Geochemical study on oil-cracked gases and kerogen-cracked gases (II)—Discrimination methods between oil-cracked gases and kerogen-cracked gases

In the processes of discrimination between oil-cracked gases and kerogen-cracked gases, Behar and Pinzgofer et al.’s results were adopted in the former researches, in which the ratio of C₂/C₃ is basically a constant while the ratio of C₁/C₂ gradually increases in the course of primary cracking of kerogen. Otherwise in the course of secondary cracking of oil, the ratio of C₂/C₃ increases rapidly while C₁/C₂ keeps relatively stable. Our study on analogue experiment shows that, whether it is oil or kerogen, in its process of gas generating by cracking, the ratios of C₂/C₃, C₁/C₂ or C₁/C₃ will all be increased with the growth of thermal conditions. In comparison, the ratio of C₂/C₃, which is affected by genetic type to some comparatively less extent, mainly responds to the maturity of gases, while the value of C₂/C₃ is about 2, and that of C₂/iC₄ is about 10, and the corresponding value of R _o is about 1.5%–1.6%. The influence of gas source on C₂/C₃ is less than that of gas maturity, otherwise C₁/C₂ (or C₁/C₃) is obviously affected by cracking matrices. The ratios of C₁/C₂, C₁/C₃ of oil-cracked gases are less than that of kerogen-cracked gases, under the condition that the ratios of C₂/C₃ are similar in value, so are the value of dryness indexes. There exists wide diffidence between this view and the former discrimination method in theory. The analysis of the spot sample indicates that we can apply the above basic view to dealing efficiently with the problem of the discrimination between oil-cracked gas and kerogen-cracked gas.     

Eutectic between wollastonite II and calcite contrasted with thermal barrier in MgO-SiO2-CO2 at 30 kilobars,with applications to kimberlite-carbonatite petrogenesis

In the join CaCO₃-CaSiO₃ at 30 kbars, calcite melts at 1615°C, wollastonite II at 1600°C, and a binary eutectic occurs at 1365°C with liquid composition 43 wt.% CaCO₃, 57 wt.% CaSiO₃. The eutectic liquid quenches to a glass with few quench crystals. In the join MgCO₃-MgSiO₃ at 30 kbars, magnesite melts at 1590°C, enstatite at 1837°C, and the fields for the primary crystallization of magnesite and enstatite are separated by a thermal barrier near 1900°C for the melting of forsterite in the presence of CO₂. Only about 10 wt.% MgSiO₃ dissolves in the carbonate liquid. These data, are considered together with incomplete results for joins CaMgSi₂O₆-CaMg(CO₃)₂, CaMgSi₂O₆-MgCO₃, CaMgSi₂O₆-CaCO₃, and other published data in the system CaO-MgO-SiO₂-CO₂. A thermal barrier separates the silicate and carbonate liquids in MgO-SiO₂-CO₂ but, in the quaternary system, silicate liquids with dissolved CO₂ can follow fractionation paths around the forsterite field to the fields for the primary crystallization of carbonates. This suggests that fractional crystallization of CO₂-bearing ultrabasic magma at 100 km depth can produce residual carbonatite magma.     

Effect of Ozone and Ozone/Fenton in the Advanced Oxidation Process on Biodegradable Characteristics of Semi‐aerobic Stabilized Leachate

This study investigated the effects of O₃ and O₃/H₂O₂/Fe²⁺ in the advanced oxidation processes (AOPs) on the biodegradable and soluble characteristics of semi‐aerobic stabilized solid waste leachate. The biodegradability (BOD₅/chemical oxygen demand, COD) ratio improved from 0.034 to 0.05 and 0.1 following O₃ and O₃/H₂O₂/Fe²⁺, respectively. Fractions of biodegradable COD_(bi) (24%), non‐biodegradable COD_(ubi) (76%), soluble COD_(s) (59%), biodegradable soluble COD_(bsi) (38%), non‐biodegradable soluble COD_(ubsi) (62%), and particulate COD (PCOD) (41%) in stabilized leachate were also investigated. The fraction of COD_(bi) increased to 28 and 36% after applying O₃ and O₃/AOPs, respectively. COD_(S) increased to 59% after O₃ and to 72% after O₃/AOPs, whereas COD_(bsi) increased to 38 and 51% after O₃ and O₃/AOPs, respectively. The removal efficiency of COD_(S) was obtained at 5% after O₃ alone and improved to 51% following ozone‐based AOPs, whereas the removal efficiency of PCOD improved from 25% after O₃ to 71% after ozone‐based AOPs.     

