Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.     

Arsenic and antimony in geothermal waters of Yellowstone National Park,Wyoming, USA

A total of 268 thermal spring samples were analyzed for total soluble As using reduced molybdenum-blue; 27 of these samples were also analyzed for total Sb using flame atomic absorption spectrometry. At Yellowstone the $\text{Cl}\text{As}$ atomic ratio is nearly constant among neutral-alkaline springs with Cl > 100 mg L^?1, and within restricted geographic areas, indicating no differential effects of adiabatic vs. conductive cooling on arsenic. The $\text{Cl}\text{As}$ ratio increases with silica and decreases with decreasing $\text{Cl}\text{ΣCO}{}_3$; the latter relationship is best exemplified for springs along the extensively sampled SE-NW trend within the Lone Star-Upper-Midway Basin region. The relationship between $\text{Cl}\text{As}$ and $\text{Cl}\text{ΣCO}{}_3$ at Yellowstone suggests a possible rock leaching rather than magmatic origin for much of the Park's total As flux. Condensed vapor springs are low in both As and Cl. Very high $\text{Cl}\text{As}$ ratios ( > 1000) are associated exclusively with highly diluted (Cl < 100 mg L^?1) mixed springs in the Norris and Shoshone Basins and in the Upper White Creek and Firehole Lake areas of Lower Basin. The high ratios are associated with acidity and/or oxygen and iron; they indicate precipitation of As following massive dilution of the Asbearing high-Cl parent water.Yellowstone Sb ranged from 0.009 at Mammoth to 0.166 mg L^?1 at Joseph's Coat Spring. Within basins, the $\text{Cl}\text{Sb}$ ratio increases as the $\text{Cl}\text{ΣCO}{}_3$ ratio decreases, in marked contrast to As. Mixed springs also have elevated $\text{Cl}\text{Sb}$ ratios. White (1967) and Weissberg (1969) previously reported stibnite (Sb₂S₃), but not orpiment (As₂S₃), precipitating in the near surface zone of alkaline geothermal systems.     

Environmental impact of salmon net-pen culture on marine benthic communities in Maine: A case study

The environmental impacts of salmon net-pen aquaculture on the benthic environment were investigated at a commercial fish farm located in coastal Maine waters. This site has a sandy mud bottom and low current velocities, is subjected to episodic sediment resuspension, and way in production for 3 yr prior to this study: We examined both the increase in carbon flux to the benthos caused by the net-pen and the effects of the elevated flux on sediment biogeochemistry and the microbenthic communities. The experimental design involved the establishment of two study sites, an ambient site ca. 100 m from the net-pen and a treatment site around the pen. Sediment traps deployed 1 m above the sediment-water interface indicated that carbon flux to the benthos was increased 1-fold to 6-fold (to a maximum of 5 g m^?2d^?1) at the edge of the net-pen with little or no increase in carbon flux 10 m from the pen. Unlike carbon flux rates, sediment organic matter inventories showed a complex pattern of change over time. Mineral surface area, organic carbon and nitrogen, digestible protein, and sterol content were initially (April 1991) lower beneath the pen than in ambient sediments. During 1991 ambient sediment accumulated organic matter until July after which it decreased, to a low during November. In contrast, organic matter inventories of sediment beneath the pen remained low until July and then increased to a high during November. These latter gains were associated with the development of bacterial mats at the sediment-water interface. Beneath the pen, microbial and macrofaunal communities were shifted toward those commonly associated with organic enrichment but seasonal trends and storm-related resuspension events also significantly affected these sediment communities. When abundant, most epibenthic organisms were more numerous near the pen than in adjacent ambient areas. These results suggest that net-pen aquaculture can alter the benthic ecosystem in Maine Coastal waters but indicate that the effects are spatially limited.     

Freshwater reserves of mid-atlantic coast barrier Islands

A multiple regression model was constructed for the purpose of predicting barrier island hydrology from easily measureable island characteristics. The model was developed using data obtained from 17 sites on the Outer Banks of North Carolina. The accuracy of the model for predicting key hydrologic variables was evaluated by statistical and graphic procedures. In general, agreement between observed and predicted values of the hydrologic variables was very good, suggesting that the quantity of potable water at various island sites can be estimated without resorting to extensive field investigations. The model was then applied to Assateague Island, a barrier island located off the coasts of Maryland and Virginia. Results indicate that the original model developed for the Outer Banks may be applied to other barrier islands but that errors involved may necessitate corrections in detailed studies. Correction for bias in predictions for Assateague was shown to be possible with limited field data from surface resistivity surveys.     

