The sea as a source of atmospheric phosphorus

The geochemical fractionation of phosphorus on the drop produced by bubbles bursting in seawater has been studied using a field sampling system called the Bubble Interfacial Microlayer Sampler (BIMS). The droplets from bursting bubbles were collected on filter samples in Narragansett Bay, Rhode Island during the summer of 1975. Phosphorus was found to be fractionated by the bubble-bursting process. The enrichment factor ranged from 4 to 170. Enrichment was found to increase with decreasing phosphorus concentration at 20 cm depth while it decreases with increasing wind velocity. Enrichment was independent of bubbling depth. Together these facts suggest that the sea-surface microlayer is the source of the phosphorus on the ejected drops. Organic phosphorus on the filter samples was found to be enriched relative to surface-water phosphorus by factors of 100–200, while reactive phosphorus was enriched by factors of only 6–8. This suggests that surface-active organic phosphorus compounds are the source phosphorus in the microlayer.The organic phosphorus content of samples of atmospheric particulates collected over the phosphate-rich upwelling waters near the Peru coast was found to correlate significantly with sea-salt sodium. Enrichments calculated using the average phosphorus concentration of the surface water in this area agree well with the results of the BIMS study. Thus it appears that phosphorus fractionation does occur in nature and may be important in supplying this nutrient to some coastal regions of the world.     

The role of overwash in the evolution of mixing zone morphology within barrier islands

Overwash is a major controlling factor in the morphology of the mixing zone of coastal aquifers. Conceptual models of the mixing zone describe an interface controlled by tidal oscillations, wave run-up, and other factors; however, few describe the influence of large storm events. In August 1993, Hatteras Island, North Carolina, USA, experienced a 3-m storm surge due to Hurricane Emily. Sound-side flooding infiltrated a wellfield, causing a dramatic increase in TDS levels that persisted for more than 3 years. Two-dimensional simulations with SUTRA, the USGS finite-element model, are calibrated to the TDS breakthrough data of this storm to infer model dispersivity values. Simulations using the calibrated dispersivity values, predicted flooding levels, and 54 years of hurricane records to determine the influence of the overwash events suggest that it is rare for the mixing zone to approximate the conceptual morphology. Even during quiescent periods such as between 1965 and 1975, TDS levels do not return to theoretical levels before being elevated by a subsequent storm event. Thus, while tidal oscillations and other factors are important to mixing zone development, basic wind events and more severe storm events may have more influence and lasting effect on the morphology of the mixing zone.     

Distribution and Trophic Importance of Anthropogenic Nitrogen in Narragansett Bay: An Assessment Using Stable Isotopes

Narragansett Bay has been heavily influenced by human activities for more than 200 years. In recent decades, it has been one of the more intensively fertilized estuaries in the USA, with most of the anthropogenic nutrient load originating from sewage treatment plants (STP). This will soon change as tertiary treatment upgrades reduce nitrogen (N) loads by about one third or more during the summer. Before these reductions take place, we sought to characterize the sewage N signature in primary (macroalgae) and secondary (the hard clam, Mercenaria mercenaria) producers in the bay using stable isotopes of N (δ¹⁵N) and carbon (δ¹³C). The δ¹⁵N signatures of the macroalgae show a clear gradient of approximately 4‰ from north to south, i.e., high to low point source loading. There is also evidence of a west to east gradient of heavy to light values of δ¹⁵N in the bay consistent with circulation patterns and residual flows. The Providence River Estuary, just north of Narragansett Bay proper, receives 85% of STP inputs to Narragansett Bay, and lower δ¹⁵N values in macroalgae there reflected preferential uptake of ¹⁴N in this heavily fertilized area. Differences in pH from N stimulated photosynthesis and related shifts in predominance of dissolved C species may control the observed δ¹³C signatures. Unlike the macroalgae, the clams were remarkably uniform in both δ¹⁵N (13.2 ± 0.54‰ SD) and δ¹³C (−16.76 ± 0.61‰ SD) throughout the bay, and the δ¹⁵N values were 2–5‰ heavier than in clams collected outside the bay. We suggest that this remarkable uniformity reflects a food source of anthropogenically heavy phytoplankton formed in the upper bay and supported by sewage derived N. We estimate that approximately half of the N in the clams throughout Narragansett Bay may be from anthropogenic sources.     