Effective Removal of Microorganisms and Biostimulants of Wastewater by the Application of Various Electrolytes

A variety of electrolytes FeCl₃, CaCl₂, CuSO₄, Al₂(SO₄)₃, and LaCl₃ was investigated for their efficiency in removing biostimulants (phosphorous and nitrogen) to improve the water quality. Results show that the removal of PO₄^3– was achieved below the detection limit (BDL) by two electrolytes, CuSO₄ and Al₂(SO₄)₃, and up to 1.0 ± 0.0 mg/L by LaCl₃ from a value of 15.0 mg/L, of the concentration of PO₄^3– in amended water. The turbidity was found to be removed significantly by FeCl₃, CuSO₄, and Al₂(SO₄)₃ by about 5.8 ± 2.6, 9.7 ± 1.0, and 5.4 ± 1.1 nephalometric turbidity unit (NTU), respectively. The removal of the members of Enterobacteriaceae viz., Escherichia coli, Enterobacter spp. Pseudomonas fluorescence, and Pseudomonas spp. was found almost in all the chemical precipitants but their removal was more significant in the water samples treated with CuSO₄, Al₂(SO₄)₃, and LaCl₃. To achieve a complete removal and to sustain the after effects of precipitation, such as recurrence of algal growth, the combination of CuSO₄ and Al₂(SO₄)₃ was investigated. Reduction in the turbidity from 30.83 to <2 NTU, phosphate ion from a value of 1.28 mg/L to BDL and ammonia ion from a value of 44.71 to 36.48 mg/L of natural pond water were observed after the treatment with CuSO₄ and Al₂(SO₄)₃ in combination.     

Oxysulfates of copper, sodium, and potassium in the lava flows of the 2012–2013 Tolbachik Fissure Eruption

Samples from the surface of lava flows discharged by the 2012–2013 Tolbachik Fissure Eruption were found to contain oxysulfates of copper, sodium, and potassium: K₂Cu₃O(SO₄)₂ (fedotovite), NaKCu₂O(SO₄)₂, and Na₃K₅Cu₈O₄(SO₄)₈. The last two phases have no naturally occurring or synthetic analogues that we are aware of. They form flattened crystals of prismatic to long-prismatic habits. The crystals of Na₃K₅Cu₈O₄(SO₄)₈ have a chemical composition corresponding to the empirical formula Na_2.22K_5.47Cu_8.02S_8.05O₃₆. An X-ray analysis of this compound showed that it has a monoclinic symmetry, P2/c, a = 13.909(4), b = 4.977(1), c = 23.525(6) Å, β = 90.021(5)°, V = 1628.3(7) ų. The crystal structure was determined by direct techniques and refined to yield R ₁ for 3955 reflexes//web// with F ² > 4σF. The compound NaKCu₂O(SO₄)₂ also belongs to the monoclinic system, P2/c, a = 14.111(4), b = 4.946(1), c = 23.673(6) Å, β = 92.052(6)°, V = 1651.1(8) ų. The structure was determined by direct techniques to yield a tentative structural model that has been refined up to R ₁ = 0.135 for 4088 reflexes with F ² > 4σF. The crystal structure of Na₃K₅Cu₈O₄(SO₄)₈ is based on chains of [O₂Cu₄]⁴⁺ consisting of rib-coupled oxy-centered tetrahedrons of (OCu₄)⁶⁺. The chains are surrounded by sulfate radicals, resulting in columns of {[O₂Cu₄](SO₄)₄}^4? aligned along the b axis. The interchain space contains completely ordered positions of Na⁺ and K⁺ cations. The principle underlying the connection of NaKCu₂O(SO₄)₂ columns in the crystal structure of {[O₂Cu₄](SO₄)₄}^4? is different, in view of the relation Na:K = 1 as contrasted with 3:5 for the compound Na₃K₅Cu₈O₄(SO₄)₈. The presence of oxy-centered tetrahedrons in the structure of these new compounds furnishes an indirect hint at the importance of polynuclear copper-oxygen radicals with centering oxygen atoms as forms of transport of copper by volcanic gases.     

