Effect of pH on binding of pyrene to hydrophobic fractions of dissolved organic matter (DOM) isolated from lake water

In order to better understand the compositional and structural complexity of dissolved organic matter (DOM) macromolecules and provide mechanistic information on the binding of hydrophobic organic contaminants (HOCs) to DOM, we fractionated large amounts of lake water into three hydrophobic DOM-fractions. The variation of the partitioning coefficients (K _DOC) of pyrene at different pH levels was examined by florescence quenching titration. Results show that, relative to the more polar acidic DOM-fractions, the hydrophobic neutral fraction exhibits a higher sorption ability to pyrene. Generally, the sorption of pyrene to the three hydrophobic fractions is strongly pH-dependent. The K _DOC values of pyrene generally increase with decreasing pH levels, which is especially obvious in the sorption of pyrene to the fulvic acid fractions, suggesting that the binding is controlled by hydrophobic interactions. The mechanisms underlying the binding of pyrene to the hydrophobic fractions were also discussed. Our data are beneficial to further understanding the binding of HOCs to DOM and how it has been affected, which may result in more accurate predictions of K _DOC.     

Using Optical Properties to Quantify Fringe Mangrove Inputs to the Dissolved Organic Matter (DOM) Pool in a Subtropical Estuary

Dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) optical properties were analyzed along two estuarine river transects during the wet and dry seasons to better understand DOM dynamics and quantify mangrove inputs. A tidal study was performed to assess the impacts of tidal pumping on DOM transport. DOM in the estuaries showed non-conservative mixing indicative of mangrove-derived inputs. Similarly, fluorescence data suggest that some terrestrial humic-like components showed non-conservative behavior. An Everglades freshwater-derived fluorescent component, which is associated with soil inputs from the Northern Everglades, behaved conservatively. During the dry season, a protein-like component behaved conservatively until the mid-salinity range when non-conservative behavior due to degradation and/or loss was observed. The tidal study data suggests mangrove porewater inputs to the rivers following low tide. The differences in quantity of DOM exported by the Shark and Harney Rivers imply that geomorphology and tidal hydrology may be a dominant factor controlling the amount of DOM exported from the mangrove ecotone, where up to 21 % of the DOC is mangrove-derived. Additionally, nutrient concentrations and other temporal factors may control DOM export from the mangroves, particularly for the microbially derived fluorescent components, contributing to the seasonal differences. The wet and dry season fluxes of mangrove DOM from the Shark River is estimated as 0.27?×?10⁹ mg C d^?1 and 0.075?×?10⁹ mg C d^?1, respectively, and the Harney River is estimated as 1.9?×?10⁹ mg C d^?1 and 0.20?×?10⁹ mg C d^?1.     

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.     

Hydrogeochemical assessment of groundwater in Isfahan province, Iran

Groundwater quality in five catchment areas in Isfahan province of Iran is assessed by measuring physicochemical parameters including major cation and anion compositions, pH, total dissolved solid, electrical conductivity and total hardness. For this purpose, 567 piezometric well samples were collected in October 2007. The abundance of major ions in four of the catchment areas including Gavkhuni, Ardestan, Salt lake and Central Iran desert basins is similar and follows Cl^??>?SO₄ ^2??>?Na⁺?>?HCO₃ ^??>?Ca²⁺?>?Mg²⁺?>?K⁺?>?CO₃ ^2? trend, while in the fifth basin (Karoon), the trend changes into HCO₃ ^??>?Ca²⁺?>?Cl^??>?SO₄ ^2??>?Mg²⁺?>?Na⁺?>?K⁺?>CO₃ ^2?. In general, four water facies are determined and it is shown that alkali elements and strong acids are dominating over alkaline earth and weak acids. Statistical analysis including Mann?CWhitney U test indicate that physicochemical parameters in three of the five investigated basins [Gavkhuni, Ardestan and Central Iran desert (CID)] are similar, while Karoon and salt lake basins display different characteristics. The result indicate that groundwater west of the province is suitable for irrigation, while in the central and eastern parts of the province the groundwater loses its quality for this purpose. It is concluded that mineral dissolution and evapotranspiration are the main processes that determine major ion compositions.     

