A Strain Rate Dependent Constitutive Model for the Lower Silurian Longmaxi Formation Shale in the Fuling Gas Field of the Sichuan Basin,China

Shale, as a kind of brittle rock, often exhibits different nonlinear stress-strain behavior, failure and time-dependent behavior under different strain rates. To capture these features, this work conducted triaxial compression tests under axial strain rates ranging from 5×10?6 s?1 to 1×10?3 s?1. The results show that both elastic modulus and peak strength have a positive correlation relationship with strain rates. These strain rate-dependent mechanical behaviors of shale are originated from damage growth, which is described by a damage parameter. When axial strain is the same, the damage parameter is positively correlated with strain rate. When strain rate is the same, with an increase of axial strain, the damage parameter decreases firstly from an initial value (about 0.1 to 0.2), soon reaches its minimum (about 0.1), and then increases to an asymptotic value of 0.8. Based on the experimental results, taking yield stress as the cut-off point and considering damage variable evolution, a new measure of micro-mechanical strength is proposed. Based on the Lemaitre’s equivalent strain assumption and the new measure of micro-mechanical strength, a statistical strain-rate dependent damage constitutive model for shale that couples physically meaningful model parameters was established. Numerical back-calculations of these triaxial compression tests results demonstrate the ability of the model to reproduce the primary features of the strain rate dependent mechanical behavior of shale.     

Flow behavior and microstructures of hydrous olivine aggregates at upper mantle pressures and temperatures

Deformation experiments on olivine aggregates were performed under hydrous conditions using a deformation-DIA apparatus combined with synchrotron in situ X-ray observations at pressures of 1.5–9.8 GPa, temperatures of 1223–1800 K, and strain rates ranging from 0.8 × 10^?5 to 7.5 × 10^?5 s^?1. The pressure and strain rate dependencies of the plasticity of hydrous olivine may be described by an activation volume of 17 ± 6 cm³ mol^?1 and a stress exponent of 3.2 ± 0.6 at temperatures of 1323–1423 K. A comparison between previous data sets and our results at a normalized temperature and a strain rate showed that the creep strength of hydrous olivine deformed at 1323–1423 K is much weaker than that for the dislocation creep of water-saturated olivine and is similar to that for diffusional creep and dislocation-accommodated grain boundary sliding, while dislocation microstructures showing the [001] slip or the [001](100) slip system were developed. At temperatures of 1633–1800 K, a much stronger pressure effect on creep strength was observed for olivine with an activation volume of 27 ± 7 cm³ mol^?1 assuming a stress exponent of 3.5, water fugacity exponent of 1.2, and activation energy of 520 kJ mol^?1 (i.e., power-law dislocation creep of hydrous olivine). Because of the weak pressure dependence of the rheology of hydrous olivine at lower temperatures, water weakening of olivine could be effective in the deeper and colder part of Earth’s upper mantle.     

The effects of undercooling and deformation rates on the crystallization kinetics of Stromboli and Etna basalts