High-pressure decomposition of Ca2GeO4 and Ca2MnO4 with the K2NiF4-type structures

By using the diamond-anvil pressure cell coupled with laser heating, Ca₂GeO₄ in the K₂NiF₄-type structure has been found to decompose into the mixture Ca₃Ge₂O₇ plus CaO at pressures greater than 200 kbar and at about 1000°C, and the same type of structure for Ca₂MnO₄ has been found to decompose into the mixture CaMnO₃ (perovskite) plus CaO at pressures greater than 100 kbar and at about 1400°C. The decomposition product of Ca₃Ge₂O₇ is a new compound which is isostructural with Sr₃Ti₂O₇ and has the lattice parameters of a = 3.72 ± 0.01 and $\text{c = 19.32 ± 0.05}\text{A}\text{?}$ at room temperature and 1 bar pressure. The results of the study of Ca₂GeO₄ and Ca₂MnO₄ (both with the K₂NiF₄-type structure) strongly support the view that compounds possessing the K₂NiF₄-type structure are unstable relative to corresponding mixtures possessing the perovskite and rocksalt structures. It is concluded that, in the earth's mantle, the K₂NiF₄-type Ca₂SiO₄ would ultimately decompose into the mixture CaSiO₃ (perovskite) + CaO or would otherwise transform to other as-yet-unknown phase(s), and that the mixture of MgSiO₃ (perovskite) + MgO (the post-spinel phase of Mg₂SiO₄) would not adopt the K₂NiF₄-type structure.     

MnO/TiO2/P2O5: a minor element discriminant for basaltic rocks of oceanic environments and its implications for petrogenesis

A ternary diagram using MnO, TiO₂, P₂O₅ can discriminate between five petrotectonic environments of basaltic rocks (45–54% SiO₂). Fields for mid-ocean ridge, island arc tholeiite, island arc calc-alkaline, ocean island tholeiite, and ocean island alkalic rocks were distinguished on the basis of 507 analyses from well-defined environments. Boninites plot within island arc fields. Continental tholeiites, such as the Columbia River basalts, are high in P₂O₅ relative to MnO and TiO₂, and overlap portions of all five oceanic fields.MnO is depleted relative to TiO₂ in mid-ocean ridge analyses and may be controlled by early fractionation of olivine and/or clinopyroxene under conditions of lowf_O2. In island arc rocks, MnO is enriched relative to TiO₂ due to early crystallization of titanomagnetite in a high-f_O2 environment. Primitive mid-ocean ridge and arc tholeiites have similar MnO/TiO₂/P₂O₅ ratios which indicate a grossly similar parent magma. Increasingly differentiated basaltic rocks are more easily classified by the diagram. High relative abundances of TiO₂ and P₂O₅ in ocean island rocks are consistent with their derivation from a separate source.Despite the purported high mobility of MnO, the MnO/TiO₂/P₂O₅ discriminant diagram may be applied to unspilitized and moderately spilitized zeolite to greenschist facies greenstones with good agreement between the environment determined by MnO/TiO₂/P₂O₅ and by other means such as trace elements, REE, or field relations.     