Stenols and stanols in the oxic and anoxic waters of the Black Sea

Water samples collected from a slope station and two deep stations in the western basin of the Black Sea were analyzed for stenols and stanols by glass capillary gas chromatography. These results were used in conjuction with hydrographic, particulate organic carbon, and chlorophyll a data to better understand sterol sources and their transport and transformation mechanisms in anoxic basins.The total free sterol concentrations found in the surface waters were 450–500 ng/l dropping rapidly to values well below 100 ng/l at depths below the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the upper 200 m of the water column a strong association of sterols with particulate matter is suggested. Structural elucidation by a gas chromatograph-mass spectrometer-computer system revealed the presence of at least sixteen different stenols and stanols in the surface waters of the Black Sea. Cholesterol, 24-methylenecholesterol and 24-methylcholesta-5,22-dien-3β-ol were the major sterols in the surface waters. Cholesterol and 24-ethylcholesterol both exhibited a subsurface maximum at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the anoxic deep waters (200–2000 m) only cholesterol and 24-ethylcholesterol were found. Two stenols were found that have not been reported in seawater: a C₂₆ stenol with a saturated C₇H₁₅ side chain (presumably 24-norcholesterol) and 24-ketocholesterol. At least six 5α-stanols could be identified in the surface samples, each of them comprising about 10–20% of the concentration of the corresponding Δ5-stenol. From these comparatively high surface values the stanol concentrations drop rapidly to values near zero at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. Except for very low concentrations of 5α-cholestanol (< 4ng/l) no other stanols could be detected in the anoxic zone.From this data it appears that no detectable stenol → stanol conversion is occurring at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface or in the deep anoxic waters of the Black Sea.     

Petrogenesis of Archaean ultrabasic and basic volcanics: Evidence from rare earth elements

Rare earth element (REE) and major element data are presented on 44 Archaean samples which include spinifex textured ultramagnesian lavas (STPK) spinifex textured basalts (STB) and low MgO tholeiites. The samples come from the Yilgarn and Pilbara Blocks (W. Australia), Barberton (South Africa), Belingwe and Que Que (Rhodesia), Abitibi (Canada) and the 3.7 b.y. Isua Belt of Western Greenland. In addition REE data are given on three near primitive mid-ocean ridge basalts (MORB) and a glassy MORB-type basalt from Taiwan. We suggest that REE patterns, particularly the light REE and Eu, can be affected by metamorphism, but argue that the consistency of pattern from samples both within and between areas enables recognition of primary patterns. La/Sm ratios of 2.7 b.y. STPK are characterised by being lower than those of associated basalts. The 3.5 b.y. STPK Barberton material does not show this feature but instead displays significant heavy REE depletion. The separation of garnet from these liquids is suggested as a possible mechanism for the high CaO/Al₂O₃ ratios, (Al loss) and the heavy REE and Sc depletion. The REE data on Barberton material is equivocal on the derivation of the so-called basaltic komatiites from the peridotitic komatiites. However, REE analyses on STPK and high magnesian lavas from elsewhere suggests that crystal fractionation is not a viable mechanism to produce one from the other. We suggest instead, that varying amounts of partial melting of different sources is responsible for the spectrum of compositions. The STB appear to be an easily recognised rock type within the Archaean. They are characterised by quench (clinopyroxene) textures and a light REE enriched pattern. It is suggested that these are near primary melts and that their REE patterns mirror their mantle source. We propose a two stage model for the 2.7 b.y. mafic complexes, in which, prior to the generation of ultrabasic magmas, the source underwent a small amount of partial melting which resulted in the removal of a melt enriched in incompatible elements. The depletion process could be achieved either during mantle diapirism or by upward migration of interstitial melts into an Archaean low velocity zone. The spread of La/Sm ratios in STPK and STB is used as an argument that the Archaean mantle was chemically heterogeneous and that the degree of heterogeneity was similar to that observed in modern ocean volcanics. As a result, partial melting of the mantle under different P-T conditions produced a spectrum of magma types. The information presently available on Archaean mafic and silicic magmatism and the incompleteness of geochemical data on present day tectonic environments are two major obstacles in formulating Archaean tectonic models. In addition a comparison of present day and Archaean ultramafic and silicic rocks suggests that plate tectonic models as presently understood may not be suitable analogues for all Archaean tectonic environments.     

Geochemistry and hydrothermal alteration of the Kern Mountains plutonic complex,White Pine County,Nevada and Juab County,Utah

The Kern Mountains plutonic complex is composed of multiple intrusions referred as the Cove, Tungstonia and Hoodoo Canyon plutons, whose emplacement was structurally controlled. The plutons are members of the calc-alcaline granite series, leucogranite type that are relatively alkali rich. The complex is of epizone (4–10 km) and was emplaced during Jurassic time into the carbonates and quartzite of Paleozoic age. Trace and major element data indicate that the complex was derived from the partial melting of rocks similar to Canadian Shield rocks. Analysis of variance of chemical data suggets that hydrothermal solutions carried K₂O, Na₂O and SiO₂ and raised the levels of original oxides in the plutons. Hydrothermal activity is evidenced by the occurrence of second generation muscovite, potassium feldspar and quartz in the complex and tungsten and sulphide mineralization in the area.

