Using δ18O and δ2H to Detect Hydraulic Connection Between a Sinkhole Lake and a First-Magnitude Spring

Oxygen and hydrogen isotopes were used in this study to detect a hydraulic connection between a sinkhole lake and a karst spring. In karst areas, surface water that flows to a lake can drain through sinkholes in the lakebed to the underlying aquifer, and then flows in karst conduits and through aquifer matrix. At the study site located in northwest Florida, USA, Lake Miccosukee immediately drains into two sinkholes. Results from a dye tracing experiment indicate that lake water discharges at Natural Bridge Spring, a first-magnitude spring 32 km downgradient from the lake. By collecting weekly water samples from the lake, the spring, and a groundwater well 10 m away from the lake during the dry period between October 2019 and January 2020, it was found that, when rainfall effects on isotopic signature in spring water are removed, increased isotope ratios of spring water can be explained by mixing of heavy-isotope-enriched lake water into groundwater, indicating hydraulic connection between the lake and the spring. Such a detection of hydraulic connection at the scale of tens of kilometers and for a first-magnitude spring has not been previously reported in the literature. Based on the isotope ratio data, it was estimated that, during the study period, about 8.5% the spring discharge was the lake water that drained into the lake sinkholes.     

Alternative climate data sources for distributed hydrological modelling on a daily time step

Two major criteria in choosing climate data for use in hydrological modelling are the period of record of the data set and the proximity of the collection platform(s) to the basin under study. Conventional data sets are derived from weather stations; however, in many cases there are no weather stations sufficiently close to a basin to be representative of climate conditions in that basin. In addition, it is often the case either that the period of record for the weather station(s) does not cover the period of the proposed simulation or that there are gaps in the data. Therefore, the objectives of this study are to investigate alternative climate data sources for use in hydrological modelling and to develop a protocol for creating hydrological data sets that are spatially and temporally harmonized. The methods we used for constructing daily, spatially distributed, climatic data sets of precipitation, maximum and minimum temperature, wind speed, solar radiation, potential evapotranspiration, and relative humidity are described. The model used in this study was the Soil and Water Assessment Tool implemented on the Mimbres River Basin located in southwestern New Mexico, USA, for the period 2003–2006. Our hydrological simulations showed that two events in January and February 2005 were missed, while an event in August 2006 was well simulated. We have also investigated the usefulness of several other precipitation data sets and compared the simulation results. Copyright © 2010 John Wiley & Sons, Ltd.     

Adsorption Characteristics of Reactive Black 5 from Aqueous Solution onto Chitosan

Adsorption of reactive black 5 (RB5) from aqueous solution onto chitosan was investigated in a batch system. The effects of solution pH, initial dye concentration, and temperature were studied. Adsorption data obtained from different batch experiments were modeled using both pseudo first‐ and second‐order kinetic equations. The equilibrium adsorption data were fitted to the Freundlich, Tempkin, and Langmuir isotherms over a dye concentration range of 45–100 µmol/L. The best results were achieved with the pseudo second‐order kinetic and Langmuir isotherm equilibrium models, respectively. The equilibrium adsorption capacity (q_e) was increased with increasing the initial dye concentration and solution temperature, and decreasing solution pH. The chitosan flakes for the adsorption of the dye was regenerated efficiently through the alkaline solution and was then reused for dye removal. The activation energy (E_a) of sorption kinetics was estimated to be 13.88 kJ/mol. Thermodynamic parameters such as changes in free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) were evaluated by applying the van't Hoff equation. The thermodynamics of reactive dye adsorption by chitosan indicates its spontaneous and endothermic nature.     

Full scale experimental study on vibration scattering using open and in-filled (GeoFoam) wave barriers

Ground vibrations induced by machine foundations can cause unfavourable effects on the nearby buildings ranging from annoyance to structural damage. Most of these vibrations propagate in the form of surface (Rayleigh) waves. Machine foundations produce a steady state vibration, for which, wave barriers can be a successful technique to minimize these effects by scattering the generated steady state surface waves. A full scale field experimental study has been conducted to investigate the protective performance of both open and in-filled trench with GeoFoam material as well as to examine the influences of wall geometry and location from the vibratory source on the isolation efficiency. An innovative approach to construct GeoFoam trench as a wave barrier is proposed in this study as well. The results of the field experimental investigations are analyzed and interpreted to provide recommendations for implementation in design. Experimental results show that both open and GeoFoam barriers can effectively reduce the transmitted waves. The field experimental results have been compared with those obtained from the developed numerical model using a finite element package, ABAQUS.     