We have investigated the effect of undercooling and deformation on the evolution of the texture and the crystallization kinetics of remelted basaltic material from Stromboli (pumice from the March 15, 2007 paroxysmal eruption) and Etna (1992 lava flow). Isothermal crystallization experiments were conducted at different degrees of undercooling and different applied strain rate (T = 1,157–1,187 °C and $ \dot{\gamma }_{i} $ γ · i  = 4.26 s^?1 for Stromboli; T = 1,131–1,182 °C and $ \dot{\gamma }_{i} $ γ · i  = 0.53 s^?1 for Etna). Melt viscosity increased due to the decrease in temperature and the increase in crystal content. The mineralogical assemblage comprises Sp + Plg (dominant) ± Cpx with an overall crystal fraction (?) between 0.06 and 0.27, increasing with undercooling and flow conditions. Both degree of undercooling and deformation rate deeply affect the kinetics of the crystallization process. Plagioclase nucleation incubation time strongly decreases with increasing ΔT and flow, while slow diffusion-limited growth characterizes low ΔT—low deformation rate experiments. Both Stromboli (high strain rate) and Etna (low strain rate) plagioclase growth rates (G) display relative small variations with Stromboli showing higher values (4.8 ± 1.9 × 10^?9 m s^?1) compared to Etna (2.1 ± 1.6 × 10^?9 m s^?1). Plagioclase average nucleation rates J continuously increase with undercooling from 1.4 × 10⁶ to 6.7 × 10⁶ m^?3 s^?1 for Stromboli and from 3.6 × 10⁴ to 4.0 × 10⁶ m^?3 s^?1 for Etna. The extremely low value of 3.6 × 10⁴ m^?3 s^?1 recorded at the lowest undercooling experiment for Etna (ΔT = 20 °C) indicates that the crystallization process is growth-dominated and that possible effects of textural coarsening occur. G values obtained in this paper are generally one or two orders of magnitude higher compared to those obtained in the literature for equivalent undercooling conditions. Stirring of the melt, simulating magma flow or convective conditions, facilitates nucleation and growth of crystals via mechanical transportation of matter, resulting in the higher J and G observed. Any modeling pertaining to magma dynamics in the conduit (e.g., ascent rate) and lava flow emplacement (e.g., flow rate, pāhoehoe–‘a‘ā transition) should therefore take the effects of dynamic crystallization into account.     

Active and passive measurements of radon diffusion coefficient from building construction materials

The gaseous state and chemical inert behavior of radon make it important tracer for the radon transport study through the building materials. The radon resistant property of building construction materials is important parameter to control the indoor radon levels in living and workplaces. The materials with higher radium content can be made less severe by the use of some building materials of low diffusion coefficient and diffusion length. This makes the study of radon diffusion through building material more important along with the study of exhalation and radioactivity content. Keeping this in mind the radon diffusion study was carried out through different building construction materials used for wall and floor by active and passive techniques. The diffusion coefficient from these building materials measured by passive methods varied from (0.9 ± 0.5) × 10^?7 to (22.95 ± 13.19) × 10^?6 m²s^?1 and radon diffusion length varied from 0.21 to 3.31 m for cement, soil, sand, wall putty and plaster of Paris (POP) etc. The radon diffusion coefficient measured by active technique varied from 1.93 × 10^?10 to 1.36 × 10^?7 m²s^?1 for samples with definite geometry like paper, polyethylene, marble, granite etc. The radon diffusion coefficient and diffusion length depend upon the porosity and density of materials for powder samples.     

Effects of size and strain rate on the mechanical behaviors of rock specimens under uniaxial compression

Size and strain rate are two key factors that dramatically influence the estimation of rock mechanical behaviors. To better understand the effects of size and strain rate on measured rocks, rock specimens with six different sizes were tested at six different strain rates under uniaxial compression using the MTS 815 Rock Mechanics Test System. Having determined that the size and strain rate significantly affect the peak strain, peak stress, elastic modulus, acoustic emission (AE), and failure pattern of the rock specimens, the relation was established between the strength and the size and strain rate of red sandstone. And the variation was revealed among the size and strain rate, the AE, and the failure pattern. It turned out that the peak stress was negatively correlated with the rock size and was positively correlated with the strain rate. When the length to diameter ratio (L/D) of the rock specimen was less than 2.0, the AE appeared mildly. The AE quantities gradually increased before the peak stress, and then sharply decreased after the peak stress. The failure pattern of the rock specimen was relatively complicated, with a fracture plane appearing along the axial direction. Conical failure type was also presented. When the L/D ratio of the specimen was greater than 2.0, the AE characteristics of red sandstone showed the radical model. There were relatively few AE rings before the peak stress. But the AE rings increased suddenly and dramatically during the peak stress. The rock specimens primarily failed with a single shear plane. Moreover, with an increase in the strain rate, the AE activities were enhanced and the AE quantities increased. When the strain rate of the rock specimen was less than 5.0?×?10^?4/s, the rock specimen failed with a shear or tensile-shear pattern. And when the strain rate was greater than 5.0?×?10^?4/s, the rock specimen tended to fail in a conical pattern.     