High-pressure behaviour and equation of state of calcite, CaCO3

The high-pressure response of the cell parameters of calcite, CaCO₃, has been investigated by single crystal X-ray diffraction. The unit cell parameters have been refined from 0 to 1.435?GPa, and the linear and volume compressibilities have been measured as β _a =2.62(2)?×?10^?3?GPa^?1,β _c =7.94(7)?×?10^?3?GPa^?1, β _v =13.12?×?10^?3?GPa^?1. The bulk modulus has been obtained from a fit to the Birch-Murnaghan equation of state, giving K ₀=73.46?±?0.27?GPa and V ₀=367.789 ±?0.004?ų with K′=4. Combined with earlier data for magnesite, ankerite and dolomite, these data suggest that K ₀ V ₀ is a constant for the Ca-Mg rhombohedral carbonates.     

Magnetic properties related to hydrothermal alteration processes at the Escondida porphyry copper deposit,northern Chile

Fluid–rock interaction related to the circulation of hydrothermal fluids can strongly modify the physicochemical properties of wall rocks in porphyry Cu deposits. These processes can also produce compositional and textural changes in ferromagnetic minerals, which can be quantified using magnetic methods. In the Escondida porphyry Cu deposit of northern Chile, each hydrothermally altered lithology is characterized by a discrete assemblage of Fe–Ti oxide minerals. These minerals have distinctive bulk magnetic susceptibility (K _bulk), temperature-dependent magnetic susceptibility, and magnetic hysteresis parameters. Selectively altered rocks (i.e., potassic and chloritic alteration types) exhibit the highest K _bulk values (>3.93?×?10^?3 SI units), and their hysteresis parameters indicate multidomain magnetic mineral behavior. This suggests that these rocks are composed of the coarsest magnetic grain sizes within the deposit. Optical analyses and susceptibility–temperature curves confirm that the magnetic signals in selectively altered rocks are mainly carried by secondary magnetite. In contrast, pervasively altered rocks (i.e., quartz-sericite and argillic alteration types) exhibit low K _bulk values (<1.93?×?10^?4 SI units) and contain smaller pseudo-single domain magnetic grain assemblages. This is consistent with the destruction and/or reduction in size of magnetite under acidic conditions. The results therefore demonstrate a genetic relationship between the hydrothermal alteration processes, Fe–Ti oxide minerals, and magnetic properties of the wall rock in the Escondida deposit. These magnetic methods can be considered a sensitive and efficient petrophysical tool for the identification and semi-quantification of alteration assemblages, and facilitating the recognition and mapping of discrete hydrothermal zones during exploration and operation of porphyry Cu deposits.     

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10⁻¹³ to 7.16 × 10⁻¹² mol Hg (mg C)⁻¹ m⁻²s⁻¹. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R² = 0.88), aromaticity (R² = 0.80), and molecular weight (R² = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.     

Equations of state of magnesium silicates anhydrous B and superhydrous B

High-pressure single crystal X-ray diffraction experiments of phase anhydrous B and superhydrous B have been carried out to 7.3 and 7.7?GPa, respectively, at room temperature. Fitting a third-order Birch-Murnaghan equation of state to the P-V data yields values of V ₀?=?838.86?±?0.04?ų, K_T,0?=?151.5?±?0.9?GPa and K′?=?5.5?±?0.3 for Anhy-B and V ₀?=?624.71?± 0.03?ų, K_T,0?=?142.6?±?0.8?GPa and K′?=?5.8?±?0.2 for Shy-B. A similar analysis of the axial compressibilities in Anhy-B reveals that the c-axis is most compressible (K_c?=?137?±?3?GPa), the b-axis is least compressible (K_b?=?175?±?4?GPa), and the a-axis is intermediate (K_a?=?148?±?1?GPa). In Shy-B, the a-axis is most compressible (K_a?=?135?±?1?GPa), followed by the b- and c-axes which have similar compressibilities (K_b?=?146?±?3?GPa; K_c?=?148?±?3?GPa). The fact that the b-axis of Shy-B is approximately 16% more compressible than Anhy-B is primarily due to differences in the O-T layer in which the H atoms are located and the linkages with the adjacent O layers. The rigid edge-sharing chains of MgO₆ and SiO₆ octahedra in the O layer control compressibility along the a- and c-axes in both structures. The net result is a reduction in the overall anisotropic compression from ～22% in Anhy-B to ～9% in Shy-B.     

Copper, nickel and zinc contamination in soils within the precincts of mining and landfilling environments

This study determined copper, nickel and zinc concentrations in soils within the precincts of a copper-nickel mining and urban landfilling environments, and used obtained values to appraise the degree of soil contamination and pollution based on geoaccumulation index, contamination factor and pollution load index. Mean concentrations of copper (252.4?mg/kg), nickel (153.0?mg/kg) and zinc (30.4?mg/kg) in soils around the mining area were considerably higher than those around the landfill (4.3, 0.91, and 13.7?mg/kg, respectively, for copper, nickel and zinc). The mining area was moderate to heavily contaminated with copper, nickel and zinc (1?<?I _geo?<?4), whereas the landfill area was moderately contaminated (1?<?I _geo?<?3). In both areas, the level of copper contamination was higher than that of nickel and zinc. Contamination around the mining environment was attributed to mining activities whereas around the landfill area, migration of leachate from the disposed waste could have been responsible.     

