Application of Geochemistry and VNIR Spectroscopy in Mapping Heavy Metal Pollution of Stream Sediments in the Takab Mining Area, NW of Iran

This study considered the possibility of using visible and near infrared (VNIR) spectral absorption feature parameters (SAFPs) in predicting the concentration and mapping the distribution of heavy metals in sediments of the Takab area. In total, 60 sediment samples were collected along main streams draining from the mining districts and tailing sites, in order to measure the concentration of As, Co, V, Cu, Cr, Ni, Hg, Ti, Pb and Zn and the reflectance spectra (350–2500 nm). The quantitative relationship between SAFPs (Depth500nm, R610/500nm, R1344/778nm, Area500nm, Depth2200nm, Area2200nm, Asym2200nm) and geochemical data were assessed using stepwise multiple linear regression (SMLR) and enter multiple linear regression (EMLR) methods. The results showed a strong negative correlation between Ni and Cr with Area2200nm, a significant positive correlation between As and Asym2200nm, Ni and Co with Depth2200nm, as well as Co, V and total values with Depth500nm. The EMLR method eventuated in a significant prediction result for Ni, Cr, Co and As concentrations based on spectral parameters, whereas the prediction for Zn, V and total value was relatively weak. The spatial distribution pattern of geochemical data showed that mining activities, along with the natural weathering of base metal occurrences and rock units, has caused high concentrations of heavy metals in sediments of the Sarough River tributaries.     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

The role of stratification in the deoxygenation of Mobile Bay and adjacent shelf bottom waters

Oxygen depletion in the shallow bottom waters of Mobile Bay, Alabama, and in adjacent nearshore and continental shelf waters, is shown to be directly related to the intensity of water column stratification. Low winds speeds are coincidental with the onset of water column stratification and the occurrence of hypoxic events. Hourly, daily, and seasonal changes in the relationship between percent oxygen saturation or oxygen concentration in the bottom waters and surface-bottom density differences indicate that the oxidized materials are recently formed, and not relic or overwintering carbon sources. The influence of density structure (water column stratification) in other oxygen-depleted coastal water masses is compared to Mobile Bay.     

Complex formation in the ternary system Mg(II)-CO2-H2O

The carbonato and hydrogencarbonato complexes of Mg²⁺ were investigated at 25 and 50° in solutions of the constant ClO₄^? molality (3 M) consisting preponderantly of NaClO₄. The experimental data could be explained assuming the following equilibria: Mg²⁺ + CO_2B + H₂O ag MgHCO⁺₃ + H⁺, $\text{log}{}^1\text{β}{}_1\text{= ?7.64}{}_4\text{± 0.01}{}_7\text{(25°), ?7.46}{}_2\text{± 0.01}{}_1\text{(50°)}$, Mg²⁺ + 2 CO_2g + 2 H₂Oag Mg(HCO₃)⁰₂ ± 2 H⁺, $\text{log}{}^1\text{β}{}_2\text{= ?15.00 ± 0.14 (25°)}$, ?15.37 ± 0.39 (50°), Mg²⁺ + CO_2g + H₂Oag MgCO⁰₃ + 2 H⁺, $\text{log}{}^1\text{k}{}_1\text{= ?15.64 ± 0.06 (25°)}$,?15.23 ± 0.02 (50°), with the assumption γ_MgCO3⁰ = γ_Mg(HCO3)⁰2, ΔG⁰(I = 0) for the reaction MgCO⁰₃ + CO_2g + H₂O = Mg(HCO₃)⁰₂ was estimated to be ?3.9₁ ± 0.8₆ and 0.6 ± 2.4 kJ/mol at 25 and 50°C, respectively. The abundance of carbonate linked Mg(II) species in fresh water systems is discussed.     