High-temperature stress relaxation of synthetic,polycrystalline galena

Stress relaxation experiments were performed on hot-pressed cylinders of synthetic, polycrystalline galena at temperatures of 500°, 600°, 700° and 800°C at atmospheric pressure after various levels of axial strain, in the range from 2% to 25%, had been imposed at a constant strain rate (?) of 3×10^?4 s^?1. For this study a new apparatus was built which can measure small changes in applied stress (σ), better than ±0.5 × 10⁵ Pa, and which incorporates a facility whereby the composition of the test specimen can be fixed through equilibration with a gas atmosphere of controlled composition. Deformation mechanism maps constructed largely on theoretical grounds predict that, under the conditions studied here, high-temperature dislocation creep, for which ?∝σ⁵, gives way on lowering the applied stress to diffusion creep, for which ?∝σ. The experimental results agree in large measure with these theoretical predictions. However, it is not possible in this preliminary study to conclusively identify the dominant deformation mechanisms.     

High temperature creep of single crystal gadolinium gallium garnet

High temperature creep of single crystal gadolinium gallium garnet (GGG) was studied in the temperature range of 1723–1853 K (0.86–0.94 T_m, T_m: melting temperature) and strain rate from 9 · 10^?7 s^?1 to 2 · 10^?5 s^?1. The compression tests were made along the 〈100〉 and 〈111〉 orientations. We have performed both constant strain-rate and stress-dip tests. For the 〈100〉 orientation, deformation occurs via the 〈111〉 slip systems. For the 〈111〉 orientation, both the 〈100〉 {010} and the 〈111〉 slip systems can be activated. GGG garnet is very strong under these conditions: σ/μ=(1–3)×10^?3 (σ: creep strength, μ: shear modulus). The creep behavior is characterized by a power law with stress exponent n=2.9–3.3 and high activation energies E^*=612–743 kJ/mol (E^*～45×RT_m, at zero stress which decrease with the increase of stress). Stress-dip tests suggest a small internal stress (σ_i/σ～0.62; σ_i: internal stress, σ: applied stress) compared to other materials. These results suggest that the high creep strength of GGG is mainly due to difficulty of dislocation glide rather than dislocation climb.     

Semi-brittle behavior of wet olivine aggregates: the role of aqueous fluid in faulting at upper mantle pressures

The role of aqueous fluid in fracturing in subducting slabs was investigated through a series of deformation experiments on dunite that was undersaturated (i.e., fluid-free) or saturated with water (i.e., aqueous-fluid bearing) at pressures of 1.0–1.8 GPa and temperatures of 670–1250 K, corresponding to the conditions of the shallower regions of the double seismic zone in slabs. In situ X-ray diffraction, radiography, and acoustic emissions (AEs) monitoring demonstrated that semi-brittle flow associated with AEs was dominant and the creep/failure strength of dunite was insensitive to the dissolved water content in olivine. In contrast, aqueous fluid drastically decreased the creep/failure strength of dunite (up to ~?1 GPa of weakening) over a wide range of temperatures in the semi-brittle regime. Weakening of the dunite by the aqueous fluid resulted in the reduction of the number of AE events (i.e., suppression of microcracking) and shortening of time to failure. The AE hypocenters were located at the margin of the deforming sample while the interior of the faulted sample was aseismic (i.e., aseismic semi-brittle flow) under water-saturated conditions. A faulting (slip rate of ~?10^?3 to 10^?4 s^?1) associated with a large drop of stress (Δσ?~?0.5 to 1 GPa) and/or pressure (ΔP?~?0.5 GPa) was dominant in fluid-free dunite, while a slow faulting (slip rate?<?8?×?10^?5 s^?1) without any stress/pressure drop was common in water-saturated dunite. Aseismic semi-brittle flow may mimic silent ductile flow under water-saturated conditions in subducting slabs.     

