The objective of this study is to evaluate the hydrological impacts of climate change on rainfall, temperature and streamflow in a west flowing river originating in the Western Ghats of India. The long-term trend analysis for 110 yr of meteorological variables (rainfall and temperature) was carried out using the modified Mann–Kendall trend test and the magnitude of the trend was quantified using the Sen’s slope estimator. The Regional Climate Model (RCM), COordinated Regional climate Downscaling EXperiment (CORDEX) simulated daily weather data of baseline (1951–2005) and future RCP 4.5 scenarios (2006–2060) were used to run the hydrological model, Soil and Water Assessment Tool (SWAT), in order to evaluate the effect of climate change on rainfall, temperature and streamflow. Significant changes were observed with regard to rainfall, which have shown decreasing trend at the rate of 2.63 mm per year for the historical and 8.85 mm per year for RCP 4.5 future scenarios. The average temperature was found to be increasing at \(0.10\,^{\circ }\hbox {C}\) per decade for both historical and future scenarios. The impact of climate change on the annual streamflow yielded a decreasing trend at the rate of \(1.2\,\hbox {Mm}^{3}\) per year and 2.56 \(\hbox {Mm}^{3},\) respectively for the past and future scenarios. The present work also investigates the capability of SWAT to simulate the groundwater flow. The simulated results are compared with the recession limb of the hydrograph and were found to be reasonably accurate.     

Probabilistic seismic hazard at the archaeological site of Gol Gumbaz in Vijayapura,south India

Probabilistic seismic hazard analysis (PSHA) is carried out for the archaeological site of Vijayapura in south India in order to obtain hazard consistent seismic input ground-motions for seismic risk assessment and design of seismic protection measures for monuments, where warranted. For this purpose the standard Cornell-McGuire approach, based on seismogenic zones with uniformly distributed seismicity is employed. The main features of this study are the usage of an updated and unified seismic catalogue based on moment magnitude, new seismogenic source models and recent ground motion prediction equations (GMPEs) in logic tree framework. Seismic hazard at the site is evaluated for level and rock site condition with 10% and 2% probabilities of exceedance in 50 years, and the corresponding peak ground accelerations (PGAs) are 0.074 and 0.142 g, respectively. In addition, the uniform hazard spectra (UHS) of the site are compared to the Indian code-defined spectrum. Comparisons are also made with results from National Disaster Management Authority (NDMA 2010), in terms of PGA and pseudo spectral accelerations (PSAs) at T = 0.2, 0.5, 1.0 and 1.25 s for 475- and 2475-yr return periods. Results of the present study are in good agreement with the PGA calculated from isoseismal map of the Killari earthquake, \({\hbox {M}}_{\mathrm{w}} = 6.4\) (1993). Disaggregation of PSHA results for the PGA and spectral acceleration (\({\hbox {S}}_{\mathrm{a}}\)) at 0.5 s, displays the controlling scenario earthquake for the study region as low to moderate magnitude with the source being at a short distance from the study site. Deterministic seismic hazard (DSHA) is also carried out by taking into account three scenario earthquakes. The UHS corresponding to 475-yr return period (RP) is used to define the target spectrum and accordingly, the spectrum-compatible natural accelerograms are selected from the suite of recorded accelerograms.     

Lithologic boundaries from gravity and magnetic anomalies over Proterozoic Dalma volcanics

Dalma volcanics (DVs) has intruded the older Singhbhum Group of Metapelites. Despite DVs being rich in mineralisation, its boundaries are not clearly demarcated. Gravity and magnetic surveys have been attempted for mapping the boundaries in DVs. These surveys were made in the northern fringe of the DVs over an area of \(\sim \)0.70 \(\hbox {km}^{2}\) along 13 parallel lines at 50 m spacing. The data was acquired at \(\sim \)25 \(\hbox {m}\) spacing. The surveys were taken for determination of lithological boundaries, depths and nature of causative source using Euler depth solutions and radially averaged power spectrum (RAPS). Residual anomaly maps of gravity and magnetic intensity show the same trend as that of Bouguer gravity anomaly and total magnetic intensity anomaly map indicating towards shallow sources. The magnetic map in general follows the same pattern as that of gravity anomaly maps. The map shows coincident high gravity and magnetic anomalies. These anomalies together with resistivity signatures confirm that the northern fringe of DVs hosts volcanogenic massive sulphide settings. The Euler depth solution delineated the lateral boundaries and nature of the source. It seems that the source is of spherical nature lying within a depth range of 25–40 m. The obtained lithological (vertical) units from RAPS are between Lower DVs, Upper DVs and Singhbhum Group Metapelites at depths of \(\sim \)15, \(~\sim \)25 and \(\sim \)40 \(\hbox {m}\), respectively. The metallogeny is associated with the Upper DVs and the corresponding delineated lithological (vertical) unit is indicative of the top of the ore body. Good agreement is observed with the geological succession from the drilling data and resistivity data. The findings suggest that the northern fringe of DVs could be a preferred target for drilling.