Determination of atrazine isotherms on agricultural soils

For determination of atrazine isotherms in agricultural soils of Fars Province, composite soil samples from 0 to 5 cm depth with textures of silty clay loam, clay loam and loam were collected. In order to form the atrazine isotherms, 10, 50 and 100 µg atrazine g^?1 soil was added to the soil samples. Soluble atrazine in water:soil ratios of 10:1, 50:1 and 200:1 was measured after 3-h shaking. Finally, for each cases of applied atrazine, water extractable atrazine was determined and quantified using gas chromatography instrument. The results indicated that there was a linear relationship between the logarithms of water extractable atrazine and added atrazine for different water:soil ratios. A general equation of WEA = K(WS) ^α (AA) ^β is obtained experimentally between water extractable atrazine, µg g^?1(WEA), and added atrazine, µg g^?1 (AA), where K, α and β are absorption constants; WS is the water:soil ratio, g g^?1. For the loam, silty clay loam and clay loam soil textures, the α were 0.49, 0.23 and 0.13, respectively, the β were 0.55, 0.806 and 0.21, respectively, and the K were 1.44, 0.78 and 25.38, respectively.     

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.     

Groundwater use by plants in a semi-arid coal-mining area at the Mu Us Desert frontier

The hydrogen isotope (deuterium- $ \delta D $ ) composition at natural abundance levels of xylem water, soil water, groundwater, river water, and rainwater was used to evaluate whether adult plant species use groundwater and to detect seasonal shifts (dry/wet season) in water sources for plants growing in a semi-arid coal-mining area (located at the frontier of the Mu Us Desert). A direct inference approach and the IsoSource mixing model were used to estimate the contributions of different sources to the plant xylem water. The results showed that (1) the $ \delta D $ values of rainfall fluctuated considerably, while those of groundwater were generally constant during the experimental period; (2) the $ \delta D $ patterns in plant xylem water suggest that groundwater was a significant source of water for transpiration in the dry season, while all five selected species reduced dependence on groundwater sources in the wet season; and (3) soil water from the deep layer (50–100 cm) was used largely by adult species possibly because of interspecific competition. These results indicated that coal mining would significantly affect plant growth by reducing the water supply if it leads to a water table decrease. Therefore, it is necessary to protect groundwater resources during the coal mining operations in the region.     

Experimentelle Untersuchung der Reaktion Dolomit + Kalifeldspat + H2O ⇌ Phlogopit + Calcit + CO2

The equilibrium curve for the reaction 3 dolomite + 1 K-feldspar + 1 H₂O=1 phlogopite + 3 calcite + 3 CO₂ was determined experimentally at a total gas pressure of 2000 bars using two different methods.

1. In the first case water alone was added to the reactants. The CO₂ component of the gas phase was producted solely by the reaction under favourable P-T conditions. This manner of carrying out the reaction is called the “water method”. With this method sufficient time must be allowed for the gas phase to attain a constant composition (see Fig. 1). Reverse reactions were carried out using reaction products of the forward reaction.
2. In the second case silver oxalate + water were added to the reactants. Breakdown of the silver oxalate leads to formation of a CO₂-H₂O gasphase of definite composition. At constant temperature and gas pressure the \(X_{{\text{CO}}_{\text{2}} } \) determines whether the reaction products will be phlogopite + calcite or dolomite + K-feldspar. In this case it is not necessary to wait for equilibrium to be attained. This method is abbreviated the “oxalate method”. Reactants for reverse reactions are not identical with the products of the forward reaction.

At high temperatures the results of the two different methods agree well (see Tables 1 and 2). Equilibrium was attained in one case at 490° C and \(X_{{\text{CO}}_{\text{2}} } \) of approximately 0.77, and in the other case at 520° C and \(X_{{\text{CO}}_{\text{2}} } \) of 0.90. At lower temperatures there are considerable differences in the results. With the water method an \(X_{{\text{CO}}_{\text{2}} } \) of about 0.25 was reached at 450° C. With the oxalate method dolomite K-feldspar and water still react with each other at even higher \(X_{{\text{CO}}_{\text{2}} } \) values. Phlogopite, calcite and CO₂ are formed together with metastable talc. There are no criteria to indicate which of the methods is the correct one at lower temperatures and in Fig. 2, therefore, both equilibrium curves are plotted.     