Environmental impact assessment of air and heavy metal concentration in groundwater of Maheshwaram watershed, ranga reddy district, Andhra Pradesh

Anthropogenic activities in Maheshwaram watershed have deteriorated water, air and soil quality during the last ten years due to rapid urbanisation and industrial development. Maheshwaram watershed experienced drastic changes in land use pattern, being very close to the Hyderabad city. Base-line data was collected during post monsoon season (October-November) of 2010 in Maheshwaram watershed to assess the impacts of change in land use, urbanisation and industrialisation on air, water and soil quality for Environmental Impact Assessment (EIA). Air samples were analysed for Suspended Particulate Matter (SPM) and Respirable Suspended Particulate Matter (RSPM). Groundwater samples were analysed for pH; EC; TDS; TH; cations, anions and heavy metals viz., Fe, Mn, Al, Si, V, Cr, As, Sr, Rb, Se, Ba, Li, B, Be, Co, Ni, Zn, Cd, and Pb using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Analysed data were compared with the National and International Standards and subjected to Factor Analysis (FA) for six chemical variables to assess and characterise hydro-chemical processes. A comparison of the results of groundwater samples with WHO and BIS guidelines show that most of the groundwater samples are heavily contaminated with heavy metals like lead, chromium, nickel, barium, aluminium, boron and selenium, which was quantified and presented in the form of spatial variation diagrams prepared using ArcGIS. 9.3.1. Similarly the results of air samples compared with the Central Pollution Control Board, Ministry of Environment and Forests, Government of India guidelines show that most of the air samples for residential, rural and industrial areas are contaminated by SPM and RSPM.     

Comprehensive physicochemical study of dioctahedral palygorskite-rich clay from Marrakech High Atlas (Morocco)

This study is devoted to the physicochemical and mineralogical characterizations of palygorskite from Marrakech High Atlas, Morocco. The raw clay and its Na⁺-saturated <2 μm fraction were characterized using chemical, structural, and thermal analytical techniques. Measurements of specific surface area and porous volume are reported. The clay fraction was found to be made up of 95 % of palygorskite and 5 % of sepiolite. An original feature of this palygorskite is its deficiency in zeolitic H₂O. The half-cell structural formula of its dehydrated form was determined on the basis of 21 oxygens to be (Si_7.92Al_0.08)(Mg_2.15Al_1.4Fe_0.4Ti_0.05 $ \square_{1} $ )(Ca_0.03Na_0.08K_0.04)O₂₁, while the hydrated form could be formulated as (Si_7.97Al_0.03)(Mg_2.17Al_1.46Fe_0.40Ti_0.05)(Ca_0.03Na_0.07K_0,03)O_20.18(OH)_1.94(OH₂)_3.88·2.43 H₂O. These formulas show that the (Al³⁺+Fe³⁺)/Mg²⁺ ratio is around 0.84, revealing a pronounced dioctahedral character. Further, inside its octahedral sheet, it was determined that the inner M₁ sites are occupied by vacancies, whereas the M₂ sites are shared between 90 % of trivalent cations (78 % for Al³⁺ and 22 % for Fe³⁺), 7.5 % of Mg²⁺, and 2.5 % of Ti⁴⁺, all of them linked to 1.94 of structural hydroxyls. The two remaining Mg²⁺ by half-cell occupy edge M₃ sites and are coordinated to 3.88 molecules of OH₂. Channels of this palygorskite are deficient in zeolitic H₂O since they contain only 2.43 H₂O molecules. A correlation was found between these results and the observation of very intense and well-resolved FTIR bands arising from dioctahedral domains (mainly Al₂OH, Fe₂OH, and AlFeOH) along with very small responses from a trioctahedral domain (Mg₃OH). Accordingly, a schematic representation of the composition of the octahedral sheet was proposed. The cation exchange capacity, specific surface area, and total pore volume were also assessed to be ca. 21.2 meq/100 g, 116 m²/g, and 0.458 cm³/g, respectively.     

Stability and equation of state of post-aragonite BaCO3

At ambient conditions, witherite is the stable form of BaCO₃ and has the aragonite structure with space group Pmcn. Above ~10 GPa, BaCO₃ adopts a post-aragonite structure with space group Pmmn. High-pressure and high-temperature synchrotron X-ray diffraction experiments were used to study the stability and equation of state of post-aragonite BaCO₃, which remained stable to the highest experimental P–T conditions of 150 GPa and 2,000 K. We obtained a bulk modulus K ₀ = 88(2) GPa with $K'$  = 4.8(3) and V ₀ = 128.1(5) ų using a third-order Birch-Murnaghan fit to the 300 K experimental data. We also carried out density functional theory (DFT) calculations of enthalpy (H) of two structures of BaCO₃ relative to the enthalpy of the post-aragonite phase. In agreement with previous studies and the current experiments, the calculations show aragonite to post-aragonite phase transitions at ~8 GPa. We also tested a potential high-pressure post–post-aragonite structure (space group C222 ₁ ) featuring four-fold coordination of oxygen around carbon. In agreement with previous DFT studies, ΔH between the C222 ₁ structure and post-aragonite (Pmmn) decreases with pressure, but the Pmmn structure remains energetically favorable to pressures greater than 200 GPa. We conclude that post–post-aragonite phase transformations of carbonates do not follow systematic trends observed for post-aragonite transitions governed solely by the ionic radii of their metal cations.     

