Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts

Configurational changes with temperature are important for the thermodynamic and transport properties of most aluminosilicate melts, but in general are not well understood. Here, we present high-resolution ²⁷Al and ¹⁷O NMR data on several calcium aluminosilicate glasses prepared with varying quench rates and thus with fictive temperatures that span ranges up to about 200 K. In all compositions the content of five-coordinated aluminum increases with fictive temperature, in agreement with recent high temperature NMR data on melts. In a glass of CaAl₂Si₂O₈ (“anorthite”) composition, the content of non-bridging oxygens also increases with temperature; however this effect was not observed in a sample with a much higher CaO/Al₂O₃ ratio. We present a consistent notation for reactions among structural species in these systems that clarify why in some cases, high-coordinated network cations may appear on the same side of the reaction, while in others they occur on the opposite sides: the key difference is in accounting for all coordination changes for oxygens. Mixing of non-bridging oxygens and of high-coordinated aluminum make significant contributions to the overall configurational entropy and heat capacity of the melts, as does the mixing of various bridging oxygens and of tetrahedral network cations. Other, less well known, types of increase in disorder with temperature may be important as well.     

Stability of outer planetary orbits around binary stars: A comparison of Hill's and Laplace's stability criteria

A comparison is made between the stability criteria of Hill and that of Laplace to determine the stability of outer planetary orbits encircling binary stars. The restricted, analytically determined results of Hill's method by Szebehely and co-workers and the general, numerically integrated results of Laplace's method by Graziani and Black are compared for varying values of the mass parameter =m ₂/(m ₁+m ₂). For 00.15, the closest orbit (lower limit of radius) an outer planet in a binary system can have and still remain stable is determined by Hill's stability criterion. For >0.15, the critical radius is determined by Laplace's stability criterion. It appears that the Graziani-Black stability criterion describes the critical orbit within a few percent for all values of .     

An experimental study of magnesium-isotope fractionation in chlorophyll-a photosynthesis

Measurements are presented of the magnesium isotopic composition of chlorophyll-a, extracted from cyanobacteria, relative to the isotopic composition of the culture medium in which the cyanobacteria were grown. Yields of 50-93% chlorophyll-a were achieved from the pigment extracts of Synechococcus elongatus, a unicellular cyanobacteria. This material was then digested using concentrated nitric acid to extract magnesium. Separation was accomplished using columns of cation-exchange resin, which achieved a 103 ± 10% yield of magnesium from chlorophyll-a. This procedure ensured accurate measurement of the magnesium-isotopic ratios without isobaric interferences using a multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We find a slight depletion in the heavier isotopes of magnesium in chlorophyll-a relative to culture medium, early growth phase: Δ²⁶Mg = −0.71(±0.35)‰ and Δ²⁵Mg = −0.37(±0.18)‰; late growth phase: Δ²⁶Mg = −0.53(±0.20)‰ and Δ²⁵Mg = −0.26(±0.11)‰, due to an apparent mass-dependent fractionation. We suggest that the small fractionation results from chelation during intracellular processes. A likely candidate for this chelation step involves the magnesium-chelatase enzyme, which mediates the insertion of magnesium to the tetrapyrrole ring during chlorophyll-a biosynthesis. Proof of this hypothesis can be tested with biological controls whereby steps in the enzymatic pathways of chlorophyll synthesis are selectively suppressed.     

Validation of a fish farm waste resuspension model by use of a particulate tracer discharged from a point source in a coastal environment

