Contamination of two Oregon reservoirs by cinnabar mining and mercury amalgamation

 Two reservoirs in western Oregon contain mercury-contaminated sediment and fish as a result of historic mercury mining in the Cottage Grove Lake watershed and mercury amalgamation used in gold mining in the Dorena Lake watershed. On average, sediment in Cottage Grove Lake contains ten times as much mercury as sediment from Dorena Lake (2.720 versus 0.242 ppm). Mercury content in Cottage Grove Lake sediment shows a sharp initial decrease and leveling off with time that reflects the end of the major cinnabar mining phase; deposition of other heavy metals appears to be linked to the clay content of sediment. Mercury input to Dorena Lake has remained fairly constant with time, but small increases in mercury are associated with the deposits of large floods. Copper, lead, and zinc input to Dorena Lake exhibits a marked decrease and leveling off related to the end of commercial mining for these metals. Received: 12 October 1999 · Accepted: 22 March 2000     

Early generation of 20S-5α(H),14α(H),17α(H)- and 5α(H),14β(H),17β(H)-steranes in low salinity lacustrine shales

A quantitative sterane biomarker study was conducted on a series of paralic freshwater lacustrine shale samples ranging in maturity from immature to near oil window maturity taken from Section 3 of the Shahejie Formation (Es3) in the Liaohe Basin, N.E. China. Concentrations of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes remain nearly constant throughout the sample suite. However, the decrease in the absolute concentrations of the 20R-5α(H),14α(H),17α(H)-C₂₉ steranes with increasing maturity results in an increase in the conventionally defined maturity parameters, 20S/(20S + 20R)-ααα and αββ/(ααα + αββ) sterane ratios. In addition, the data suggest that relatively early generation of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes has occurred in lacustrine sediments with a vitrinate reflectance 0.3% (R_o). The data provide strong support for the major importance of relative thermal stability of epimers, but do not exclude the possibility of isomerization as a viable mechanism for production.     

A groundwater isoscape (δD, δO) for Mexico

Numerous studies have shown that precipitation isocapes drive δD and δ¹⁸O patterns in surficial waters and in terrestrial food webs. While the GNIP (Global Network for Isotopes in Precipitation) dataset provided a key foundation for linking precipitation-terrestrial isoscapes globally, it has insufficient spatial coverage in many countries like Mexico. To overcome this limitation, we hypothesized that shallow phreatic groundwaters in Mexico could be used as an isotopic integrator of long-term seasonally weighted precipitation inputs to the landscape to aid in calibrating spatial H and O isotope datasets for terrestrial, biological and hydrological research. Groundwater was sampled from 234 sites in Mexico at ~ 50 km latitudinal spacing to obtain high spatial resolution and country-wide coverage for the construction of a groundwater isoscape. Our data revealed that shallow groundwater infiltration in Mexico appears largely unaffected by evaporation and reflects seasonally weighted precipitation inputs. These precipitation inputs are primarily biased to summertime when highest rainfall occurs, but a small degree of post-precipitation evaporation revealed a lower d-excess zone that corresponded to the interior semi-arid ecozone. We developed a predictive general linear model (GLM) for hydrogen and oxygen isotopic spatial patterns in Mexican groundwater and then compared the results to a validation subset of our field data, as well external data reported in the literature. The GLM used elevation, latitude, drainage basin (Atlantic vs. Pacific), and rainfall as the most relevant predictive variables. The GLM explained 81% of the overall isotopic variance observed in groundwater, 68% of the variance within our validation subset, and 77% of the variance in the external data set. Our predictive GLM is sufficiently accurate to allow for future ecological, hydrological and forensic isoscape applications in Mexico, and may be an approach that is applicable to other countries and regions where GNIP stations are lacking.     

α- and β-diversity Change of Late Ordovician Hirnantia Fauna of Changning, Sichuan, Southwest China

A continuous Ordovician-Silurian boundary section from the upper Wufeng Formation through the Kuanyinchiao Formation to the lower Lungmachi Formation has been carefully measured and collected at Shuanghe of Changning, southern Sichuan Province. For the first time, the temporal changes of α- and β-diversities of the Hirnantia fauna have been discussed in great detail. The general trend of brachiopod diversity change, increasing upward, is consistent with the regional trend of the Yangtze Platform, which had been controlled by both intrinsic and extrinsic factors. However, the sudden drop of diversity for a short period in the upper Kuanyinchiao Formation might have been controlled by environmental factors rather than normal faunal turnover. Synecological analysis using numerical methods recognizes two brachiopod-dominated associations of the Hirnantia fauna, the Dalmanella-Kinnella Association and the Mirorthis Association, both living in an offshore, deeper water environment corresponding to BA3-upper BA4, particularly lower BA3.     