Water diffusion in Mount Changbai peralkaline rhyolitic melt

Diffusion couple experiments with wet half (up to 4.6 wt%) and dry half were carried out at 789–1,516 K and 0.47–1.42 GPa to investigate water diffusion in a peralkaline rhyolitic melt with major oxide concentrations matching Mount Changbai rhyolite. Combining data from this work and a related study, total water diffusivity in peralkaline rhyolitic melt can be expressed as:

$ D_{{{\text{H}}_{ 2} {\text{O}}_{\text{t}} }} = D_{{{\text{H}}_{ 2} {\text{O}}_{\text{m}} }} \left( {1 - \frac{0.5 - X}{{\sqrt {[4\exp (3110/T - 1.876) - 1](X - X^{2} ) + 0.25} }}} \right), $

$ {\text{with}}\;D_{{{\text{H}}_{ 2} {\text{O}}_{\text{m}} }} = \exp \left[ { - 1 2. 7 8 9- \frac{13939}{T} - 1229.6\frac{P}{T} + ( - 27.867 + \frac{60559}{T})X} \right], $

where D is in m² s^?1, T is the temperature in K, P is the pressure in GPa, and X is the mole fraction of water and calculated as X = (C/18.015)/(C/18.015 + (100 ? C)/33.14), where C is water content in wt%. We recommend this equation in modeling bubble growth and volcanic eruption dynamics in peralkaline rhyolitic eruptions, such as the ~1,000-ad eruption of Mount Changbai in North East China. Water diffusivities in peralkaline and metaluminous rhyolitic melts are comparable within a factor of 2, in contrast with the 1.0–2.6 orders of magnitude difference in viscosities. The decoupling of diffusivity of neutral molecular species from melt viscosity, i.e., the deviation from the inversely proportional relationship predicted by the Stokes–Einstein equation, might be attributed to the small size of H₂O molecules. With distinct viscosities but similar diffusivity, bubble growth controlled by diffusion in peralkaline and metaluminous rhyolitic melts follows similar parabolic curves. However, at low confining pressure or low water content, viscosity plays a larger role and bubble growth rate in peralkaline rhyolitic melt is much faster than that in metaluminous rhyolite.

     

Concentration dependence of water diffusion in obsidian and dacitic melts at high-pressures

The diffusion of water in natural obsidian and model dacitic melts (Ab90Di8Wo2, mol %) has been studied at water vapor pressure up to 170 MPa, temperatures of 1200°C, H₂O contents in melts up to ～6 wt % using a high gas pressure apparatus equipped with a unique internal device. The experiments were carried out by a new low-gradient technique with application of diffusion hydration of a melt from fluid phase. The water solubility in the melts and its concentration along $C_{H_2 O} $ diffusion profiles were determined using IR microspectrometry by application of the modified Bouguer-Beer-Lambert equation. A structural-chemical model was proposed to calculate and predict the concentration dependence of molar absorption coefficients of the hydroxyl groups (OH^?) and water molecules (H₂O) in acid polymerized glasses (quenched melts) in the obsidian-dacite series. The water diffusion coefficients $D_{H_2 O} $ were obtained by the mathematical analysis of concentration profiles and the analytical solution of the second Fick diffusion law using the Boltzman-Matano method. It was shown experimentally that $D_{H_2 O} $ exponentially increases with a growth of water concentration in the obsidian and dacitic melts within the entire range of diffusion profiles. Based on the established quantitative correlation between $D_{H_2 O} $ and viscosity of such melts, a new method was developed to predict and calculate the concentration, temperature, and pressure dependences of $D_{H_2 O} $ in acid magmatic melts (obsidian, rhyolite, albite, granite, dacite) at crustal T, P parameters and water concentrations up to 6 wt %.     

Experimental Investigation of Seepage Properties of Fractured Rocks Under Different Confining Pressures

The effectiveness of transmitting underground water in rock fractures is strongly influenced by the widths of the fractures and their interconnections. However, the geometries needed for water flow in fractured rock are also heavily controlled by the confining pressure conditions. This paper is intended to study the seepage properties of fractured rocks under different confining pressures. In order to do this, we designed and manufactured a water flow apparatus that can be connected to the electro-hydraulic servo-controlled test system MTS815.02, which provides loading and exhibits external pressures in the test. Using this apparatus, we tested fractured mudstone, limestone and sandstone specimens and obtained the relationship between seepage properties and variations in confining pressure. The calculation of the seepage properties based on the collection of water flow and confining pressure differences is specifically influenced by non-Darcy flow. The results show that: (1) The seepage properties of fractured rocks are related to confining pressure, i.e. with the increase of confining pressure, the permeability $ k $ decreases and the absolute value of non-Darcy flow coefficient $ \beta $ increases. (2) The sandstone coefficients $ k $ and $ \beta $ range from $ 1.03 \times 10^{ - 18} $ to $ 1.53 \times 10^{ - 17} $  m² and $ - 1.13 \times 10^{17} $ to $ - 2.35 \times 10^{18} $  m^?1, respectively, and exhibit a greater change compared to coefficients of mudstone and limestone. (3) From the regression analysis of experimental data, it is concluded that the polynomial function is a better fit than the power and logarithmic functions. The results obtained can provide an important reference for understanding the stability of rock surrounding roadways toward prevention of underground water gushing-out, and for developing underground resources (e.g. coal).     

