Impact evaluation on groundwater of the infiltration of an urban wastewater geopurification system placed over a detrital aquifer in a semiarid region (Spain)

Over a period of 4 years and 4 months, the geopurification installations at Dehesas de Guadix (Granada, Spain) were monitored to determine the impact on soil and groundwater of the controlled discharge of urban wastewater, and also to identify the best indicators of the entry of the recharged water into the aquifer. The installations are located in an area where the climate is Mediterranean sub-arid, with an average precipitation of less than 287 mm/year, and a rate of evapotranspiration that is almost three times greater. The system was controlled by determining the balance of majority nutrients and boron in the soil and in the groundwater, both at the points affected directly by the wastewater discharge and at others. The quantity of mass discharged was relatively large (COD 14,656 g/m², NO₃ 85 g/m², NO₂ 4 g/m², NH₄ 2,425 g/m², PO₄ 1,143 g/m², K 1,531 g/m², B 63 g/m²). It was observed that the elimination of nutrients within the soil (COD 97.5%, PO₄ 94.4%, K 59.17%, N _total 18.8%, B 12.69%) was very efficient except for the nitrogen, which nevertheless did not reach the groundwater, as it was eliminated at deep levels of the unsaturated zone. Only 12.69% of the boron was removed, and appreciable, increasing amounts of this element did reach the groundwater. Unexpectedly, none of the majority nutrients behaved as a reliable indicator of the impact on groundwater; despite this, the boron and the bicarbonate did clearly reflect the arrival of the recharged water, and are proposed as the best indicators.     

Occurrence and evolution of the Xiaotangshan hot spring in Beijing, China

Thermal groundwater occurs in bedrock aquifers consisting of the dolomite of the Wumishan Group of the Jixianin System and the Cambrian carbonate in the Xiaotangshan geothermal field near the northern margin of the North China Plain, China. The hot water in the geothermal field of basin-type discharges partly in the form of the Xiaotangshan hot spring under natural conditions. The hot water has TDS of less than 600 mg/L and is of Na·Ca-HCO₃ type. The geothermal water receives recharge from precipitation in the mountain area with elevation of about 500 m above sea level to the north of the spring. Thermal groundwater flows slowly south and southeast through a deep circulation with a residence time of 224 years estimated with the Ra–Rn method. The Xiaotangshan hot spring dried up in the middle of the 1980s owing to the increasing withdrawal of the hot water in the geothermal field in the past decades. The water level of the geothermal system still falls continually at an annual average rate of about 2 m, although water temperature changes very little, indicating that the recharge of such a geothermal system of basin-type is limited. Over-exploitation has a dramatic impact on the geothermal system, and reduction in exploitation and reinjection are required for the sustainable usage of the hot water.     

Recharge source and hydrogeochemical evolution of shallow groundwater in a complex alluvial fan system,southwest of North China Plain

Many cities around the world are developed at alluvial fans. With economic and industrial development and increase in population, quality and quantity of groundwater are often damaged by over-exploitation in these areas. In order to realistically assess these groundwater resources and their sustainability, it is vital to understand the recharge sources and hydrogeochemical evolution of groundwater in alluvial fans. In March 2006, groundwater and surface water were sampled for major element analysis and stable isotope (oxygen-18 and deuterium) compositions in Xinxiang, which is located at a complex alluvial fan system composed of a mountainous area, Taihang Mt. alluvial fan and Yellow River alluvial fan. In the Taihang mountainous area, the groundwater was recharged by precipitation and was characterized by Ca–HCO₃ type water with depleted δ¹⁸O and δD (mean value of −8.8‰ δ¹⁸O). Along the flow path from the mountainous area to Taihang Mt. alluvial fan, the groundwater became geochemically complex (Ca–Na–Mg–HCO₃–Cl–SO₄ type), and heavier δ¹⁸O and δD were observed (around −8‰ δ¹⁸O). Before the surface water with mean δ¹⁸O of −8.7‰ recharged to groundwater, it underwent isotopic enrichment in Taihang Mt. alluvial fan. Chemical mixture and ion exchange are expected to be responsible for the chemical evolution of groundwater in Yellow River alluvial fan. Transferred water from the Yellow River is the main source of the groundwater in the Yellow River alluvial fan in the south of the study area, and stable isotopic compositions of the groundwater (mean value of −8.8‰ δ¹⁸O) were similar to those of transferred water (−8.9‰), increasing from the southern boundary of the study area to the distal end of the fan. The groundwater underwent chemical evolution from Ca–HCO₃, Na–HCO₃, to Na–SO₄. A conceptual model, integrating stiff diagrams, is used to describe the spatial variation of recharge sources, chemical evolution, and groundwater flow paths in the complex alluvial fan aquifer system.     