Ni2SiO4-enthalphy of the olivine-spinel transition by solution calorimetry at 713°C

The high pressure spinel polymorph of Ni₂SiO₄ persists metastably at 713°C and atmospheric pressure. The enthalpy of the olivine-spinel transition was obtained by measuring the heats of solution of both polymorphs in a molten oxide solvent, 2PbO · B₂O₃, at that temperature. For Ni₂SiO₄(ol)→Ni₂SiO₄, ΔH₉₈₆⁰ = +1.4 ± 0.7kcal/mol. The heat content increments, H₉₈₆ ? H₂₉₇, were found to be: olivine, 25.73 ± 0.42kcal/mol, and spinel, 25.39 ± 0.20kcal/mol. The measured enthalpy of the transformation is consistent with the low slope of the phase boundary, ?P/?T = ～ 12b/deg, observed by Akimoto and others. The entropy of the olivine-spinel transition in Ni₂SiO₄ is accordingly about a factor of three smaller in magnitude (ΔS = ～ ?1cal/deg mol) than that for Co₂SiO₄,Fe₂SiO₄,Mg₂SiO₄or Mg₂GeO₄ (ΔS = ?3to?3.5cal/deg mol).     

The system enstatite-pyrope at high pressures and temperatures and the mineralogy of the earth's mantle

In a diamond-anvil pressure cell coupled with laser heating, the system enstatite (MgSiO₃)-pyrope (3 MgSiO₃ · Al₂O₃) has been studied in the pressure region between about 100 and 300 kbar at about 1000°C using glass starting materials. The high-pressure phase behavior of the intermediate compositions of the system contrasts greatly with that of the two end-members. Differences between MgSiO₃ and 95% MgSiO₃ · 5% Al₂O₃ are especially remarkable. The phase assemblages β-Mg₂SiO₄ + stishovite and γ-Mg₂SiO₄ (spinel) + stishovite displayed by MgSiO₃ were not observed in 95% MgSiO₃ · 5% Al₂O₃, and the garnet phase, which was observed in 95% MgSiO₃ · 5% Al₂O₃ at high pressure, was not detected in MgSiO₃. These results suggest that the high-pressure phase transformations found in pure MgSiO₃ would be inhibited under mantle conditions by the presence even of small amounts of Al₂O₃ (?4% by weight). On the other hand, pyrope displays a wide stability field, finally transforming at 240–250 kbar directly to an ilmenite-type modification of the same stoichiometry. The two-phase region, within which orthopyroxene and garnet solid solutions coexist, is very broad. The structure of the earth's mantle is discussed in terms of the phase transformations to be expected in a simple mixture of 90% MgSiO₃ · 10% Al₂O₃ and Mg₂SiO₄. The seismic discontinuity at a depth of 400 km in the earth's mantle is probably due entirely to the olivine → β-phase transition in Mg₂SiO₄, with the progressive solution of pyroxene in garnet (displayed in 90% MgSiO₃ · 10% Al₂O₃) occurring at shallower depths. The inferred discontinuity at 650 km is due to the combination of the phase changes spinel → perovskite + rocksalt in Mg₂SiO₄ and garnet → ilmenite in 90% MgSiO₃ · 10% Al₂O₃. The 650-km discontinuity is thus characterized by an increase in the primary coordination of silicon from 4 to 6. A further discontinuity in the density and seismic wave velocities at greater depth associated with the ilmenite-perovskite phase transformation in 90% MgSiO₃ · 10% Al₂O₃ is expected.     

Vertical distribution of chlorofluoromethanes in the upper troposphere and lower stratosphere

Vertical profiles of CCl₄, CFCl₃, and CF₂Cl₂ mixing ratios in the upper troposphere and lower stratosphere have been measured on four flights with chartered aircraft, type HS 125. The flights were carried out in November and December 1976 over Europe at latitudes between 50 and 60°N. At least eight air samples were taken during each ascent and descent of the aircraft at altitudes between 7 and 12.5 km. The samples were analysed in the laboratory using gaschromatographic procedures. The results indicate a decrease of the CCl₄, CFCl₃, and CF₂Cl₂ mixing ratios above the tropopause. The observed average gradients in the stratosphere are 14 pptv/km for CCl₄, 12 pptv/km for CFCl₃ and 27.8 pptv/km for CF₂Cl₂. With exception of CFCl₃ these gradients are higher than those predicted by model calculations. Apparently, further sink mechanisms for CCl₄ and CF₂Cl₂ exist in the lower stratosphere not yet included in the models.