Lidar observations of turbulent vortex shedding by an isolated topographic feature

Scanning measurements by a single wavelength lidar (1.06 m) were made downwind of the Pt. Sur rock, an isolated hill (height 110 m) along the California coast. Turbulent eddies (approximate diameter 50 m) were observed detaching from a stationary aerosol feature above the rock and moving downwind. Under conditions with a high Froude number [1.8], the Strouhal number [0.22] of vortex shedding was close to that observed in tank experiments with a Reynolds number of 200.     

Paleohydrology and paleochemistry of Lake Manitoba,Canada: the isotope and ostracode records

Lake Manitoba, the largest lake in the Prairie region of North America, contains a fine-grained sequence of late Pleistocene and Holocene sediment that documents a complex postglacial history. This record indicates that differential isostatic rebound and changing climate have interacted with varying drainage basin size and hydrologic budget to create significant variations in lake level and limnological conditions. During the initial depositional period in the basin, the Lake Agassiz phase (12–9 ka), ¹⁸O of ostracodes ranged from –16 to –5 (PDB), implying the lake was variously dominated by cold, dilute glacial meltwater and warm to cold, slightly saline water.Candona subtriangulata, which prefers cold, dilute water, dominates the most negative ¹⁸O intervals, when the basin was part of proglacial Lake Agassiz. At times during this early phase, the ¹⁸O of the lake abruptly shifted to higher values; euryhaline taxa such asC. rawsoni orLimnocythere ceriotuberosa, and halobiont taxa such asL. staplini orL. sappaensis are dominant in these intervals. This positive covariance of isotope and ostracode records implies that the lake level episodically fell, isolating the Lake Manitoba basin from the main glacial lake.¹⁸O values from inorganic endogenic Mg-calcite in the post-Agassiz phase of Lake Manitoba trend from –4 at 8 ka to –11 at 4.5 ka. We interpret that this trend indicates a gradually increasing influence of isotopically low (–20 SMOW) Paleozoic groundwater inflow, although periods of increased evaporation during this time may account for zones of less negative isotopic values. The ¹⁸O of this inorganic calcite abruptly shifts to higher values (–6) after 4.5 ka due to the combined effects of increased evaporative enrichment in a closed basin lake and the increased contribution of isotopically high surface water inflow on the hydrologic budget. After 2 ka, the ¹⁸O of the Mg-calcite fluctuates between –13 and –7, implying short-term variability in the lake's hydrologic budget, with values indicating the lake varied from outflow-dominated to evaporation-dominated. The ¹³C values of Mg-calcite remain nearly constant from 8 to 4.5 ka and then trend to higher values upward in the section. This pattern suggests primary productivity in the lake was initially constant but gradually increased after 4.5 ka.This is the sixth in a series of papers published in this issue on the paleolimnology of arid regions. These papers were presented at the Sixth International Palaeolimnology Symposium held 19–21 April, 1993 at the Australian National University, Canberra, Australia. Dr A. R. Chivas served as guest editor for these papers.     