---

Zusammenfassung Der plutonische Komplex des Kerngebirges besteht aus mehrfachen Instrusionen, genannt Cove-, Tungstonia- und Hoodoo Canyon-Pluton, deren Platznahme tektonisch kontrolliert wurde. Die plutonischen Gesteine gehören zu den Kalkalkaligraniten; sie sind leucogranitisch und damit ziemlich alkalireich. Der Komplex ist epizonal (4–10 km), er drang während des Jura in die Karbonate und Quarzite des Paläozoikums ein. Spuren- und Hauptelementmeßwerte zeigen an, daß der Komplex von aufgeschmolzenen Gesteinen abgeleitet werden kann, die den Gesteinen des Kanadischen Schildes ähneln. Die Analyse der Variation von chemischen Meßwerten deutet an, daß hydrothermale Lösungen K₂O, Na₂O und SiO₂ enthielten, die das Niveau der ursprünglichen Oxide in den plutonischen Gesteinen erhöhten. Die hydrothermale Tätigkeit wird durch das Vorhandensein von Muskowit, Kaliunifeldspat und Quartz der zweiten Generation innerhalb des Komplexes und durch Wolfram- und Sulfidmineralisation in der Umgebung bewiesen.

---

Résumé L'ensemble plutonique des montagnes de Kern, consiste en de nombreuses intrusions dénommées plutons du »Cove«, de »Tungstonia«, et du »Hoodoo Canyon« dont la mise en place a été tectoniquement controlée. Ces plutons font partie de la série granitique calco-alkaline; ce sont des leucogranites relativement riches en alcali. L'ensemble est épizonal (4–10 km), et s'est mis en place au cours du Jurassique dans des Calcaires et quartzites d'âge paléozoique. Les données analytiques relatives aux élements majeurs et en trace indiquent que cet ensemble peut provenir de la fusion partielle de roches similaires à celles du Bouclier Canadien.L'analyse de la variation des données chimiques suggère aussi que l'enrichissement de ces plutons en K₂O, Na₂O, et SiO₂ s'est fait à partir de solutions minéralisantes hydrothermales, comme en témoignent non seulement la présence d'une deuxième génération de muscovite, de feldspath potassique et de quartz, mais aussi par la mineralisation en tungstène et en minerais sulfurés à leur voisinage.

---

, Cove, Tungstonia Hoodoo Canyon, . - ; , , . (4–10 ); . - , , . , K₂O, Na₂O SiO₂, . , .

     

Fatty acids and Pb-210 geochronology of a sediment core from Buzzards Bay,Massachusetts

Four sections of a Pb-210 dated core of 62 cm length from Buzzards Bay, Massachusetts, were analyzed for fatty acids. A comparison of fatty acids extracted by Soxhlet extraction (unbound fatty acids) with fatty acids extracted by subsequent saponification extraction of the same sample (bound fatty acids) showed the former did not undergo diagenetic loss any faster than the latter. However, compositional differences between bound and unbound fatty acids were apparent in the top section of 1–2 cm and were less apparent in the 54–58 cm section. At least 14% of the bound fatty acids are esterified to non-solvent extractable material. The net conversion of fatty acids to other compounds is 32 μ/g dry weight sediment over the first 30 yr after deposition.     

Ice-core records of global climate and environment changes

Precipitation accumulating on the Greenland and Antarctic ice sheets records several key parameters (temperature, accumulation, composition of atmospheric gases and aerosols) of primary interest for documenting the past global environment over recent climatic cycles and the chemistry of the preindustrial atmosphere. Several deep ice cores from Antarctica and Greenland have been studied over the last fifteen years. In both hemispheres, temperature records (based on stable isotope measurements in water) show the succession of glacial and interglacial periods. However, detailed features of the climatic stages are not identical in Antarctica and in Greenland. A tight link between global climate and greenhouse gas concentrations was discovered, CO₂ and CH₄ concentrations being lower in glacial conditions by about 80 and 0.3 ppmv, respectively, with respect to their pre-industrial levels of 280 and 0.65 ppmv. Coldest stages are also characterized by higher sea-salt and crustal aerosol concentrations. In Greenland, contrary to Antarctica, ice-age ice is alkaline. Gas-derived aerosol (in particular, sulfate) concentrations are generally higher for glacial periods, but not similar in both the hemispheres. Marine and continental biomass-related species are significant in Antarctica and Greenland ice, respectively. Finally, the growing impact of anthropogenic activities on the atmospheric composition is well recorded in both polar regions for long-lived compounds (in particular greenhouse gases), but mostly in Greenland for short-lived pollutants.