Tunisian landfill leachate treatment using <Emphasis Type="Italic">Chlorella</Emphasis> sp.: effective factors and microalgae strain performance

The potential of the autoclaved Tunisian landfill leachate treatment using microalgae (Chlorella sp.) cultivation was investigated in this study. Landfill leachate was collected from Borj Chakir landfill, Tunisia. A full factorial experimental design 2² was proposed to study the effects of the incubation time and leachate ratio factors on the organic matter removal expressed in chemical oxygen demand (COD) and ammoniacal nitrogen (NH₄─N) and on the biological response of Chlorella sp. expressed by the cell density and chlorophyll content. All experiments were batch runs at ambient temperature (25 ± 2 °C). The Chlorella sp. biomass and chlorophyll a concentrations of 1.2 and 5.32 mg L^?1, respectively, were obtained with 10% leachate spike ratio. The obtained results showed that up to 90% of the ammoniacal nitrogen in landfill leachate was removed in 10% leachate ratio spiked medium with a residual concentration of 40 mg L^?1. The maximum COD removal rate reached 60% within 13 days of incubation time indicating that microalgae consortium was quite effective for treating landfill leachate organic contaminants. Furthermore, with the 10% leachate ratio spiked medium, the maximum lipid productivity was 4.74 mg L^?1 d^?1. The present study provides valuable information for potential adaptation of microalgae culture and its contribution for the treatment of Tunisian landfill leachate.     

Probing the oxidation-reduction properties of terrestrially and microbially derived dissolved organic matter

Dissolved organic matter (DOM) has been shown to be an integral component in biogeochemical electron transfer reactions due to its demonstrated ability to facilitate redox reactions. While the role of DOM as a facilitator of electron transfer processes has been demonstrated, greater knowledge would lead to better understanding of the structural components responsible for redox behavior, such as quinones and nitrogen and sulfur (N/S) functional groups. This investigation uses direct scan voltammetry (DSV) coupled with fluorescence and NMR spectroscopy as well as thermochemolysis gas chromatography mass spectrometry (GC-MS) and X-ray photoelectron spectroscopy (XPS) to elucidate the organic moieties responsible for facilitating electron transfer reactions. We contrast electrochemical properties and structural details of three organic matter isolates from diverse sources; Great Dismal Swamp DOM (terrestrially derived, highly aromatic), Pony Lake DOM (microbially derived, highly aliphatic) and Toolik Lake (terrestrially derived, photochemically and microbially altered) with juglone (a redox-active model quinone). Aromatic and phenolic constituents were detected (by ¹³C NMR) and recovered (by thermochemolysis GC-MS) from all three fulvic acid samples, highlighting the ubiquity of these compounds and suggesting that the quinone-phenol redox couple is not limited to DOM derived from lignin precursors. The range of hydroxy-benzene and benzoic acid derivatives may explain the lack of a single pair of well-defined oxidation and reduction peaks in the DSV scans. The presence of a wide-range of hydroxylated benzoic acid isomers and other redox-active aromatic residues implies that native DOM possesses overlapping redox potentials analogous to their characteristic range of pK_a values.     

Mobilization of actinides by dissolved organic compounds at the Nevada Test Site

The effect of dissolved organic matter (DOM) on Am(III), Pu(IV), Np(V), and U(VI) sorption was investigated with natural water (pH ∼8) and zeolitized tuff samples collected from the Rainier Mesa tunnel system, Nevada Test Site, where the USA detonated underground nuclear tests prior to 1992. Perched vadose zone water at Rainier Mesa has high levels of DOM as a result of microbial degradation of mining debris (diesel, wood, etc.). The Am and Pu sorption K_ds were up to two orders of magnitude lower in water with high DOM (15-19 mg C/L) compared to the same water with DOM removed (<0.4 mg C/L) or in naturally low DOM (0.2 mg C/L) groundwater. In contrast, K_ds of Np and U were less affected by DOM at these solution conditions. Uranium sorption decreased as a result of high dissolved inorganic C (DIC) resulting from microbial degradation of DOM. Thermodynamic model predictions, based on actinide-humic acid stability constants available in the literature, are in general agreement with measured K_d data, correctly predicting the effects of DIC and DOM on actinide retardation. This agreement is encouraging to future modeling efforts and suggests that effects of DOM and DIC can be incorporated into reactive transport modeling predictions. The Am and Pu transport rates in Rainier Mesa tunnel waters will be substantially faster as a result of the elevated DOM levels. Low diffusion rates of actinide-DOM macromolecular complexes may focus Pu and Am transport into fractures and minimize retardation via matrix diffusion. The resulting transport behavior will affect actinide distribution patterns and associated risk estimates.     