Relative Sea‐Level Changes During Roman Times in the Northwest Mediterranean: The 1st Century A.D. Fish Tank of Forum Julii,Fréjus,France

Fish tanks become fashionable throughout the Mediterranean area between the 1st century B.C. and the 1st century A.D. Because of this narrow chronological window, and their link to former sea level, they constitute precious archives to investigate relative sea level (RSL) since the Roman period, especially when combined with fossilized marine benthos found attached to the fish tank walls. Here, we present new results from an integrated analysis of a fish tank located in the Roman colony of Fréjus, Southeastern France. The well‐preserved biological remains on the fish tank wall allow us to estimate an RSL rise of 40 ± 10 cm at Fréjus since Roman times, consistent with a recently published range of −32 to −58 ± 5 cm for the Northwestern Mediterranean for the same time. By contrast, the findings contradict the ∼150 cm of RSL change since Roman times reported for the Northwestern Mediterranean by some authors. © 2013 Wiley Periodicals, Inc.     

Radionuclides measurements and mineralogical studies on beach sands, East Rosetta Estuary, Egypt

Radiometric measurements were carried out for the beach sands from East Rosetta estuary to determine the activity concentrations of 238 U, 226 Ra, 232 Th, and 40 K, using a Hyper Pure Germanium spectrometer, to estimate the dose rates and radiation hazard indices. The average specific activities are 778.20 Bq/kg for 238 U; 646.89 Bq/kg for 226 Ra; 621.92 and 627.85 Bq/kg for the 222 Rn daughters 214 Pb and 214 Bi respectively. The average specific activity of 232 Th is 1510.25 Bq/kg, while the calculated specific activity for 40 K has an average of 8.41 Bq/kg. The average specific activity of 235 U is 38.61 Bq/kg. The average absorbed dose rate is 1211.36 nGy/h, 20 times higher than the estimated average global primordial radiation of 60 nGy/h and 6 times higher than that of the world range (10-200 nGy/h). The radium equivalent (Ra eq ) values are from 6 to 9 times the recommended value. The internal and external hazard indices (H int , H ex ) indicate that their values are from 6 to 11 times the permissible values of these indices. These higher values may be due to the presence of economic heavy minerals containing radionuclides as zircon and monazite as well as some trace minerals, thorite and uranothorite. The mineralogical study indicates the beach sands contain heavy minerals, zircon, monazite, rutile, ilmenite, leucoxene, magnetite and garnet. The average abundance of zircon is 0.175 wt% ranging from 0.125 wt% to 0.239 wt%, while it is 0.004wt% ranging from 0.001 wt% to 0.007 wt% for monazite. The average abundance is 0.087 wt% for rutile; 2.029 wt% for ilmenite; 1.084 wt% for magnetite; 0.384 wt% for leucoxene and 0.295 wt% for garnet.     

Trace element and isotopic fingerprints in HP–LT metamorphic rocks as a result of fluid–rock interactions (Ile de Groix,France)

Whole rock trace element and isotopic compositions of different HP–LT metamorphic rocks of the Ile de Groix were analysed to characterise geochemical fingerprints during subduction and exhumation in a late Palaeozoic HP metamorphic terrain. Massive metabasites of hydrothermally altered enriched mid-ocean ridge basalt (E-MORB) origin are in association with banded metabasic rocks of volcano-sedimentary origin and metapelites. Fluid-rock interactions that likely occurred during seafloor hydrothermal alteration and early subduction metasomatism increased δ¹⁸O values, as well as K₂O, Na₂O, MgO, and LILE contents and decreased CaO contents of metabasites. Most metabasites have retained their early-subduction and pre-HP trace element and isotopic composition, even for rocks metamorphosed to lower eclogite-facies P–T conditions. Micaschists also preserved apparent pelitic protolith trace element values and oxygen isotopic compositions. During retrograde metamorphism related to the exhumation, metabasites were rehydrated by fluids in equilibrium with the host rock compositions, which were likely derived from the basic rocks. This style of fluid–rock interaction formed a greenschist facies mineral assemblage. Metabasites that underwent pervasive alteration by seafloor hydrothermal and metasomatism processes prior to peak metamorphism, show greater effects of retrogression and albitisation, probably because they were richer in H₂O and Na₂O. The variety of metamorphic assemblages on the Ile de Groix is thus directly related to the pre-HP rock composition. The extent of retrogression in the western part of the Ile de Groix primarily reflects stronger metasomatic intensities than in the eastern part.