Estimating the hydraulic properties of an aquitard from in situ pore pressure measurements

A workflow is described to estimate specific storage (S _s) and hydraulic conductivity (K) from a profile of vibrating wire piezometers embedded into a regional aquitard in Australia. The loading efficiency, compressibility and S _s were estimated from pore pressure response to atmospheric pressure changes, and K was estimated from the earliest part of the measurement record following grouting. Results indicate that S _s and K were, respectively, 8.8?×?10^?6 to 1.2?×?10^?5 m^?1 and 2?×?10^?12 m s^?1 for a claystone/siltstone, and 4.3?×?10^?6 to 9.6?×?10^?6 m^?1 and 1?×?10^?12 to 5?×?10^?12 m s^?1 for a thick mudstone. K estimates from the pore pressure response are within one order of magnitude when compared to direct measurement in a laboratory and inverse modelled flux rates determined from natural tracer profiles. Further analysis of the evolution and longevity of the properties of borehole grout (e.g. thermal and chemical effects) may help refine the estimation of formation hydraulic properties using this workflow. However, the convergence of K values illustrates the benefit of multiple lines of evidence to support aquitard characterization. An additional benefit of in situ pore pressure measurement is the generation of long-term data to constrain groundwater flow models, which provides a link between laboratory scale data and the formation scale.     

Fracturing and Failure Behavior of Carrara Marble in Quasistatic and Dynamic Brazilian Disc Tests

The tensile strength and fracturing behavior of Carrara marble subjected to the dynamic Brazilian disc test using the split Hopkinson pressure bar technique are determined and compared with those obtained by the conventional quasistatic Brazilian disc test. Detailed observation of the cracking processes is aided by high-speed video footage captured at a frame rate of 100,000 frames per second. The dynamic increase factor is computed, revealing a strong strain rate dependence of the Carrara marble when subjected to strain rates above 1 s^?1. Similar to the quasistatic loading tests, conspicuous white zones/patches commonly appear prior to the initiation of visible cracks in the dynamic loading tests. Identification of the white patch initiation and evolution is aided by image comparison software. Comparing the cracking and failure processes under quasistatic and dynamic loading, some distinct differences in the white patch geometry and initiation load are observed. In addition, the extent of the compressive failure zones around the contact points between the loading platens and specimens is found to increase with the strain rate.     

Experimental study of the influence of loading rate on tensile mechanical behavior of sandstone damaged by blasting

The drill and blast method (D&B) is perhaps the most common excavation method for rock mass, and intense blasting vibrations would induce an excavation damage zone (EDZ) around the excavated space. The tensile failure of rock mass in EDZ at diverse rupture velocities results in various geological disasters in engineering practices. The objective of this paper is to investigate the effect of blasting on the tensile strength of sandstone rock and the influence of loading rate on the disk specimens affected by blasting. We firstly performed a D&B exercise on a sandstone block with a size of 600 mm × 600 mm × 120 mm. Then, a total number of 49 standard disk specimens were prepared from large fragments of this blasting sandstone block and an undamaged block. A series of Brazilian split tests was carried out using these specimens to determine their indirect tensile strength, and to assess the effects of the distance from the blasting source and loading rate (varying from 1.67 × 10^?5 to 8.33 × 10^?2 mm s^?1). The results show that the tensile strength of specimens exhibits an upward trend with increasing distance from the blasting source, to approach that of undamaged rock, following a power function with a positive exponent (0~1). The loading rate affects the tensile mechanical behaviors of disks, in terms of the convergence of microscopic defects, the main load-bearing area, and the absorbed energy at the fracture moment of specimens. Both the tensile strength and absorbed energy have positive linear correlations with the natural logarithm of the loading rate. In addition, the fragmentation degree of disk specimens also increases due to an increasing brittleness of sandstone with the loading rate.     