Genesis of granitoid batholiths of Peninsular Malaysia and implications for models of crustal evolution: Evidence from a NdSr isotopic and UPb zircon study

Nd, Sr and U-Pb isotopic data for the late Triassic West Coast Province batholiths and Permian to Triassic East Coast Province batholiths of Peninsular Malaysia allow estimates of the ages of the crustal fragments comprising the peninsula to be made. Initial ?_Nd and ?_Sr values for granitoids from the West Coast Province range from ?6 to ?10 and +160(0.716) to +660(0.751) respectively. Nd model ages calculated based on a depleted mantle evolution model (T_DM^Nd) range from 1300 Ma to 1800 Ma and are in general agreement with the mid-Proterozoic upper intersection ages of U-Pb zircon reverse discordia (1500–1700 Ma). Initial ?_Nd and ?_Sr values for granitoids from the East Coast Province range from ?0.8 to ?6 and +10(0.705) to +130(0.714) respectively. Calculated T_DM^Nd ages of 900–1400 Ma for these granitoids are comparable to two U-Pb zircon reverse discordia intercepts that yield 800 Ma and 1350 Ma. The general agreement of U-Pb zircon inheritance ages and T_DM^Nd ages are interpreted to correspond to the Proterozoic ‘crust formation’ ages of the continental fragments represented by the West Coast and East Coast batholithic provinces. Mid-Proterozoic (~ 1300–1900 Ma) ‘crust formation’ ages are commonly shown by other Phanerozoic continental margin plutonic and volcanic belts. The ubiquitous mid-Proterozoic ‘crust formation’ ages and the absence of Archaean signatures suggest voluminous juvenile additions to the continental crust in the mid-Proterozoic. Such ages at continental margins would imply that many continental blocks had achieved very much their present-day extent by the mid-Proterozoic.     

Hydrostatic compression of ilmenite phase of ZnSiO3 and MgGeO3

Accurate measurements of cell parameters were performed on the ilmenite phases of ZnSiO₃ and MgGeO₃ using an X-ray diffraction method under hydrostatic conditions. The linear changes in cell parameter are represented by 1?a/a ₀=(1.06±0.04)×10^?4 P(kbar) and 1?c/c ₀=(2.11±0.04)×10^?4 P for ZnSiO₃, and 1?a/a ₀=(1.37±0.03)×10^?4 P and 1?c/c ₀=(2.05±0.04)×10^?4 P for MgGeO₃. A least-squares calculation using the first-order Birch-Murnaghan equation gives K _T =2.16±0.02 Mbar and K _T =1.87±0.02 Mbar for ZnSiO₃ and MgGeO₃, respectively. Elastic systematics assuming K _T V _m =constant give a predicted value K _T =2.14 Mbar for the ilmenite phase of MgSiO₃.     

Determination of the first ionization constant of silicic acid from quartz solubility in borate buffer solutions to 350°C

The solubility of quartz has been determined in borax buffer solutions having total boron concentrations of 0.10, 0.20, 0.40 and 0.60 mol kg^?1 and over the temperature range 130–350°C at the saturated vapour pressure of the system. The first ionization constant of silicic acid was calculated from the solubility data and varied from ?logK₁ = 8.88 (± 0.15) at 130°C to ?logK₁ = 10.06 (± 0.20) at 350°C. The solubility of quartz in these solutions was due to the presence of the three species, H₄SiO₄, H₃SiO₄^? and NaH₃SiO₄°. The equilibrium constant for the reaction, Na⁺ + H₃SiO₄^? = NaH₃SiO₄° extended from log K_as = 1.18?1.40 (± 0.20) over the temperature interval 135–301°C. The formation of NaH₃SiO₄° ion pairs was concluded to contribute significantly to the solubility of quartz in alkaline hydrothermal solutions when pH > 8 and sodium concentration exceeds 0.10 mol kg^?1.     