Prevalence of pathogenic microorganisms and their correlation with the abundance of indicator organisms in riverbed sediments

The present study investigated the prevalence of pathogenic organisms (Salmonella spp, Vibrio cholerae, and Shigella spp) and their correlation to the abundance of faecal indicator organisms in water and riverbed sediments in the Apies River, South Africa. In all, 558 water and sediment samples were collected from 10 sites in the river (May 2013–February 2014) and analysed through culture and molecular (real-time PCR) techniques. Concentrations of faecal indicator organisms in sediments reached 1.39 × 10⁵ (±standard deviation) CFU/100 mL. All three pathogens were detected in water and sediments. Pathogens were mostly detected in sediments at sites influenced either by wastewater treatment works or by informal settlements. During the wet and dry seasons (water column), a strong positive correlation was observed between E. coli and all pathogens; C. perfringens only correlated with V. cholerae. Within sediments, strong positive correlations were only observed between E. coli and Salmonella spp, E. coli and V. cholerae (dry season); E. coli and V. cholerae and E. coli and Shigella spp (wet season). No correlation was observed between sediments C. perfringens counts and all the pathogens. Thus, sediments of the Apies River harbour pathogenic organisms. Correlation between E. coli and pathogenic organisms in the sediments suggests that E. coli could also be an indicator of pathogens’ presence. However, the lack of a correlation between E. coli and some pathogens in sediments and between C. perfringens and all the pathogens highlights the need to investigate for more indicators of pathogens’ presence in this complex matrix.     

Kinetic mechanism of oxygen isotope disequilibrium in precipitated witherite and aragonite at low temperatures: an experimental study

To study what dictates oxygen isotope equilibrium fractionation between inorganic carbonate and water during carbonate precipitation from aqueous solutions, a direct precipitation approach was used to synthesize witherite, and an overgrowth technique was used to synthesize aragonite. The experiments were conducted at 50 and 70°C by one- and two-step approaches, respectively, with a difference in the time of oxygen isotope exchange between dissolved carbonate and water before carbonate precipitation. The two-step approach involved sufficient time to achieve oxygen isotope equilibrium between dissolved carbonate and water, whereas the one-step approach did not. The measured witherite-water fractionations are systematically lower than the aragonite-water fractionations regardless of exchange time between dissolved carbonate and water, pointing to cation effect on oxygen isotope partitioning between the barium and calcium carbonates when precipitating them from the solutions. The two-step approach experiments provide the equilibrium fractionations between the precipitated carbonates and water, whereas the one-step experiments do not. The present experiments show that approaching equilibrium oxygen isotope fractionation between precipitated carbonate and water proceeds via the following two processes:

1.

Oxygen isotope exchange between [CO₃]²⁻ and H₂O:

(1)     

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.     

Hydrated goethite (α-FeOOH) (1 0 0) interface structure: Ordered water and surface functional groups

Goethite(α-FeOOH), an abundant and highly reactive iron oxyhydroxide mineral, has been the subject of numerous studies of environmental interface reactivity. However, such studies have been hampered by the lack of experimental constraints on aqueous interface structure, and especially of the surface water molecular arrangements. Structural information of this type is crucial because reactivity is dictated by the nature of the surface functional groups and the structure or distribution of water and electrolyte at the solid-solution interface. In this study we have investigated the goethite (1 0 0) surface using surface diffraction techniques, and have determined the relaxed surface structure, the surface functional groups, and the three dimensional nature of two distinct sorbed water layers. The crystal truncation rod (CTR) results show that the interface structure consists of a double hydroxyl, double water terminated interface with significant atom relaxations. Further, the double hydroxyl terminated surface dominates with an 89% contribution having a chiral subdomain structure on the (1 0 0) cleavage faces. The proposed interface stoichiometry is ((H₂O)(H₂O)OH₂OHFeOOFeR) with two types of terminal hydroxyls; a bidentate (B-type) hydroxo group and a monodentate (A-type) aquo group. Using the bond-valence approach the protonation states of the terminal hydroxyls are predicted to be OH type (bidentate hydroxyl with oxygen coupled to two Fe³⁺ ions) and OH₂ type (monodentate hydroxyl with oxygen tied to only one Fe³⁺). A double layer three dimensional ordered water structure at the interface was determined from refinement of fits to the experimental data. Application of bond-valence constraints to the terminal hydroxyls with appropriate rotation of the water dipole moments allowed a plausible dipole orientation model as predicted. The structural results are discussed in terms of protonation and H-bonding at the interface, and the results provide an ideal basis for testing theoretical predictions of characteristic surface properties such as pK_a , sorption equilibria, and surface water permittivity.     