To validate a resuspension model of particulate material (salmonid farm wastes), a UV fluorescent particle tracer was selected with similar settling characteristics. Tracer was introduced to the seabed (water depth ≈30 m) and sediment samples taken on days 0, 3, 10, 17 and 30 to measure the horizontal and vertical distribution of tracer in sediments. A concentric sampling grid was established at radii of 25, 50, 100, 150, 200, 400, 700 and 1, 000 m from the source on transects 30° apart. The bulk of the deployed tracer was initially concentrated in an area 25 m radius from the release point; tracer was observed to steadily decrease to zero over a period of 30 days. In a 200 m region measured from the release point in the direction of the residual current, the redeposition of tracer was low. A Lagrangian particle tracking model was validated using these observed data by varying resuspension model parameters within limits to obtain the best agreement between spatial and temporal distributions. The validated model generally gave good predictions of total mass budgets (±7% of total tracer released), particulary where tracer concentrations were high near the release point. Best fit model parameters (critical erosion shear stress=0.018 N m⁻², erodibility constan=60 g m⁻² d⁻¹) are at the low end of reported parameters for coastal resuspension models. Such a low critical erosion shear stress indicates that the frequency of resuspension and deposition events for freshly deposited material is high.     

Estimates of lichen growth–rate in northern Sweden

Two lichenometric techniques were compared in a study of lichen growth–rate in northern Sweden. The first technique, based on the maximum lichen diameter on glacier moraines, was identical to the technique used in the 1970s, whereas the other utilized the lichen diameter measured on 100 randomly selected boulders. The results indicate that it does not matter which technique is chosen, as long as the technique is used consistently on both the calibration surfaces and the surfaces to be dated. The use of data from both the 1970s and the 2000s increased the number of calibration surfaces available. The new calibration curve indicates that the age of Little Ice Age moraines was underestimated by up to about 30 years in the study conducted in the 1970s.     

Calcrete profile development in Quaternary alluvial sequences,southeast Spain: implications for using calcretes as a basis for landform chronologies

A detailed study of the morphology and micro‐morphology of Quaternary alluvial calcrete profiles from the Sorbas Basin shows that calcretes may be morphologically simple or complex. The ‘simple’ profiles reflect pedogenesis occurring after alluvial terrace formation and consist of a single pedogenic horizon near the land surface. The ‘complex’ profiles reflect the occurrence of multiple calcrete events during terrace sediment aggradation and further periods of pedogenesis after terrace formation. These ‘complex’ calcrete profiles are consequently described as composite profiles. The exact morphology of the composite profiles depends upon: (1) the number of calcrete‐forming events occurring during terrace sediment aggradation; (2) the amount of sediment accretion that occurs between each period of calcrete formation; and (3) the degree of pedogenesis after terrace formation. Simple calcrete profiles are most useful in establishing landform chronologies because they represent a single phase of pedogenesis after terrace formation. Composite profiles are more problematic. Pedogenic calcretes that form within them may inherit carbonate from calcrete horizons occurring lower down in the terrace sediments. In addition erosion may lead to the exhumation of older calcretes within the terrace sediment. Calcrete ‘inheritance’ may make pedogenic horizons appear more mature than they actually are and produce horizons containing carbonate embracing a range of ages. Calcrete exhumation exposes calcrete horizons whose morphology and radiometric ages are wholly unrelated to terrace surface age. Composite profiles are, therefore, only suitable for chronological studies if the pedogenic horizon capping the terrace sequence can be clearly distinguished from earlier calcrete‐forming events. Thus, a detailed morphological/micro‐morphological study is required before any chronological study is undertaken. This is the only way to establish whether particular calcrete profiles are suitable for dating purposes. Copyright © 2003 John Wiley & Sons, Ltd.     

Observation of gravity waves in a boreal forest

In this paper we report the results of the analysis of two 60-min wave events that occurred in a boreal aspen forest during the 1994 BOREAS (Boreal Ecosystems-Atmosphere Study) field experiment. High frequency wind and temperature data were provided by three 3-D sonic anemometer/thermometers and fourteen fine-wire thermocouples positioned within and above the forest. Wave phase speeds, estimated from information revealed by spectral analysis and linear plane wave equations, are 2.2 and 1.3 m s^-1 for the two events. The wavelengths are 130 m and 65 m respectively and are much larger than the vertical wave displacements. There is strong evidence from the present analysis and from the literature supporting our postulate that these waves are generated by shear instability. We propose that wind shear near the top of the stand is often large enough to reduce the gradient Richardson number below the critical value of 0.25 and thus is able to trigger the instability. When external conditions are favorable, the instability will grow into waves.     

