Sources and fate of nutrients in a subtropical reservoir

This study examined the sources and fate of nutrient inputs from two principal tributaries to the eutrophic subtropical Wivenhoe reservoir: an unregulated river and a dammed river with regular releases, during a period of declining reservoir water levels. Nutrient budgets were constructed over a period of 6 years, and combined with short-term data on nutrient concentrations and forms, and δ¹⁵N stable isotope data. Our study found that over a 6 year period, there was net retention of phosphorus (P) in the reservoir, with 60% of inputs retained. Most of the P input load came from the unregulated river, with an agricultural catchment, during periods of high flow. During one event half of the total TP load from the unregulated river in the study period was delivered in only 12 days. Much of the P was dissolved inorganic P (DIP) and was derived from high P concentrations in soils and sediments. This highlights the importance of appropriate catchment management practices to reduce P losses from terrestrial systems because retention of P in reservoir sediments reduces the availability of this nutrient for agricultural production. In contrast, there was negligible retention of nitrogen (N). The unregulated river was an important source of N derived from N fixation in the river and adjacent soils, while the source from the dammed river was mostly reprocessed N. The high retention of P relative to N is consistent with relatively higher accumulation of P in sediments.     

The impact of the MJO on clusters of wintertime circulation anomalies over the North American region

Recent studies have shown that the Madden–Julian Oscillation (MJO) impacts the leading modes of intraseasonal variability in the northern hemisphere extratropics, providing a possible source of predictive skill over North America at intraseasonal timescales. We find that a k-means cluster analysis of mid-level geopotential height anomalies over the North American region identifies several wintertime cluster patterns whose probabilities are strongly modulated during and after MJO events, particularly during certain phases of the El Niño-Southern Oscillation (ENSO). We use a simple new optimization method for determining the number of clusters, k, and show that it results in a set of clusters which are robust to changes in the domain or time period examined. Several of the resulting cluster patterns resemble linear combinations of the Arctic Oscillation (AO) and the Pacific/North American (PNA) teleconnection pattern, but show even stronger responses to the MJO and ENSO than clusters based on the AO and PNA alone. A cluster resembling the positive (negative) PNA has elevated probabilities approximately 8–14 days following phase 6 (phase 3) of the MJO, while a negative AO-like cluster has elevated probabilities 10–20 days following phase 7 of the MJO. The observed relationships are relatively well reproduced in the 11-year daily reforecast dataset from the National Centers for Environmental Prediction (NCEP) Climate Forecast System version 2 (CFSv2). This study statistically links MJO activity in the tropics to common intraseasonal circulation anomalies over the North American sector, establishing a framework that may be useful for improving extended range forecasts over this region.     

Reconciling theories of a mechanically driven meridional overturning circulation with thermohaline forcing and multiple equilibria

It has recently been suggested that the structure and strength of the meridional overturning circulation in the global ocean is governed by the input of mechanical energy to the system by winds and tides. However, it is not clear how this suggestion relates to the existence of multiple equilibria of the meridional overturning circulation, which depends on thermohaline feedbacks and is more consistent with a buoyancy-driven view of the circulation. Both theories have been illustrated by box models in the past (Stommel in Tellus 13:224–230, 1961; Gnanadesikan in Science 283:2077–2079, 1999). Here we incorporate these two theories into a single box model in an attempt to reconcile the roles of mechanical and buoyancy forcing in driving the meridional overturning circulation. The box model has two equilibrium solutions, one with sinking at high northern latitudes as in the present-day Atlantic, and one without. The circulation is mechanically driven, but the northern sinking can be thought of as a release valve which acts as a sink of potential energy when the surface water at high northern latitudes is dense enough to convect. While the source of energy comes from mechanical forcing, the presence or otherwise of multiple equilibria is therefore determined by thermohaline feedbacks. In some areas of parameter space an oscillation between the model’s two circulation regimes occurs, reminiscent of a bipolar seesaw.     

Apposite of atmospheric electric parameters with the energy coupling function (ε) during geomagnetic storms at high latitude

In this paper we are concerned with the variation of the atmospheric electric field and the air–earth current due to the excessive power generated by the solar wind-magnetosphere dynamo during geomagnetic storms, recorded at Maitri in Antarctica during 2004. A major part of the power generated by the solar wind-magnetosphere dynamo is used in the formation of the ring current and the rest is utilized for Joule heating and auroral particle precipitation. The method adopted by Frank-Kamenetsky et al. [Frank-Kamenetsky A.V., Troshichev O.A., Burns G.B., Papitashvili V.O., 2001. Variations of atmospheric electric field in the near-pole region related to the interplanetary magnetic field. J. Geophys. Res. 106, A1, 179–190.] was utilized to delineate the variations due to the signatures of tropical thunderstorm activity from the geoelectric data; while statistical methods used in our earlier studies were used to delimit variation due to the constant buffeting of the solar wind. We find that the solar wind-magnetosphere energy coupling function (ε) to be well correlated with the atmospheric electric parameters during the onset of geomagnetic disturbances. However the correlation breaks down during minor storms and sub-storm events.     