Fractional crystallization and zoning in igneous feldspars: ideal water-buffered liquid fractionation lines and feldspar zoning paths

Diagrams giving plagioclase and sanidine fractionation paths and liquid fractionation lines under conditions of ideal water-buffered fractional crystallization in the ternary feldspar system were constructed graphically using topological reasoning, and experimental data and calculated phase relationships from the literature. The liquidus lines and solidus or solvus paths are unique at constant P and a _{H 2}O. The composition of a liquid evolves with time and moves along a fractionation line by removal of successive crystal fractions, whereas the compositions of each of the crystal fractions lie on and define a solidus or solvus path. Most but not all such water-buffered lines and paths differ only slightly from those in which water is free to build up during crystallization and a _{H 2}O to increase, as in many rocks. Liquid compositions lying along liquidus fractionation lines are not normally preserved, unless erupted as aphyric lavas. The solidus or solvus paths may be preserved either as overgrowth zones in crystals (zoning paths) or as a series of crystal fractions in layered intrusions. The topologies of the lines and paths depend mainly on the nature of the two-feldspar boundary line separating the plagioclase and sanidine fields which is a function of P _{H 2}O or a _{H 2}O at constant P; increases in either progressively lower the liquidi and solidi and cause larger intersections of the solidi with the solvus. One-feldspar solidus paths at high P and a _{H 2}O are simple, whereas they are complex and may bend back on themselves at low P _{H 2}O or low a _{H 2}O at high P. Two-feldspar paths may be simultaneous (cotectic) or sequential (peritectic). The former are simple and do not meet at high P and a _{H 2}O, the critical solution line lying in the gap; they are complex and may bend back or overlap at low P _{H 2}O or low a _{H 2}O at high P, the position of the critical solution line being hard to determine. Liquids which have simultaneously fractionated two feldspars may fractionate only one towards the end, crystallization changing from subsolvus to hypersolvus. Sequential paths may involve overgrowth of an early feldspar by a later one, usually sanidine overgrowths on plagioclase, but plagioclase overgrowths on sanidine occur. These complexities explain in part the difficulties of unravelling the textural and compositional relationships of ternary feldspars in water-poor felsic igneous rocks (even in the absence of alteration or complex magma dynamics) and of trying to deduce phase relationships from natural occurrences of feldspars.C.R.P.G. contribution number 948     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

Monitoring changes of clouds

An analysis of the spatial and temporal scales of cloud variability and their coupling provided by the results from existing cloud observing systems allows us to reach the following conclusions about the necessary attributes of a cloud monitoring system. (1) Complete global coverage with uniform density is necessary to obtain an unbiased estimate of cloud change and an estimate of the reliability with which that change can be determined. (2) A spatial sampling interval of less than 50 km is required so that cloud cover distributions will generally be homogeneous, or statistically homogeneous, within a sample. (3) A sampling frequency of at least six times a day ensures not only that the diurnal and semi-diurnal cycles are not aliased into long term mean values, but also that changes in them can be monitored. (4) Since estimated climate changes are only evident on a decadal time-scale, unless cloud monitoring is continuous with a record length greater than 10 years and has very high precision ( 1%) instrument calibration with overlapping observations between each pair of instruments, it will not be possible either to detect or to diagnose the effects of cloud changes on the climate.     

Channel overflows of the Pōhue Bay flow,Mauna Loa,Hawai'i: examples of the contrast between surface and interior lava

A number of overflows from a large lava channel and tube system on the southwest rift zone of Mauna Loa were studied. Initial overflows were very low viscosity gas-rich phoehoe evidenced by flow-unit aspect ratios and vesicle sizes and contents. Calculated volumetric flow-rates in the channel range between 80 and 890 m³/s, and those of the overflows between 35 and 110 m³/s. After traveling tens to hundreds of meters the tops of these sheet-like overflows were disrupted into a surface composed of clinker and phoehoe fragments. After these 'a' overflows came to rest, lava from the interiors was able to break out on to the surface as phoehoe. The surface structure of a lava flow records the interaction between the differential shear rate (usually correlated with the volumetric flow-rate) and viscosity-induced resistance to flow. However, the interior of a flow, being better insulated, may react differently or record a later set of emplacement conditions. Clefts of toothpaste lava occurring within fields of clinker on proximal-type 'a' flows also record different shear rates during different times of flow emplacement. The interplay between viscosity and shear rate determines the final morphological lava type, and although no specific portion of lava ever makes a transition from 'a' back to phoehoe, parts of a flow can appear to do so.