Metamorphism and metamorphic K–Ar ages of the Mesozoic accretionary complex in Northland, New Zealand

Abstract A southwest dipping Mesozoic accretionary complex, which consists of tectonically imbricated turbiditic mudstone and sandstone, hemipelagic siliceous mudstone, and bedded cherts and basaltic rocks of pelagic origin, is exposed in northern North Island, New Zealand. Interpillow limestone is sometimes contained in the basaltic rocks. The grade of subduction‐related metamorphism increases from northeast to southwest, indicating an inverted metamorphic gradient dip. Three metamorphic facies are recognized largely on the basis of mineral parageneses in sedimentary and basaltic rocks: zeolite, prehnite‐pumpellyite and pumpellyite‐actinolite. From the apparent interplanar spacing d₀₀₂ data for carbonaceous material, which range from 3.642 to 3.564 Å, the highest grade of metamorphism is considered to have attained only the lowermost grade of the pumpellyite‐actinolite facies for which the highest temperature may be approximately 300°C. Metamorphic white mica K–Ar ages are reported for magnetic separates and <2 µm hydraulic elutriation separates from 27 pelitic and semipelitic samples. The age data obtained from elutriation separates are approximately 8 m.y. younger, on average, than those from magnetic separates. The age difference is attributed to the possible admixture of nonequilibrated detrital white mica in the magnetic separates, and the age of the elutriation separates is considered to be the age of metamorphism. If the concept, based on fossil evidence, of the subdivision of the Northland accretionary complex into north and south units is accepted, then the peak age of metamorphism in the north unit is likely to be 180–130 Ma; that is, earliest Middle Jurassic to early Early Cretaceous, whereas that in the south unit is 150–130 Ma; that is, late Late Jurassic to early Early Cretaceous. The age cluster for the north unit correlates with that of the Chrystalls Beach–Taieri Mouth section (uncertain terrane), while the age cluster for the south unit is older than that of the Younger Torlesse Subterrane in the Wellington area, and may be comparable with that of the Nelson and Marlborough areas (Caples and Waipapa terranes).     

Characterizing and classifying urban watersheds with compositional and structural attributes

Current land-use classifications used to assess urbanization effects on stream water quality date back to the 1980s when limited information was available to characterize watershed attributes that mediate non-point source pollution. With high resolution remote sensing and widely used GIS tools, there has been a vast increase in the availability and precision of geospatial data of built environments. In this study, we leverage geospatial data to expand the characterization of developed landscapes and create a typology that allows us to better understand the impact of complex developed landscapes across the rural to urban gradient. We assess the ability of the developed landscape typology to reveal patterns in stream water chemistry previously undetected by traditional land-cover based classification. We examine the distribution of land-cover, infrastructure, topography and geology across 3876 National Hydrography Dataset Plus catchments in the Piedmont region of North Carolina, USA. From this dataset, we generate metrics to evaluate the abundance, density and position of landscape features relative to streams, catchment outlets and topographic wetness metrics. While impervious surfaces are a key distinguishing feature of the urban landscape, sanitary infrastructure, population density and geology are better predictors of baseflow stream water chemistry. Unsupervised clustering was used to generate a distinct developed landscape typology based on the expanded, high-resolution landscape feature information. Using stream chemistry data from 37 developed headwater catchments, we compared the baseflow water chemistry grouped by traditional land-cover based classes of urbanization (rural, low, medium and high density) to our composition and structure-based classification (a nine-class typology). The typology based on 22 metrics of developed landscape composition and structure explained over 50% of the variation in NO₃⁻-N, TDN, DOC, Cl⁻, and Br⁻ concentration, while the ISC-based classification only significantly explained 23% of the variation in TDN. These results demonstrate the importance of infrastructure, population and geology in defining developed landscapes and improving discrete classes for water management.