Regional hydrogeochemical patterns in ground water of Northwestern Ohio and their relation to Mississippi valley—type mineral occurrences

A cluster of minor Mississippi Valley-type deposits occurs in northwestern Ohio. The district, which forms a northeasterly trending belt that cuts across the Findlay Arch, extends from the Indiana border to the Lake Erie Islands. The minerals of the deposits — chiefly celestite, fluorite and sphalerite with lesser amounts of barite and galena — show variation in both geographic and stratigraphic distribution. Dolomites of Middle Silurian to Middle Devonian age, which are the host rocks, also form an important aquifer system. The deposits are of interest because they might be indicators of economic mineralization at depth.Through a reconnaissance study, one-hundred ground-water samples from shallow wells (less than 50 m deep) were collected across an area of approximately 19 000 km². Recharge takes place in the southern part of the area while ground-water flow is northward towards Lake Erie. The majority of the samples are high in sulfate with the source being evaporites within the carbonate sequence. The remainder of the water samples are rich in bicarbonate. Trend surface maps for the major constituents indicate that the ground-water chemistry for the region is established chiefly by the lithology and the flow system. Trend surface maps for F⁻, Sr and Ba reflect the geographic distribution of the minerals in the deposits. Correlations are weakened, however, due to the influence of geochemical barriers such as SO₄²⁻ on Ba and Sr, and Ca on F⁻. The map for Pb follows the trends of the major constituents instead of the mineralization.In a detailed study across northwestern Sandusky County, which lies near the center of the district, 46 samples were collected in an area of 78 km². Trend surface maps for Ca, Mg, SO₄²⁻ and total dissolved solids reflect the chemistry of the bedrock and display concentrations that increase along the local flow path. Maps for F⁻, Sr and Ba correlate with mineralization in the vicinity, the first of these displaying a local trend and the last two correlating with regional trends.     

Gaseous and Particulate Oxidized and Reduced Nitrogen Species in the Atmospheric Boundary Layer in Scandinavia in Spring

Observations of the concentration of several nitrogen containing compounds at five rural Scandinavian sites during March–June 1993 are reported. Total nitrate (NO ₃ ^- + HNO₃) and total ammonium (NH ₄ ⁺ + NH₃) were measured by denuder and filter pack. In general the methods agree well. At all sites the particulate fraction dominated, with the largest fraction of NO ₃ ^- and the lowest of NH ₄ ⁺ at the sites which were closest to the emission sources. The fraction of NO ₃ ^- of total nitrate increased with increasing NO₂ concentrations, indicating that the nighttime conversion of NO₂ to NO ₃ ^- is an important route of formation for NO ₃ ^- . A positive correlation was found between HNO₃ and O₃ in June at all sites, while no correlation was found early in the spring. Model calculations were made with a lagrangian boundary layer photooxidant model for the whole period, and compared to the measured concentrations. The calculated ratio between mean observed and modelled daily maximum concentrations of ozone over the measurement period were within +/–10% at all sites. The models ability to describe the daily ozone maximum concentration was satisfactory with an average deviation of 19–22% from the observed concentrations. HNO₃ was underestimated by over 50% at all sites except the one closest to the emission sources. The correlation between modelled and observed concentrations was generally best for the sites with shortest transport distance from the sources of emission.     

Carbonyls and nonmethane hydrocarbons at rural European sites from the mediterranean to the arctic

Results of regular measurements during 1992–1995 of hydrocarbons and carbonyl compounds for a number of rural European monitoring sites are presented. The measurements are part of the EMEP programme for VOC measurements in Europe. In addition, several years of regular measurements are included from the Norwegian stations Birkenes at the south coast, and Zeppelin Mountain on Spitsbergen in the Arctic. The sampling frequency has been about twice per week throughout the years, implying that a substantial amount of measurement data are available. Almost all the chemical analyses have been performed by one laboratory, the EMEP Chemical Co-ordinating Centre located at NILU, which avoids problems of intercomparison and intercalibration among different laboratories. For the measured concentrations both seasonal and geographical variations are shown and discussed. The diurnal cycles of the hydrocarbon concentrations were studied in detail at one site, where the grab samples by EMEP where compared with a parallel continuous sampler, operated by EMPA, Switzerland. Hydrocarbons linked to natural gas and fuel evaporation become well mixed into the Arctic in the winter, whereas combustion products show a latitudinal gradient. The sum of oxygenated species constitutes about 5–15% of the sum of C₂–C₅ hydrocarbons in winter. In summer they are almost equal in magnitude, consistent with an increasing oxidation of hydrocarbons.     