Analysis of low-flow characteristics for catchments in Dongjiang Basin, China

Low-flow indices have been determined from long-term daily streamflow data for 13 catchments in Dongjiang Basin in southern China. The Brutsaert-Nieber method was applied to estimate catchment-scale effective groundwater parameters; representative values were 4.5?×?10^?4 m² s^?1 for the hydraulic diffusivity; 3.19?×?10^?5 m² s^?1/2 for the hydraulic desorptivity; 2.27?×?10^?4 m s^?1 for the hydraulic conductivity; and 0.2617 for the drainable porosity. The response constants correlate well with the total stream length and catchment area. Solutions of the linearised Boussinesq equation were used to guide the development of regional multivariate regression models for estimating low-flow indices from the catchment-scale effective parameters. Results showed that these catchments exhibit similar low-flow characteristics. The 7-day lowest average streamflows with return periods of 10 and 2 years (7Q10 and 7Q2) are highly correlated with the catchment-scale response constants. The low-flow ratio Q95/Q50 (ratio of daily streamflow exceeded 95 and 50% of the time, respectively) varied between 0.3 and 0.5, indicating a high proportion of groundwater in the streamflow. The advantage of the regional regression model is its conceptual basis and use of the catchment-scale effective parameters. The method has the potential to be applied to ungauged catchments for estimating low-flow statistics from stream length and catchment area.     

A comparative study of aquifer systems occurring at the Paraná sedimentary basin, Brazil: U-isotopes contribution

The radioactivity due to ²³⁸U and ²³⁴U in three aquifer systems occurring within the Paraná sedimentary basin, South America, has been investigated. Uranium is much less dissolved from fractured igneous rocks than from the porous sedimentary rocks as indicated by the U-mobility coefficients between 7.6 × 10^?6 and 1.2 × 10^?3 g cm^?3. These values are also compatible with the U preference ratios relative to Na, K, Ca, Mg and SiO₂, which showed that U is never preferentially mobilized in the liquid phase during the flow occurring in cracks, fissures, fractures and faults of the igneous basaltic rocks. Experimental dissolution of diabase grains on a time-scale laboratory has demonstrated that the U dissolution appeared to be a two-stage process characterized by linear and second-order kinetics. The U dissolution rate was 8 × 10^?16 mol m^?2 s^?1 that is within the range of 4 × 10^?16–3 × 10^?14 mol m^?2 s^?1 estimated for other rock types. The ²³⁴U/²³⁸U activity ratio of dissolved U in solutions was higher than unity, a typical result expected during the water–rock interactions when preferential ²³⁴U-leach from the rock surfaces takes place. Some U-isotopes data allowed estimating 320 ka for the groundwater residence time in a sector of a transect in São Paulo State. A modeling has been also realized considering all U-isotopes data obtained in Bauru (35 samples), Serra Geral (16 samples) and Guarani (29 samples) aquifers. The results indicated that the Bauru aquifer waters may result from the admixture of waters from Guarani (1.5 %) and Serra Geral (98.5 %) aquifers.     

Rheological Properties of Mantle Peridotites at Yushigou in the North Qilian Mountains and Their Implicationsfor Plate Dynamics

This paper discusses in detail the deformation textures, glide system, petrofabrics and olivine dislocation microstructures of mantle peridotites at Yushigou in the North Qilian Mountains, northwestern China. The peridotites have undergone high-pressure, high-temperature and low-strain rate plastic flow deformation. According to the dynamic recrystallized-grain size of olivine and the average spacing between the dislocation walls as well as the chemical composition of enstatite, the authors calculated the rheological parameters of the ancient upper mantle in the study area as follows: temperatures 1025-1093℃; pressures 3043-4278 MPa; depths 95-132 km; deviatoric stress 28-32 MPa; strain rates 0.2×10-14-2.13×10-14s-1 and equivalent viscosities 0.45×1020-4.65×1020 Pa · s. These parameters suggest that the position where plastic flow took place was correspondent to the low-velocity zone beneath the oceanic lithosphere and that oceanization characterized by middle-velocity (1-3 cm/a) sea-floor spreadi     