Biostratigraphy and depositional environment of the Miocene limestone bed of Baripada,Mayurbhanj district,Odisha: Foraminiferal,sedimentological and bulk organic geochemical evidences

Baripada Marine Beds (BMB) have been studied extensively in terms of its mega fossil content. However, not much has been discussed about the foraminiferal content and the organic matter assemblage in these beds. The fossiliferous sequence of BMB consists of sandstone, shale and limestone units. The present study is persued on the limestone unit of BMB. Foraminiferal, thin section and rock-eval pyrolysis studies were performed on the 33 surface samples collected from five sections of Jamdapal and Mukurmatia region along the Budhabalang river bank. Foraminifera are less abundant in the samples of Jamdapal, whereas Mukurmatia is comparatively rich. First appearance datum of Globorotalia menardii[ranges since middle Miocene (12.6 Ma); FAD at planktic foraminiferal zone N12] and last appearance datum of Neogloboquadrina continuosa [ranges between early Miocene (23.2 Ma) to late Miocene (8.3 Ma); FAD at planktic foraminiferal zone N4B and LAD at N16] together suggest that the limestone unit was deposited in between 12.6 to 8.3 Ma within the upper Miocene. Also, the association of shallow water benthic foraminifera (Species of Ammonia, Asterorotalia, Bolivina, Buliminella, Cibicides, Challengerella, Criboelphidium, Cribononion, Elphidium, Hanzawaia, Nonionella) and planktic foraminifera (Globigerina falcoensis, Globigerina woodi, Globorotalia menardii, Neogloboquadrina continuosa) together with oyster bank and shark teeth suggest deposition of limestone within well oxygenated, tropical, shallow water, open marine condition (within 40m water depth). Lithological and thin section studies together with global sea level fluctuation history advocate that upper Miocene marine transgression promoted the formation of this unit. Bulk organic geochemical data obtained by the rock-eval pyrolysis studies on selected samples indicate a low total organic carbon (TOC), with low hydrogen index (HI), high oxygen index (OI). The organic facies is characterised by type-IV kerogen with major contribution from near shore terrestrial plants. This also suggests deposition in shallow, oxygenated environments that did not promote significant accumulation and preservation of organic content in sediments.     

Impact of pore water conductivity and porosity on the electrical conductivity of kaolinite

The purpose of this study is to quantify the magnitudes of surface conduction and pore water conduction from the measured electrical conductivity of kaolinite, with the ultimate goal of estimating the electrical conductivity of kaolinite with a wide range of pore water conductivities (σ _w = 0.013–3.356 S/m) and porosities (n = 0.368–1.0). Therefore, the theoretical background of the electrical conductivity in soils was reviewed, and electrical conductivity measurements on kaolinite were performed using both slurry and consolidation tests in this study. The results of this study demonstrate that the variations of measured electrical conductivity (σ _mix) with n are debatable according to the values of σ _w, because a decrease in n results in both an increase in surface conduction (K _s) and a decrease in pore water conduction (K _w); this causes the relative magnitude of K _s compared to that of K _w to vary with σ _w and n. Consequently, this study develops the relation between the porosity-normalized K _s/K _w and 1/σ _w. Additionally, the surface conductivity of the tested kaolinite is back-calculated and compared with the previous relationship between K _s and zeta potential of kaolinite. The measured and estimated σ _mix values are compared with the varying pore water conductivity and porosity values.     

Weakly bound water structure,bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

Background

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

Results

The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe³⁺ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe³⁺. The water molecules capping surface Fe³⁺ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe³⁺ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe³⁺ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe³⁺, those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe³⁺ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism.

Conclusions

Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe–OH₂ distances in the DFT calculations it was proposed that the surface Fe³⁺ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination.

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Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe³⁺ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe³⁺ is coordinated with only 5 neighbors.