Continental crust under the southern Porcupine Seabight west of Ireland

Two new seismic refraction/wide-angle reflection profiles demonstrate that the crust beneath the southern Porcupine Seabight, out to water depths in excess of 4000 m, is of continental type. They also reveal the rifted margin of the Porcupine basin on its eastern side. Crustal thickness under the Seabight, inclusive of sediments which are up to 6 km thick, decreases from 23 km in the east to about 10 km at a sharp continent-ocean transition in the west.     

Chemical processes and migration of elements during retrogression of a staurolite-zone assemblage in western North Carolina

A detailed study of retrograde alteration of a staurolite porphyroblast and its surrounding matrix of mica schist has made use of petrographic, modal, and microprobe analysis. Retrogression was to the garnet zone of metamorphism and apparently occurred largely after a temperature decline of 70–100° C. The event caused metasomatic removal of Zn but may have been isochemical relative to other analyzed elements. The best estimate of the overall reaction is: 1 staurolite+3.018 biotite+3.550 quartz+0.629 albite +0.014 anorthite+0.678 NaCl+14.004 H₂O =3.274 Na-rich muscovite+3.561 chlorite +0.273 ilmenite+0.110 chloritoid+0.039 garnet +0.339 ZnCl₂.Non-systematic variation in composition of analyzed minerals is revealed by statistical treatment of replicate analyses. Such variation involves monovalent and divalent cations within many minerals, but is most pronounced within retrograde muscovite. Muscovite variation involves Si and Al as well as FM and alkalis and does not follow a phengite law of charge-coupled substitution.Relative to the core of the retrograded staurolite crystal, zoning is seen in averaged muscovite compositions and in development of incompatible mineral assemblages, which include chloritoid well within retrograded staurolite but biotite within the matrix. A local gradient in the chemical potential of an Al-bearing component was likely present during retrogression.Alteration of staurolite was probably accomplished by reaction and diffusion through the medium of an intergranular fluid phase. Relative to staurolite, migration of elements involved immigration of considerable amounts of Mg, Na, K, and H and expulsion of Al, Fe, Zn, and O. It is inferred that concentration of Al within the fluid phase was considerably lower than those of monovalent and divalent cations.Preservation of considerable staurolite and evidence for a local concentration gradient of Al in the fluid phase suggest that limited amounts of H₂O were available. Expulsion of Zn suggests that much water was not consumed locally but exited the terrane. An attempt at resolution of this dilemna involves fracture-channelized infiltration of H₂O into the rock. A more regional petrographic study of retrogression suggests that H₂O which entered the rock may have been liberated initially by prograde dehydration at a moderately greater depth of 2–3 km.Results of this study, especially the non-phengitic nature of crystal-chemical substitution within muscovite, indicate chemical reaction under conditions of disequilibrium. Apparently, extent of retrogression was controlled by availability of H₂O rather than by thermochemical equilibria.     

Direct N-body modelling of stellar populations: blue stragglers in M67

We present a state-of-the-art N -body code which includes a detailed treatment of stellar and binary evolution as well as the cluster dynamics. This code is ideal for investigating all aspects relating to the evolution of star clusters and their stellar populations. It is applicable to open and globular clusters of any age. We use the N -body code to model the blue straggler population of the old open cluster M67. Preliminary calculations with our binary population synthesis code show that binary evolution alone cannot explain the observed numbers or properties of the blue stragglers. On the other hand, our N -body model of M67 generates the required number of blue stragglers and provides formation paths for all the various types found in M67. This demonstrates the effectiveness of the cluster environment in modifying the nature of the stars it contains, and highlights the importance of combining dynamics with stellar evolution. We also perform a series of N =10 000 simulations in order to quantify the rate of escape of stars from a cluster subject to the Galactic tidal field.     