Estimating hydraulic conductivity using grain-size analyses, aquifer tests, and numerical modeling in a riverside alluvial system in South Korea

Hydraulic conductivity (K) for an alluvial system in a riverbank filtration area in Changwon City, South Korea, has been studied using grain-size distribution, pumping and slug tests, and numerical modeling. The alluvial system is composed of layers: upper fine sand, medium sand, lower fine sand, and a highly conductive sand/gravel layer at the base. The geometric mean of K for the sand/gravel layer (9.89?×?10^?4 m s^?1), as determined by grain-size analyses, was 3.33 times greater than the geometric mean obtained from pumping tests (2.97?×?10^?4 m s^?1). The geometric mean of K estimates obtained from slug tests (3.08?×?10^?6 m s^?1) was one to two orders of magnitude lower than that from pumping tests and grain-size analyses. K estimates derived from a numerical model were compared to those derived from the grain-size methods, slug tests and pumping tests in order to determine the degree of deviation from the numerical model. It is considered that the K estimates determined by the slug tests resemble the uppermost part of the alluvial deposit, whereas the K estimates obtained by grain-size analyses and pumping tests are similar to those from the numerical model for the sand/gravel layer of the riverside alluvial system.     

Static elasticity of cordierite I: Effect of heavy ion irradiation on the compressibility of hydrous cordierite

The effect of ion beam irradiations on the elastic properties of hydrous cordierite was investigated by means of Raman and X-ray diffraction experiments. Oriented single crystals were exposed to swift heavy ions (Au, Bi) of various specific energies (10.0–11.1 MeV/u and 80 MeV/u), applying fluences up to 5 × 10¹³ ions/cm². The determination of unit-cell constants yields a volume strain of 3.4 × 10^?3 up to the maximum fluence, which corresponds to a compression of non-irradiated cordierite at ~480 ± 10 MPa. The unit-cell contraction is anisotropic (e ₁ = 1.4 ± 0.1 × 10^?3, e ₂ = 1.5 ± 0.1 × 10^?3, and e ₃ = 7 ± 1 × 10^?4) with the c-axis to shrink only half as much as the axes within the ab-plane. The lattice elasticity for irradiated cordierite (? = 1 × 10¹² ions/cm²) was determined from single-crystal XRD measurements in the diamond anvil cell. The fitted third-order Birch–Murnaghan equation-of-state parameters of irradiated cordierite (V ₀ = 1548.41 ± 0.16 Å³, K ₀ = 117.1 ± 1.1 GPa, ?K/?P = ?0.6 ± 0.3) reveal a 10–11 % higher compressibility compared to non-irradiated cordierite. While the higher compressibility is attributed to the previously reported irradiation-induced loss of extra-framework H₂O, the anomalous elasticity as expressed by elastic softening (β _a ^?1 , β _b ^?1 , β _c ^?1  = 397 ± 9, 395 ± 28, 308 ± 11 GPa, ?(β ^?1)/?P = ?4.5 ± 2.7, ?6.6 ± 8.4, ?5.4 ± 3.0) appears to be related to the framework stability and to be independent of the water content in the channels and thus of the ion beam exposure.     

Strain rates from snowball garnet

Spiral inclusion trails in garnet porphyroblasts are likely to have formed due to simultaneous growth and rotation of the crystals, during syn‐metamorphic deformation. Thus, they contain information on the strain rate of the rock. Strain rates may be interpreted from such inclusion trails if two functions are known: (1) The relationship between rotation rate and shear strain rate; (2) the growth rate of the crystal. We have investigated details of both functions using a garnetiferous mica schist from the eastern European Alps as an example. The rotation rate of garnet porphyroblasts was determined using finite element modelling of the geometrical arrangement of the crystals in the rock. The growth rate of the porphyroblasts was determined by using the major and trace element distributions in garnet crystals, thermodynamic pseudosections and information on the grain size distribution. For the largest porphyroblast size fraction (size L=12 mm) we constrain a growth interval between 540 and 590 °C during the prograde evolution of the rock. Assuming a reasonable heating rate and using the angular geometry of the spiral inclusion trails we are able to suggest that the mean strain rate during crystal growth was of the order of =6.6 × 10^?14 s^?1. These estimates are consistent with independent estimates for the strain rates during the evolution of this part of the Alpine orogen.     

