Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.     

Climatic change and quasi-oscillations in central-west Argentina summer precipitation: main features and coherent behaviour with southern African region

Summer rainfall variability (October to March) shows inter-annual to multi-decadal fluctuations over a vast area of subtropical Argentina between 28°S–38°S and 65°W–70°W. Statistically significant oscillations of quasi-period in the bands of 18–21, 6, 4 and 2 years can be found throughout the region and intra-regionally, though the latter are variable. The lower frequency variation produces alternating episodes of above and below normal rainfall each lasting roughly 9 years. This quasi-fluctuation appears to be shared with the summer rainfall region of South Africa and were in-phase related one another until mid-1970s. The teleconnection between both subtropical regions could be generated by an atmospheric-oceanic bridge through the global sea surface temperatures (SSTs), particularly those of the equatorial-tropical South Atlantic. From mid-1970s, the alternating wet and dry pattern has been interrupted in the Argentine region producing the longest, as yet unfinished, wet spell of the century. Thus, a significant change of the long-term variation was observed around 1977 toward lower frequencies. Since then the statistical model that explains more than 89% of the variance of the series until 1977, diverges from the observed values in the 1980s and 1990s. In addition the Yamamoto statistical index, employed to detect a climatic jump, reaches its major value in 1973 at the beginning of the current long wet spell. Therefore the change could be located between 1973 and 1977. Application of the t-student's test gives significant differences of mean values for pre-1977 and post-1977 sub-samples from both individual time series and the regional index series. The spectral analysis also shows changes in energy bands in concordance with the features of the change that occurred from mid-1970s. The change gives rise to a significant increment of more than 20% in average of normal rainfall over the region. Conversely, a drought between mid-1980s and the 1990s has been observed in the South African counterpart with severe characteristics, thereby continuing the quasi-18-year oscillation. Consequently, the low-frequency coherent behaviour between both the Argentine and South African regions is lost from the mid-1970s. The analysis of association of wet/dry spells and warm/cold, El Niño/La Niña episodes appears to be not significant at scales of year-to-year variability although at decadal to multi-decadal scales the association could be relevant. More than one process of multi-decadal variability of global SSTs could influence the Argentine summer rainfall region and the former bi-decadal teleconnection. Finally, potential hypothetical factors of change are discussed, such as the strengthening of direct and indirect mechanisms of moisture flux transport associated with global warming, low-level atmospheric circulation changes and/or to SSTs mean condition long-term variations over tropical and subtropical South Atlantic and South Pacific oceans.     

Rapid evolution of redox processes in a petroleum hydrocarbon-contaminated aquifer

Ground water chemistry data collected over a six-year period show that the distribution of contaminants and redox processes in a shallow petroleum hydrocarbon-contaminated aquifer has changed rapidly over time. Shortly after a gasoline release occurred in 1990, high concentrations of benzene were present near the contaminant source area. In this contaminated zone, dissolved oxygen in ground water was depleted, and by 1994 Fe(III) reduction and sulfate reduction were the predominant terminal electron accepting processes. Significantly, dissolved methane was below measurable levels in 1994, indicating the absence of significant methanogenesis. By 1996, however, depletion of solid-phase Fe(III)-oxyhydrox ides in aquifer sediments and depletion of dissolved sulfate in ground water resulted in the onset of methanogenesis. Between 1996 and 2000, water-chemistry data indicated that methanogenic metabolism became increasingly prevalent. Molecular analysis of 16S-rDNA extracted from sediments shows the presence of a more diverse methanogenic community inside as opposed to outside the plume core, and is consistent with water-chemistry data indicating a shift toward methanogenesis over time. This rapid evolution of redox processes reflects several factors including the large amounts of contaminants, relatively rapid ground water flow (approximately 0.3 m/day [approximately foot/day]), and low concentrations of microbially reducible Fe(III) oxyhydroxides ( approximately 1 micromol/g) initially present in aquifer sediments. These results illustrate that, under certain hydrologic conditions, redox conditions in petroleum hydrocarbon-contaminated aquifers can change rapidly in time and space, and that the availability of solid-phase Fe(III)-oxyhydroxides affects this rate of change.     