Filtering vibroseis data in the precorrelation domain

Vibroseis data recorded at short source–receiver offsets can be swamped by direct waves from the source. The signal-to-noise ratio, where primary reflections are the signal and correlation side lobes are the noise, decreases with time and late reflection events are overwhelmed. This leads to low seismic resolution on the vibroseis correlogram. A new precorrelation filtering approach is proposed to suppress correlation noise. It is the ‘squeeze-filter-unsqueeze’ (SFU) process, a combination of ‘squeeze’ and ‘unsqueeze’ (S and U) transformations, together with the application of either an optimum least-squares filter or a linear recursive notch filter. SFU processing provides excellent direct wave removal if the onset time of the direct wave is known precisely, but when the correlation recognition method used to search for the first arrival fails, the SFU filtering will also fail. If the tapers of the source sweeps are badly distorted, a harmonic distortion will be introduced into the SFU-filtered trace. SFU appears to be more suitable for low-noise vibroseis data, and more effective when we know the sweep tapers exactly. SFU requires uncorrelated data, and is thus cpu intensive, but since it is automatic, it is not labour intensive. With non-linear sweeps, there are two approaches to the S,U transformations in SFU. The first requires the non-linear analytical sweep formula, and the second is to search and pick the zero nodes on the recorded pilot trace and then carry out the S,U transformations directly without requiring the algorithm or formula by which the sweep was generated. The latter method is also valid for vibroseis data with a linear sweep. SFU may be applied to the removal of any undesired signal, as long as the exact onset time of the unwanted signal in the precorrelation domain is known or determinable.     

Solubilities of some hydrous REE phosphates with implications for diagenesis and sea water concentrations

Solubility product determinations suggest that the hydrous phosphates of the rare earths, REPO₄ · $\text{xH}{}_2\text{O}$, are important in controlling the sea water REE concentrations. Two of these solids, rhabdophane, (P6₂22) and “hydrous xenotime”, (14₁/amd), have been synthesized at 100°C via the acid hydrolysis of the respective REE pyrophosphate. The solubility products at infinite dilution were determined to be $\text{pK}{}^0\text{= 24.5}$, (La at 25°C); 26.0, (Pr at 100°C); 25.7, (Nd at 100°C): and 25.5, (Er at 100°C). On the basis of calculations involving the reaction of RE³⁺ with apatite to form the hydrous phosphate, the lanthanum concentration in sea water is predicted to be about 140 pmol/L. Laboratory experiments support the hypothesis that apatite is a substrate for reactions with dissolved REE.     

Growth patterns and implications of complex dendrites in calcite travertines from Lýsuhóll, Snæfellsnes, Iceland

Calcite dendrite crystals are important but poorly understood components of calcite travertine that forms around many hot springs. The Lýsuhóll hot-spring deposits, located in western Iceland, are formed primarily of siliceous sinters that were precipitated around numerous springs that are now inactive. Calcite travertine formed around the vent and on the discharge apron of one of the springs at the northern edge of the area. The travertine is formed largely of two types (I and II) of complex calcite dendrite crystals, up to 1 cm high, that grew through the gradual addition of trilete sub-crystals. The morphology of the dendrite crystals was controlled by flow direction and the competition for growth space with neighbouring crystals. Densely crowded dendrites with limited branching characterize the rimstone dams whereas widely spaced dendrites with open branching are found in the pools. Many dendrite bushes in the pools nucleated around plant stems. Growth of the dendrite crystals was seasonal and incremental. Calcite precipitation was driven by rapid CO₂ degassing of CO₂-rich spring waters during the spring and summer. During winter, when snow covered the ground and temperatures were low, opal-A precipitated on the exposed surfaces of the dendrites. Segmentation of dendrite branches by discontinuities coated with opal-A and overgrowth development around sub-crystals resulted from this seasonal growth cycle. The calcite dendrite crystals in the Lýsuhóll travertine differ in morphology from those at other hot springs, such as those at Lake Bogoria, Kenya, and Waikite in New Zealand. Comparison with the calcite dendrite crystals found at those sites shows that dendrite morphology is site-specific and probably controlled by carbonate saturation levels that, in turn, are controlled by the rate of CO₂ degassing and location in the spring outflow system.