Thermal expansion and crystal structure of FeSi between 4 and 1173 K determined by time-of-flight neutron powder diffraction

The thermal expansion and crystal structure of FeSi has been determined by neutron powder diffraction between 4 and 1173?K. No evidence was seen of any structural or magnetic transitions at low temperatures. The average volumetric thermal expansion coefficient above room temperature was found to be 4.85(5)?×?10^?5?K^?1. The cell volume was fitted over the complete temperature range using Grüneisen approximations to the zero pressure equation of state, with the internal energy calculated via a Debye model; a Grüneisen second-order approximation gave the following parameters: θ_D=445(11)?K, V ₀=89.596(8)?ų, K ₀′=4.4(4) and γ′=2.33(3), where θ_D is the Debye temperature, V ₀ is V at T=0?K, K ₀′ is the first derivative with respect to pressure of the incompressibility and γ′ is a Grüneisen parameter. The thermodynamic Grüneisen parameter, γ_th, has been calculated from experimental data in the range 4–400?K. The crystal structure was found to be almost invariant with temperature. The thermal vibrations of the Fe atoms are almost isotropic at all temperatures; those of the Si atoms become more anisotropic as the temperature increases.     

A GIS mapping assessment of the suitability of the Oued Rmel aquifer for irrigation in the Zaghouan district (north-eastern Tunisia)

A total of twenty-three water samples were collected in winter 2013 to assess groundwater quality in the Oued Rmel aquifer in the Zaghouan governate in Tunisia. These samples were subject to in-field measurements of some physico-chemical parameters (temperature, pH, and salinity), and laboratory analysis of major elements. Several parameters were used to assess the quality of water destined for irrigation, including electrical conductivity (EC) and sodium adsorption ratio (SAR). As part of this work, GIS was used to study spatial distributions of SAR, EC, residual sodium carbonate, sodium percentage (%Na), Doneen’s permeability index, Kelly’s ratio, and magnesium hazard and, therefore, evaluated the water quality of Oued Rmel (good, fair, or poor) regarding irrigation. The major ions most abundantly found in the waters of Oued Rmel were in the following order: Na⁺?>?Ca²⁺?>?Mg²⁺?>?K⁺ and Cl^??>?SO₄^2??>?HCO₃. 56% of water samples from the Oued Rmel aquifer showed a low alkalinization risk, where SAR was lower than 10, 39% have a medium soil destabilization risks (10?<?SAR?<?18), and just 5% indicated high alkalinity hazards (SAR?>?26). Samples of water intended for irrigation showed a medium to high sodicity and alkalinization risk. It is expected that output may help in assessing the impacts of water quality of the Oued Rmel aquifer used for irrigation.     

The heat capacity of two natural chlorite group minerals derived from differential scanning calorimetry

The heat capacity of natural chamosite (X_Fe=0.889) and clinochlore (X_Fe=0.116) were measured by differential scanning calorimetry (DSC). The samples were characterised by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy. DSC measurements between 143 and 623?K were made following the procedure of Bosenick et?al. (1996). The fitted data for natural chamosite (CA) in J?mol^?1?K^?1 give: C _p,CA = 1224.3–10.685?×?10³?×?T ^??0.5???6.4389?× 10⁶?×T ^??2?+?8.0279?×?10⁸?×?T ^??3 and for the natural clinochlore (CE): C _p,CE = 1200.5–10.908?×?10³?×T ^??0.5?? 5.6941?×?10⁶?×?T ^??2?+?7.1166?×?10⁸?×?T ^??3. The corrected C _p-polynomial for pure end-member chamosite (Fe₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CAcor = 1248.3–11.116?× 10³?×?T ^??0.5???5.1623?×?10⁶?×?T ^??2?+?7.1867?×?10⁸×T ^??3 and the corrected C _p-polynomial for pure end-member clinochlore (Mg₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CEcor = 1191.3–10.665?×?10³?×?T ^??0.5???6.5136?×?10⁶?×?T ^??2?+ 7.7206?×?10⁸?×?T ^??3. The corrected C _p-polynomial for clinochlore is in excellent agreement with that in the internally consistent data sets of Berman (1988) and Holland and Powell (1998). The derived C _p-polynomial for chamosite (C _p,CAcor) leads to a 4.4% higher heat capacity, at 300?K, compared to that estimated by Holland and Powell (1998) based on a summation method. The corrected C _p-polynomial (C _p,CAcor) is, however, in excellent agreement with the computed C _p-polynomial given by Saccocia and Seyfried (1993), thus supporting the reliability of Berman and Brown's (1985) estimation method of heat capacities.