Challenges and strategies for better use of scientific information in the management of coastal estuaries

Numerous studies have concluded that better use of scientific information could improve the quality of coastal and estuarine environmental management. Approaches for effecting such a change include ecosystem-based, integrated, and adaptive management, but such basic re-orientation of estuarine and coastal management has proved difficult to achieve. Even environmental indicators, seemingly straightforward ways of injecting scientific information into decision making, have achieved broad on-the-ground use in relatively few instances—principally the largest estuary management programs. A conceptual framework useful for examining environmental management systems affecting the five PNCERS (Pacific Northwest coastal Ecosystems Regional Study) estuaries conceives of environmental managers, researchers, and interested and affected parties in the public as interacting through the multi-layered institutional arrangements that currently promote the utilization, management, or protection of coastal and estuarine resources. Considerable variation exists in the approach and effectiveness of the region's environmental management organizations. Interaction between science and management in the region appears to be limited to an extent by high transaction costs; a cultural divide between environmental scientists and environmental managers is perceived by members of both groups who work with the PNCERS estuaries as inhibiting communications between them. Mechanisms that both groups identify as useful for improving the flow of information between science and management are little used, perhaps as a result. The two groups have very different patterns of information dissemination and acquisition, and though both chose agency archives and databases as their top methods for disseminating information, neither group relies much on these vehicles for information they seek. Both residents' and practitioners' perceptions of threats to the PNCERS estuaries show patterns of estuary-to-estuary variation. One theme that emerges is that problems associated with poor land management in adjacent uplands are common to most of these estuaries, potentially providing a sense of commonality through which a more regional approach to estuary management could emerge. A common set of estuarine environmental indicators implemented for all estuaries could help instigate such a regional approach, but resource constraints, especially at the local level, will have to be overcome for that to occur. There is currently substantial lack of common vision among coastal practitioners as to the purpose and desirability of indicators, and relatively little experience or knowledge of their use, particularly at the local level. Use of estuarine science in the management of these estuaries appears to be greatest during periods in which the largest programmatic shifts in environmental management approaches occur, an observation consistent with other studies that have concluded that the use of environmental science in environmental management tends to be episodic.     

Spatial and temporal variability in the stable isotope systematics of modern precipitation in China: implications for paleoclimate reconstructions

The stable isotopic composition of materials such as glacial ice, tree rings, lake sediments, and speleothems from low-to-mid latitudes contains information about past changes in temperature (T) and precipitation amount (P). However, the transfer functions which link δ¹⁸O_p to changes in T or P, dδ¹⁸O_p/dT and dδ¹⁸O_p/dP, can exhibit significant temporal and spatial variability in these regions. In areas affected by the Southeast Asian monsoon, past variations in δ¹⁸O and δD of precipitation have been attributed to variations in monsoon intensity, storm tracks, and/or variations in temperature. Proper interpretation of past δ¹⁸O_p variations here requires an understanding of these complicated stable isotope systematics. Since temperature and precipitation are positively correlated in China and have opposite effects on δ¹⁸O_p, it is necessary to determine which of these effects is dominant for a specific region in order to perform even qualitative paleoclimate reconstructions. Here, we evaluate the value of the transfer functions in modern precipitation to more accurately interpret the paleorecord. The strength of these transfer functions in China is investigated using multiple regression analysis of data from 10 sites within the Global Network for Isotopes in Precipitation (GNIP). δ¹⁸O_p is modeled as a function of both temperature and precipitation. The magnitude and signs of the transfer functions at any given site are closely related to the degree of summer monsoon influence. δ¹⁸O_p values at sites with intense summer monsoon precipitation are more dependent on the amount of precipitation than on temperature, and therefore exhibit more negative values in the summer. In contrast, δ¹⁸O_p values at sites that are unaffected by summer monsoon precipitation exhibit strong relationships between δ¹⁸O_p and temperature. The sites that are near the northern limit of the summer monsoon exhibit dependence on both temperature and amount of precipitation. Comparison with simple linear models (δ¹⁸O_p as a function of T or P) and a geographic model (δ¹⁸O_p as a function of latitude and altitude) shows that the multiple regression model is more successful at reproducing δ¹⁸O_p values at sites that are strongly influenced by the summer monsoon. The fact that the transfer function values are highly spatially variable and closely related to the degree of summer monsoon influence suggests that these values may also vary temporally. Since the Southeast Asian monsoon intensity is known to exhibit large variations on a number of timescales (annual to glacial–interglacial), and the magnitude and sign of the transfer functions is related to monsoon intensity, we suggest that as monsoon intensity changes, the magnitude and possibly even the sign of the transfer functions may vary. Therefore, quantitative paleoclimate reconstructions based on δ¹⁸O_p variations may not be valid.     