Modelling of the thermal dependence of structural and elastic properties of calcite, CaCO3

A computational method, based on the quasiharmonic approximation, has been computer-coded to calculate the temperature dependence of elastic constants and structural features of crystals. The model is applied to calcite, CaCO₃; an interatomic potential based on a C-O Morse function and Ca-O and O-O Borntype interactions, including a shell model for O, has been used. Equilibrations in the range 300–800 K reproduce the experimental unit-cell edges and bond lengths within 1%. The simulated thermal expansion coefficients are 22.3 (//c) and 2.6 (⊥ c), against 25.5 and-3.7×10^?6K^?1 experimental values, respectively. The thermal coefficients of elastic constants tend to be underestimated; for the bulk modulus, -2.3 against-3.7×10^?4K^?1 is obtained.     

Degradation of β-blockers in water by sulfate radical-based oxidation: kinetics,mechanism and ecotoxicity assessment

This study investigated the kinetics and degradation pathway of acebutolol, metoprolol and sotalol in a sulfate radical-based advanced oxidation process. The selected pharmaceuticals were β-blockers which have been used to treat cardiovascular diseases. Due to its frequent use, the presence of these pharmaceuticals in the environment has been regularly reported. In this study, sulfate radicals were generated using peroxymonosulfate with cobalt (II) as activator. At pH 7 and 25 °C, the second-order rate constant for the reaction between SO₄ ^·? with metoprolol, acebutolol and sotalol was (1.0 ± 0.1) × 10¹⁰, (2.0 ± 0.1) × 10¹⁰ and (3.0 ± 0.2) × 10¹⁰ M^?1 s^?1, respectively. Sixteen transformation by-products were identified from the selected β-blockers. These transformation by-products were mainly formed through the hydroxylation, aromatic ring-opening reaction and aliphatic chain oxidation. The decomposition of β-blockers by sulfate radicals was found to start from the formation of hydroxylated β-blockers followed by an aromatic ring-opening reaction. In general, this study showed that β-blockers reacted favorably with sulfate radicals, and various transformation by-products could be produced. The result from the ecotoxicity assessment showed that almost all of the transformation by-products were less toxic than its parent compound. Therefore, a sulfate radical-based advanced oxidation process could be an effective method for the treatment of β-blockers in water.     

Rate constants of dissolution derived from the measurements of mass balance in hydrological catchments

The experimental rate constant of dissolution of oligoclase, 1.7 × 10 ^{? 2} mol · m^?2 · s^?1 (Busenberg and Clemency, 1976), is compared with rate constants, 5.2 × 10^?15 to 6.8 × 10^?13 mol · m^?2· s^?1, derived from mass-balance measurements of sodium in hydrological catchments. The wide range of the field-based rate constants mainly reflects the uncertainty in the evaluation of the specific wetted surface of rock in aquifer. The most probable order of magnitude of the field rate constant is 10^?14 mol · m^?2· s^?1. The difference between the experimental and field rate constant is only partly caused by lower temperature and lowerP_CO2 in the aquifer. The main reason for the discrepancy is the diverse history of the mineral surfaces undergoing reaction.It is suggested that the feldspar surfaces in an aquifer are old, compared to those of feldspars utilized in laboratory experiments. They have fewer defects and are smooth. The fresh surfaces of feldspars studied in the laboratory consist of many kinks and ledges and small-area terraces which dissolve faster.The differences in rate constants derived from field data on several specific catchments indicate that the anthropogenic processes which have operated during this century in Central Europe speed up the rate of dissolution by a factor of three. Modern agricultural practices speed up the rate by a factor of five.