Flow behaviour of the submarine glacigenic debris flows on the Bear Island Trough Mouth Fan, western Barents Sea

Using 3·5 kHz high-resolution seismic data, gravity cores and side-scan sonar imagery, the flow behaviour of submarine, glacigenic debris flows on the Bear Island Trough Mouth Fan, western Barents Sea was studied. During their downslope movement, the sediments within the uppermost part of the debris flows (<3 m) are inferred to have been deformed as a result of the shear stress at the debris–water interface. Thus, the uppermost part of the flow did not move downslope as a rigid plug. If present, a rigid part of the flow was located at least some metres below the surface. At c . 1000 to at least 1600 m water depth, the debris flows eroded and probably incorporated substrate debris. Further downslope, the debris flows moved passively over substrate sediments. The hypothesis of hydroplaning of the debris flow front may explain why the debris flows moved across the lower fan without affecting the underlying sediments. Detailed morphological information from the surface of one of the debris flow deposits reveals arcuate ridges. These features were probably formed by flow surge. Hydroplaning of the debris flow front may also explain the formation of flow surge. The long runout distance of some of the large debris flows could be due to accretion of material to the base of the debris flow, thereby increasing in volume during flow, and/or to hydroplaning suppressing deceleration of the flow.     

Nondestructive spectroscopic and petrochemical investigations of Paleoarchean spherule layers from the ICDP drill core BARB5, Barberton Mountain Land,South Africa

A Paleoarchean impact spherule‐bearing interval of the 763 m long International Continental Scientific Drilling Program (ICDP) drill core BARB5 from the lower Mapepe Formation of the Fig Tree Group, Barberton Mountain Land (South Africa) was investigated using nondestructive analytical techniques. The results of visual observation, infrared (IR) spectroscopic imaging, and micro‐X‐ray fluorescence (μXRF) of drill cores are presented. Petrographic and sedimentary features, as well as major and trace element compositions of lithologies from the micrometer to kilometer‐scale, assisted in the localization and characterization of eight spherule‐bearing intervals between 512.6 and 510.5 m depth. The spherule layers occur in a strongly deformed section between 517 and 503 m, and the rocks in the core above and below are clearly less disturbed. The μXRF element maps show that spherule layers have similar petrographic and geochemical characteristics but differences in (1) sorting of two types of spherules and (2) occurrence of primary minerals (Ni‐Cr spinel and zircon). We favor a single impact scenario followed by postimpact reworking, and subsequent alteration. The spherule layers are Al₂O₃‐rich and can be distinguished from the Al₂O₃‐poor marine sediments by distinct Al‐OH absorption features in the short wave infrared (SWIR) region of the electromagnetic spectrum. Infrared images can cover tens to hundreds of square meters of lithologies and, thus, may be used to search for Al‐OH‐rich spherule layers in Al₂O₃‐poor sediments, such as Eoarchean metasediments, where the textural characteristics of the spherule layers are obscured by metamorphism.     

A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism and degassing of Devonian evaporites in the Norilsk aureoles, Siberia

Devonian evaporites and associated sedimentary rocks in the Norilsk region were contact metamorphosed during emplacement of mafic sills that form part of the end-Permian (~252 Ma) Siberian Traps. We present mineralogical, geochemical and Sr–Nd isotopic data on sedimentary rocks unaffected by metamorphism, and meta-sedimentary rocks from selected contact aureoles at Norilsk, to examine the mechanisms responsible for magma-evaporite interaction and its relation to the end-Permian environmental crisis. The sedimentary rocks include massive anhydrite, rock salt, dolostone, calcareous siltstones and shale, and the meta-sedimentary rocks comprise calcareous hornfels, siliceous hornfels and minor meta-anhydrite and meta-sandstone. Contact metamorphism took place at low pressure and at maximum temperatures corresponding to the phlogopite-diopside stability field. Calcareous hornfels have high CaO, MgO, CΟ₂, SΟ₃, low SiO₂ and initial Sr isotopic ratios of 0.7079–0.7092, features indicative of calcareous siltstone protoliths. Siliceous hornfels, in contrast, have high SiO₂, Al₂O₃, Na₂O, low in other major element oxides and initial Sr isotopic ratios of 0.7083–0.7152, consistent with pelitic or shaley protoliths. Loss of CO₂ in a subset of calcareous hornfels can be explained by decarbonation reactions during metamorphism, but release of SO₂ from evaporites cannot be accounted for by a similar mechanism. Occurrences of wollastonite and a variety of hydrous minerals in the calcareous hornfels are consistent with equilibration with hydrous fluid, which was capable of leaching large quantities of anhydrite in the presence of dissolved NaCl. In this way, substantial sediment-derived sulfur could have been mobilized, incorporated into the magmatic system and released to the atmosphere. The release of CO₂ and SO₂ from Siberian evaporites added to the variety of toxic gases generated during metamorphism of organic matter, coal and rock salt, contributing to the end-Permian environmental crisis.