Geochemistry of intrusive rocks associated with the Latir volcanic field,New Mexico,and contrasts between evolution of plutonic and volcanic rocks

Plutonic rocks associated with the Latir volcanic field comprise three groups: 1) 25 Ma high-level resurgent plutons composed of monzogranite and silicic metaluminous and peralkaline granite, 2) 23–25 Ma syenogranite, and alkali-feldspar granite intrusions emplaced along the southern caldera margin, and 3) 19–23 Ma granodiorite and granite plutons emplaced south of the caldera. Major-element compositions of both extrusive and intrusive suites in the Latir field are broadly similar; both suites include high-SiO₂ rocks with low Ba and Sr, and high Rb, Nb, Th, and U contents. Moreover, both intermediateto siliciccomposition volcanic and plutonic rocks contain abundant accessory sphene and apatite, rich in rare-earth elements (REE), as well as phases in which REE's are essential components. Strong depletion in Y and REE contents, with increasing SiO₂ content, in the plutonic rocks indicate a major role for accessory mineral fractionation that is not observed in volcanic rocks of equivalent composition. Considerations of the rheology of granitic magma suggest that accessory-mineral fractionation may occur primarily by filter-pressing evolved magmas from crystal-rich melts. More limited accessory-mineral crystallization and fractionation during evolution of the volcanic magmas may have resulted from markedly lower diffusivities of essential trace elements than major elements. Accessory-mineral fractionation probably becomes most significant at high crystallinities. The contrast in crystallization environments postulated for the extrusive and intrusive rocks may be common to other magmatic systems; the effects are particularly pronounced in highly evolved rocks of the Latir field. High-SiO₂ peralkaline porphyry emplaced during resurgence of the Questa caldera represents non-erupted portions of the magma that produced the Amalia Tuff during caldera-forming eruption. The peralkaline porphyry continues compositional and mineralogical trends found in the tuff. Amphibole, mica, and sphene compositions suggest that the peralkaline magma evolved from metaluminous magma. Extensive feldspar fractionation occurred during evolution of the peralkaline magmas, but additional alkali and iron enrichment was likely a result of high halogen fluxes from crystallizing plutons and basaltic magmas at depth.     

Chemical Separation and Isotopic Variations of Cu and Zn From Five Geological Reference Materials

This paper presents an adapted anion exchange column chemistry protocol which allowed separation of high-purity fractions of Cu and Zn from geological materials. Isobaric and non-spectral interferences were virtually eliminated for consequent multiple-collector ICP-MS analysis of the isotopic composition of these metals. The procedure achieved ∼ 100% recoveries, thus ensuring the absence of column-induced isotopic fractionation. By employing these techniques, we report isotopic analyses for Cu and Zn from five geological reference materials: BCR-027 blende ore (BCR), δ⁶⁵Cu = 0.52 ± 0.15‰ (n = 10) and δ⁶⁶Zn = 0.33 ± 0.07‰ (n = 8); BCR-030 calcined calamine ore (BCR), δ⁶⁶Zn = -0.06 ± 0.09‰ (n = 8); BCR-1 basalt (USGS), δ⁶⁶Zn = 0.29 ± 0.12‰ (n = 8); NOD-P-1 manganese nodule (USGS), δ⁶⁵Cu = 0.46 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.78 ± 0.09‰ (n = 9); SU-1 Cu-Co ore (CCRMP), δ⁶⁵Cu = -0.018 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.13 ± 0.17‰ (n = 6). All uncertainties are ± 2s; copper isotope ratios are reported relative to NIST SRM-976, and zinc isotope ratios relative to the Lyon-group Johnson Matthey metal (batch 3-0749 L) solution, JMC Zn. These values agree well with the limited data previously published, and with results reported for similar natural sample types. Samples were measured using a GVi IsoProbe MC-ICP-MS, based at the Natural History Museum, London. Long-term measurement reproducibility has been assessed by repeat analyses of both single element and complex matrix samples, and was commonly better than ± 0.07‰ for both δ⁶⁶Zn and δ⁶⁵Cu.     

Origin of metaluminous and alkaline volcanic rocks of the Latir volcanic field,northern Rio Grande rift,New Mexico