Theoretical Prediction of Gibbs Free Energies of Formation for Crystalline α-MOOH and α-M2O3 Based on a Linear Free-Energy Relationship

In the present study, the modified Sverjensky–Molling equation, derived from a linear-free energy relationship, is used to predict the Gibbs free energies of formation of crystalline phases of α-MOOH (with a goethite structure) and α-M2O3 (with a hematite structure) from the known thermodynamic properties of the corresponding aqueous trivalent cations (M3+). The modified equation is expressed as ΔG0f,MVX=aMVXΔG0n,M3++bMVX+βMVXγM3+, where the coefficients aMVX, bMVX, and βMVX characterize a particular structural family of MvX (M is a trivalent cation [M3+] and X represents the remainder of the composition of solid); γ3+ is the ionic radius of trivalent cations (M3+); ΔG0f,MVX is the standard Gibbs free energy of formation of MvX; and ΔG0n,M3+ is the non-solvation energy of trivalent cations (M3+). By fitting the equation to the known experimental thermodynamic data, the coefficients for the goethite family (α-MOOH) are aMVX=0.8838, bMVX=?424.4431 (kcal/mol), and βMVX=115 (kcal/mol.?), while the coefficients for the hematite family (α-M2O3) are aMVX=1.7468, bMVX=?814.9573 (kcal/mol), and βMVX=278 (kcal/mol.?). The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases (i.e. phases that are thermodynamically unstable and do not occur at standard conditions) within the isostructural families of goethite (α-MOOH) and hematite (α-M2O3) if the standard Gibbs free energies of formation of the trivalent cations are known.     

Antarctic Ice‐Core Water (USGS49) – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice‐core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual‐inlet isotope‐ratio mass spectrometry. The δ²H and δ¹⁸O values of USGS49 are ?394.7 ± 0.4 and ?50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope‐ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.     

Thermodynamic stability of various alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers using molecular mechanics calculations

The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C₂₇, C₂₈, C₂₉, C₃₀ and C₃₁ families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C₂₇ compounds, Ts/Tm.     

Implementation of hierarchical single surface δ0 and δ1 models in finite element procedure

Hierarchical single surface (HISS) δ₀ and δ₁ models are briefly discussed. An algorithm for the implementation of δ₀ and δ₁ models in a finite element code and the associated subroutines, written in FORTRAN 77, are presented. The algorithm is general and can be adopted for other computer codes with minor changes. Detailed steps and subroutines are included for easy implementation of the models in specific codes. Two example problems are also presented to enable the user to verify the implementation.     

Surface and rheological properties of as-received colloidal goethite (α-FeOOH) suspensions: pH and polyethylenimine effects

The yield stress and zeta potential (ζ) of slurries prepared from as-received goethite were evaluated as a function of pH, solids concentration, cationic polyethylenimine (PEI) concentration and molecular weight (Mw). The goethite slurries displayed a maximum yield stress at the isoelectric point (pI). These slurries do not have a low pH dispersed region. The yield stress obeyed the yield stress–DLVO force model. The maximum yield stress displayed a dependence on the solids volume fraction to a power of 3.8.PEI adsorbed and changed both the surface chemistry and rheological yield stress of the slurries. At most additive concentration ranging from 0.1 to 0.4dwb% for PEI of Mw 600, 1800 and 70,000, the maximum yield stress of the slurries is larger than that with no adsorbed additives. At low PEI concentration of 0.1dwb%, the same maximum yield stress of 30 Pa was obtained for three Mws; 600, 1800 and 70,000 representing a 1.5-fold increase. The increased attraction between particles was attributed to charge patch attraction at low surface coverages and hydrogen bonding at high coverages. Adsorbed PEI decreased the yield stress at low pH. However complete dispersion was observed only for 0.4dwb% PEI with Mw 70,000, at pH below 7. Complete dispersion was not observed at high pH for the same polymer at all concentrations.     