Assessment of frozen-ground conditions for engineering geology along the Qinghai–Tibet highway and railway, China

The Qinghai–Tibet Highway and Railway (the Corridor) across the Qinghai–Tibet Plateau traverses 670 km of permafrost and seasonally frozen-ground in the interior of the Plateau, which is sensitive to climatic and anthropogenic environmental changes. The frozen-ground conditions for engineering geology along the Corridor is complicated by the variability in the near-surface lithology, and the mosaic presence of warm permafrost and talik in a periglacial environment. Differential settlement is the major frost-effect problem encountered over permafrost areas. The traditional classification of frozen ground based on the areal distribution of permafrost is too generalized for engineering purposes and a more refined classification is necessary for engineering design and construction. A proposed classification of 51 zones, sub-zones, and sections of frozen ground has been widely adopted for the design and construction of foundations in the portion of the Corridor studied. The mean annual ground temperature (MAGT), near-surface soil types and moisture content, and active faults and topography are most commonly the primary controlling factors in this classification. However, other factors, such as local microreliefs, drainage conditions, and snow and vegetation covers also exert important influences on the features of frozen ground. About 60% of the total length of the Corridor studied possesses reasonably good frozen-ground conditions, which do not need special mitigative measures for frost hazards. However, other sections, such as warm and ice-rich or -saturated permafrost, particularly in the sections in wetlands, ground improvement measures such as elevated land bridges and passive or proactive cooling techniques need to be applied to ensure the long-term stability of thermally unstable, thick permafrost subsoils, and/or refill with non-frost-susceptible soils. Due to the long-history of the construction and management of the Corridor by various government departments, adverse impacts of construction and operation on the permafrost environment have been resulted. It is recommended that an integrated, executable plan for the routing of major construction projects within this transportation corridor be established and long-term monitoring networks installed for evaluating and mitigating the impact from anthropogenic and climatic changes in frozen-ground conditions.     

Diamond formation in sulfide pyrrhotite-carbon melts: Experiments at 6.0–7.1 GPa and application to natural conditions

Experiments at 6.0–7.1 GPa and 1500–1700°C were carried out to explore the boundary conditions of diamond nucleation and growth in pyrrhotite-carbon melt-solutions. Pyrrhotite is one of the main sulfide minerals of the pyrrhotite-pentlandite-chalcopyrite assemblage of mantle rocks and primary inclusions in diamond. Solutions of carbon in sulfide melts oversaturated with respect to diamond at the expense of the dissolution of starting graphite (thermodynamically unstable phase) are formed owing to the difference between the solubilities of graphite and diamond, which increases under the influence of temperature gradients in experimental samples. We determined the fields of carbon solutions in pyrrhotite melt showing labile and metastable oversaturation with respect to diamond, which correspond to the spontaneous nucleation of the diamond phase and diamond growth on seeds, respectively. The linear growth rate of diamond in sulfide-carbon melts is rather high (on average, 10 μ/min during the first 1–2 min from the onset of spontaneous crystallization). The nucleation density is estimated as 180 grains per cubic centimeter. Diamonds crystallized from sulfide melts show octahedral and spinel twin shapes. Diamond polycrystals were synthesized for the first time from a sulfide medium as intergrowths of skeletal (edge) or “cryptocrystalline” microdiamonds, from 1 to 100 μm in size, their spinel twins and, occasionally, polysynthetic (star-shaped) twins. During diamond growth from sulfidecarbon melts on smooth faces of cuboctahedral diamond seeds synthesized in metal systems, smooth-faced layer-by-layer step-like growth was observed on their octahedral (111) faces, whereas growth on the (100) cubic faces produced rough-surfaced layers of intergrown micropyramids, whose axes were oriented normal to the (100) face. The obtained experimental results were applied to the problem of diamond genesis under the conditions of the Earth’s mantle in the framework of the model of carbonate-silicate parental melts with blebs of immiscible sulfide melts.     

Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.     

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H₂S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO₄ in the presence of variable H₂S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H₂S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H₂S concentrations. To investigate whether the reaction of H₂S_(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO₄ and variable H₂S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO₄ reduction was not measurable in the absence of paraffin even with high H₂S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H₂S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H₂S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H₂S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H₂S pressure. Thus, we propose that the LSC produced from H₂S reaction with HC are most likely the reactive intermediates for H₂S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

A strong temperature effect on U/Ca in planktonic foraminiferal carbonates

Three planktonic foraminiferal species Globigerina bulloides, Neogloboquadrina pachyderma (d), and Globorotalia inflata collected from core-tops spanning 35° to 65°N in the North Atlantic were used for U/Ca and Mg/Ca and foraminiferal shell weight analyses. Except for U/Ca in G. bulloides calcified under warm conditions (>∼13 °C), U/Ca ratios in all three studied species increase with decreasing latitude and show strong positive correlations with Mg/Ca ratios. A dissolution effect on planktonic U/Ca is suggested by decreased shell weight and U/Ca and Mg/Ca ratios for shells from very deep water depth (>4.4 km) along the latitudinal transect. G. bulloides from down core samples in the North Atlantic show low U/Ca ratios during the last glacial and high ratios during the Holocene, similar to the Mg/Ca evolution trend. In general, our data indicate that the U incorporation into planktonic foraminiferal carbonates is strongly influenced by calcification temperature, although U/Ca in G. bulloides may be affected by seawater carbonate ion concentration under warm conditions and/or other factors.     

The posthumous tectonics and mechanism of exhumation of granitic plutons: The case of the Transbaikal region and the Tien Shan

The study of granitic plutons of the Baikal Highland and the Tien Shan has made it possible to establish new features of their posthumous (after incorporation into the consolidated Earth’s crust) structural reworking and to understand the implications of the cataclastic flow for the exhumation of the crystalline basement in the studied regions. It is shown that granitic plutons undergo appreciable structural transformation at the stages of tectonic reactivation that is significantly separated in time from the moment of formation of plutons as geological bodies. The 3D cataclastic deformation is the main mode of structural reworking of granitic plutons, while the cataclastic flow is the main form of their mobility. Newly recognized slice structures characterize the volumetric deformation of granites.