Volcanic rocks of the Latir volcanic field evolved in an open system by crystal fractionation, magma mixing, and crustal assimilation. Early high-SiO₂ rhyolites (28.5 Ma) fractionated from intermediate compositionmagmas that did not reach the surface. Most precaldera lavas have intermediate-compositions, from olivine basaltic-andesite (53% SiO₂) to quartz latite (67% SiO₂). The precaldera intermediate-composition lavas have anomalously high Ni and MgO contents and reversely zoned hornblende and augite phenocrysts, indicating mixing between primitive basalts and fractionated magmas. Isotopic data indicate that all of the intermediate-composition rocks studied contain large crustal components, although xenocrysts are found only in one unit. Inception of alkaline magmatism (alkalic dacite to high-SiO₂ peralkaline rhyolite) correlates with, initiation of regional extension approximately 26 Ma ago. The Questa caldera formed 26.5 Ma ago upon eruption of the >500 km³ high-SiO₂ peralkaline Amalia Tuff. Phenocryst compositions preserved in the cogenetic peralkaline granite suggest that the Amalia Tuff magma initially formed from a trace element-enriched, high-alkali metaluminous magma; isotopic data suggest that the parental magmas contain a large crustal component. Degassing of water- and halogen-rich alkali basalts may have provided sufficient volatile transport of alkalis and other elements into the overlying silicic magma chamber to drive the Amalia Tuff magma to peralkaline compositions. Trace element variations within the Amalia Tuff itself may be explained solely by 75% crystal fractionation of the observed phenocrysts. Crystal settling, however, is inconsistent with mineralogical variations in the tuff, and crystallization is thought to have occurred at a level below that tapped by the eruption. Spatially associated Miocene (15-11 Ma) lavas did not assimilate large amounts of crust or mix with primitive basaltic magmas. Both mixing and crustal assimilation processes appear to require development of relatively large magma chambers in the crust that are sustained by large basalt fluxes from the mantle. The lack of extensive crustal contamination and mixing in the Miocene lavas may be related to a decreased basalt flux or initiation of blockfaulting that prevented pooling of basaltic magma in the crust.     

Simulating Climate over Western North America Using Stochastic Weather Generators

The climatologies of daily precipitation and of maximum and minimum temperatures over western North America are simulated using stochastic weather generators. Two types of generator, differentiated only by their method of modeling precipitation occurrence, are investigated. A second-order Markov model, in which the probability of the occurrence of precipitation is modeled as contingent upon its occurrence on the previous two days, is compared with a spell-length model, in which mass functions of wet- and dry-spell lengths are modeled. Both models are able to reproduce the observed annual and monthly climatology in the region to a high degree of accuracy. However, there is considerable over-dispersion in annual precipitation, resulting primarily from an underestimation in the interannual variability of precipitation intensity. The interannual variability of temperatures is similarly underestimated, and is most severe for minimum temperatures. There is a severe problem in estimating minimum temperature extremes, which can be attributed to the negatively skewed distribution of daily minimum temperatures. Non-normality in the distribution of daily temperatures is shown to be a problem in simulating extreme temperature maxima as well as of minima. It is suggested that the normal distribution used in the generation of daily temperatures in the widely used Richardson (1981) generator, and its derivations, be supplanted by a more appropriate distribution that permits skewness in either direction.     

Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces

The types and structures of adsorption complexes formed by oxalate at boehmite (γ-AlOOH)/water and corundum (α-Al₂O₃)/water interfaces were determined using in situ attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy and quantum chemical simulation methods. At pH 5.1, at least four different oxalate species were found at or near the boehmite/water interface for oxalate surface coverages (Γ_ox) ranging from 0.25 to 16.44 μmol/m². At relatively low coverages (Γ_ox < 2.47), strongly adsorbed inner-sphere oxalate species (IR peaks at 1286, 1418, 1700, and 1720 cm⁻¹) replace weakly adsorbed carbonate species, and a small proportion of oxalate anions are adsorbed in an outer-sphere mode (IR peaks at 1314 and 1591 cm⁻¹). IR peaks indicative of inner-sphere adsorbed oxalate are also observed for oxalate at the corundum/water interface at Γ_ox = 1.4 μmol/m². With increasing oxalate concentration (Γ_ox > 2.47 μmol/m²), the boehmite surface binding sites for inner-sphere adsorbed oxalate become saturated, and excess oxalate ions are present dominantly as aqueous species (IR peaks at 1309 and 1571 cm⁻¹). In addition to these adsorption processes, oxalate-promoted dissolution of boehmite following inner-sphere oxalate adsorption becomes increasingly pronounced with increasing Γ_ox and results in an aqueous Al(III)-oxalate species, as indicated by shifted IR peaks (1286 → 1297 cm⁻¹ and 1418 → 1408 cm⁻¹). At pH 2.5, no outer-sphere adsorbed oxalate or aqueous oxalate species were observed. The similarity of adsorbed oxalate spectral features at pH 2.5 and 5.1 implies that the adsorption mechanism of aqueous HOx⁻ species involves loss of protons from this species during the ligand-exchange reaction. As a consequence, adsorbed inner-sphere oxalate and aqueous Al(III)-oxalate complexes formed at pH 2.5 have coordination geometries very similar to those formed at pH 5.1.The coordination geometry of inner-sphere adsorbed oxalate species was also predicted using quantum chemical geometry optimization and IR vibrational frequency calculations. Geometry-optimized Al₈O₁₂ and Al₁₄O₂₂ clusters with the reactive surface Al site coordinated by three oxygens were used as model substrates for corundum and boehmite surfaces. Among the models considered, calculated IR frequencies based on a bidentate side-on structure with a 5-membered ring agree best with the observed frequencies for boehmite/oxalate/water samples at Γ_ox = 0.25 to 16.44 μmol/m² and pH 2.5 and 5.1, and for a corundum/oxalate/water sample at Γ_ox = 1.4 μmol/m² and pH 5.1. Based on these results, we suggest that oxalate bonding on boehmite and corundum surfaces results in 5-coordinated rather than 4- or 6-coordinated Al surface sites.