The origin of chloritoid – 3‐mica pseudomorph growth in staurolite–muscovite schist,Bangriposi (Eastern India)

At Bangriposi, variable stages in replacement of staurolite by chloritoid – Na–K–Ca mica shimmer aggregates in muscovite schists provides insight into the complex interplay between fluid flow, mass transfer, and dissolution–precipitation during pseudomorph growth. Idioblastic chloritoid growing into mica caps without causing visible deformation, and monomineralic chloritoid veins (up to 300 μm wide) within shimmer aggregates replacing staurolite attest to chloritoid nucleation in fluid‐filled conduits along staurolite grain boundaries and crystallographic planes. The growth of shimmer aggregates initiated along staurolite margins, and advanced inwards into decomposing staurolite along networks of crystallographically controlled fluid‐filled conduits. Coalescence among alteration zones adjacent to channel fills led to dismemberment and the eventual demise of staurolite. Mass balance calculation within a volume‐fixed, silica‐conserved reference frame indicate the shimmer aggregates grew via precipitation from fluids in response to mass transport that led to the addition of H₂O, K₂O, Na₂O and CaO in the reaction zone, and Al₂O₃ was transported outward from the inward‐retreating margin of decomposing staurolite. This aided precipitation of chloritoid in veins and in the outer collars, and as disseminated grains in the shimmer aggregates at mid‐crustal condition (~520 ± 20 °C, 5.5 ± 2.0 kbar). Computation using one‐dimensional transport equation suggests that staurolite decomposition involved advection dominating over diffusive transport; the permeation of externally derived H₂O caused flattening of chemical potential gradients in H₂O and aqueous species, for example, and , computed using the Gibbs method. This suggests that staurolite decomposition was promoted by the infiltration of a large volume of H₂O that flattened existing chemical potential gradients. In the initial stages of replacement, chloritoid super‐saturation in fluid caused preferential nucleation and growth of chloritoid at staurolite grain boundaries and in crystallographic planes. As reaction progressed, further chloritoid nucleation was halted, but chloritoid continued to grow as the 3‐mica aggregates continued to replace the remaining staurolite in situ, while the chloritoid‐compatible elements were transported in the water‐rich phase facilitating continued growth of the existing chloritoid grains.     

Biomarker 18α(H)-oleanane: a geochemical tool to assess Venezuelan petroleum systems

This work describes the origin, applications and limitations of a specific biomarker: 18α(H)-oleanane, which is a paleoenvironmental, organic matter type and age indicator for the assessment of oil–oil and oil–source rock correlations. Specific cases in which this compound has been detected in oils and source rocks in the two main Venezuelan petroleum basins are presented in this work, along with scenarios for future research.     

The oxidative dissolution of arsenopyrite (FeAsS) and enargite (Cu3AsS4) by Leptospirillum ferrooxidans

Arsenopyrite (FeAsS) and enargite (Cu₃AsS₄) fractured in a nitrogen atmosphere were characterised after acidic (pH 1.8), oxidative dissolution in both the presence and absence of the acidophilic microorganism Leptospirillum ferrooxidans. Dissolution was monitored through analysis of the coexisting aqueous solution using inductively coupled plasma atomic emission spectroscopy and coupled ion chromatography-inductively coupled plasma mass spectrometry, and chemical changes at the mineral surface observed using X-ray photoelectron spectroscopy and environmental scanning electron microscopy (ESEM). Biologically mediated oxidation of arsenopyrite and enargite (2.5 g in 25 ml) was seen to proceed to a greater extent than abiotic oxidation, although arsenopyrite oxidation was significantly greater than enargite oxidation. These dissolution reactions were associated with the release of ∼917 and ∼180 ppm of arsenic into solution. The formation of Fe(III)-oxyhydroxides, ferric sulphate and arsenate was observed for arsenopyrite, thiosulphate and an unknown arsenic oxide for enargite. ESEM revealed an extensive coating of an extracellular polymeric substance associated with the L. ferrooxidans cells on the arsenopyrite surface and bacterial leach pits suggest a direct biological oxidation mechanism, although a combination of indirect and direct bioleaching cannot be ruled out. Although the relative oxidation rates of enargite were greater in the presence of L. ferrooxidans, cells were not in contact with the surface suggesting an indirect biological oxidation mechanism. Cells of L. ferrooxidans appear able to withstand several hundreds of ppm of As(III) and As(V).     

Mossbauer detection of goethite (α-FeOOH) in coal and its potential as an indicator of coal oxidation

Mössbauer spectroscopy of three suites of oxidized coals shows that the transformation of pyrite to FeOOH correlates with other parameters of oxidation. As pyrite is very common in coals and the transformation to FeOOH is sensitive to small degrees of oxidation, the Mössbauer technique shows considerable promise as a means for the detection of coal oxidation.     