Holocene Climate in the Northern Great Plains Inferred from Sediment Stratigraphy, Stable Isotopes, Carbonate Geochemistry, Diatoms, and Pollen at Moon Lake, North Dakota

Seismic stratigraphy, sedimentary facies, pollen stratigraphy, diatom-inferred salinity, stable isotope (δ¹⁸O and δ¹³C), and chemical composition (Sr/Ca and Mg/Ca) of authigenic carbonates from Moon Lake cores provide a congruent Holocene record of effective moisture for the eastern Northern Great Plains. Between 11,700 and 9500¹⁴C yr B.P., the climate was cool and moist. A gradual decrease in effective moisture occurred between 9500 and 7100¹⁴C yr B.P. A change at about 7100¹⁴C yr B.P. inaugurated the most arid period during the Holocene. Between 7100 and 4000¹⁴C yr B.P., three arid phases occurred at 6600–6200¹⁴C yr B.P., 5400–5200¹⁴C yr B.P., and 4800–4600¹⁴C yr B.P. Effective moisture generally increased after 4000¹⁴C yr B.P., but periods of low effective moisture occurred between 2900–2800¹⁴C yr B.P. and 1200–800¹⁴C yr B.P. The data also suggest high climatic variability during the last few centuries. Despite the overall congruence, the biological (diatom), sedimentological, isotopic, and chemical proxies were occassionally out of phase. At these times the evaporative process was not the only control of lake-water chemical and isotopic composition.     

Paper 1. the mink methodology: background and baseline

A four step methodology has been developed for study of the regional impacts of climate change and the possible responses thereto. First the region's climate sensitive sectors and total economy are described (Task A, current baseline). Next a scenario of climate change is imposed on the current baseline (Task B, current baseline with climate change). A new baseline describing the climate sensitive sectors and total regional economy is projected for some time in the future (Task C, future baseline, year 2030) in the absence of climate change. Finally, the climate change scenario is reimposed on the future baseline (Task D, future baseline with climate change). Impacts of the climate change scenario on the current and future regional economies are determined by means of simulation models and other appropriate techniques. These techniques are also used to assess the impacts of an elevated CO₂ concentration (450 ppm) and of various forms of adjustments and adaptations. The region chosen for the first test of the methodology is composed of the four U.S. states of Missouri, Iowa, Nebraska and Kansas. The climate change scenario is the actual weather of the 1930s decade in the MINK region. ‘Current’ climate is the actual weather of the period 1951–1980.     

Sheet silicates of the Lawler Peak granite,Arizona: chemistry,structural variations,and exsolution

Coarse-grained muscovite, biotite, and chlorite from the Lawler Peak granite, Yavapai County, Arizona, have been studied with electron microprobe analysis, powder X-ray diffraction, transmission electron microscopy (TEM), electron diffraction, and analytical TEM methods. All three sheet silicates exhibit multiple polytypes and an abundance of stacking faults and dislocations. Chlorite formed by subsolidus replacement of biotite. Muscovite also may have formed by replacement of biotite and other minerals, but there is no clear microstructural evidence to support either a primary or secondary origin for the coarse-grained muscovite. X-ray and electron diffraction reveal that the muscovite consists of two separate phases, which give rise to splitting of diffraction maxima. TEM experiments suggest that the two components resulted from exsolution, which produced two symmetry-related sets of irrationally oriented lamellae with a wavelength averaging about 10 nm. Exsolution occurred in both 1M and 2M₁ muscovite. Although the lamellae are too small to analyze directly, the muscovite bulk composition and structural data are consistent with the separation of celadonitic and muscovite components.     

Distribution and characterization of luminescent bacteria in a temperate estuary

The effect of temperature and salinity on numbers of luminescent bacteria present in waters of the Mystic (Conn.) River estuary was evaluated. Counts decreased with decreasing salinity; none were detected at freshwater stations. A population maximum of 35 per ml was noted at the highest salinity station (30±2‰). Highest counts were observed during winter and spring and lowest numbers occurred during summer and fall months. Isolates (111) were identified and compared with previously-described luminescent bacteria; i.e.,Beneckea (Vibrio) harveyi, Photobacterium (V.) fischeri, P. phosphoreum, andP. leiognathi. All species were isolated but distinct seasonal differences were noted.P. (V.) fischeri andB. (V.) harveyi represented 93% of the luminous population on an annual basis. Only the former was found during the period December through March (highest count 7 per ml) whileB. (V.) harveyi was the dominant species noted between May and October (maximum count 11 per ml).P. leiognathi andP. phosphoreum were found only during July and August as 7% of the total luminous population. All isolates grew at NaCl concentrations between 6 and 30‰; none grew below 6‰