The shift of the α-β transition temperature of quartz associated with the thermal expansion of granite at high pressure

Measurements are presented of volume changes in granite during room-temperature compression to 100, 200 and 300 MPa confining pressure followed by temperature increase to 900°C. Comparison with thermal expansion and compressibility data for the constituent minerals allows changes in porosity to be estimated. Under confining pressure, porosity is found to decrease with heating to 200°C through expansion of the minerals into cracks which are thought to be related to the geological cooling history of the rock. Between 200°C and 840°C porosity increases as a result of differential thermal expansion of the constituent minerals, but crack opening is increasingly suppressed at higher confining pressures. Extrapolation of the results indicates that differential thermal expansion can no longer cause crack opening in dry granite at confining pressures in excess of 450 MPa. The quartz α-β transition temperature in granite is marked by a kink in the thermal expansion curve of the rock, and it is found to increase by 60°C–70°C per 100 MPa confining pressure, as opposed to the published value of 26°C per 100 MPa for single crystals of quartz. Equations are presented which allow calculation of the effects of confining pressure and temperature on the stresses and displacements in and around a spherical inclusion embedded in a matrix of different elasticity and thermal expansion. The theory, together with a simple self-consistent model for granite, accounts semiquantitatively for the observations of thermal expansion and the effect of confining pressure thereon, and for the observed α-β transition temperatures for quartz in granite.     

USGS46 Greenland Ice Core Water – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ²H and δ¹⁸O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.     

An infrared and <Superscript>1</Superscript>H MAS NMR investigation of strong hydrogen bonding in ussingite,Na<Subscript>2</Subscript>AlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>(OH)

The mineral ussingite, Na₂AlSi₃O₈(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm^–1, and a possible OH librational bending mode at 1295 cm^–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the ¹H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and ¹H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and ¹H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.     

The Calcium Isotope Composition (δ44/40Ca) of NIST SRM 915b and NIST SRM 1486

The calcium isotopic composition of NIST SRM 915b and 1486 provided by the National Institute of Standards and Technology was analysed. The δ^44/40Ca values of the two reference materials relative to NIST SRM 915a were: NIST SRM 915b =+0.72 ± 0.04‰ and NIST SRM 1486 =?1.01 ± 0.02‰. NIST SRM 1486 did not require any chemical separation prior to measurement.     

Use of Pitzer Equations to Examine the Formation of Mercury(II) Hydroxide and Chloride Complexes in NaClO<Subscript>4</Subscript> Media

The thermodynamic stability constants for the hydrolysis and formation of mercury (Hg²⁺) chloride complexes

Late Holocene stable isotopic (δ13C and δ15N) records of lacustrine organic matter in Guangdong Province,south China,and their palaeoenvironmental implications

This study presents the results of TOC/TN (C/N) ratio, δ¹³C and δ¹⁵N analyses of lake sedimentary organic matter (OM) from the Hedong section, western Guangdong Province in south China, with the objective to reveal the history of hydrological and ecological variations in the region influenced by both the Indian summer monsoon (ISM) and East Asian summer monsoon (EASM). Variations in δ¹³C and δ¹⁵N of sedimentary OM may be closely related to past climatic conditions, which results in variations in surface runoff, lake level, allochthonous and autochthonous sources of OM, and lake productivity. Based on the interpretation of these proxies, four periods, i.e. 4370–4100, 3700–2900, 2400–2100 and 1900–900 cal. a BP, are characterized by low lake level, weakened surface runoff and deteriorated status of terrestrial and aquatic ecosystems, whereas the periods 4100–3700, 2900–2400, 2100–1900 and 900–600 cal. a BP are dominated by high lake level, strengthened surface runoff, and flourishing terrestrial and aquatic plants. A remarkable positive correlation between the δ¹³C values of the section and the ENSO number record obtained from the tropical Pacific implies that the impact of the ISM is greater than that of the EASM in the study area. The abnormal correspondence between the δ¹³C and solar activity reconstructed from ¹⁰Be and ¹⁴C records in GRIP ice‐core occurred from 1500–800 and particularly from 4200–4000 cal. a BP, suggesting that these two cool and dry intervals may be caused by stronger volcanic activities that are recorded in the GISP2 and Dome C ice‐cores. This study reveals that changes in solar insolation and solar activity, as well as changes in oceanic–atmospheric circulation (e.g. the ENSO intensity) and intensive volcano eruptions may have exerted influence on late Holocene climate variability in the study area.