Biogeochemical impact of a model western iron source in the Pacific Equatorial Undercurrent

Trace element distributions in the source waters of the Pacific Equatorial Undercurrent (EUC) show the existence of elevated total acid-soluble iron concentrations. This region has been suggested to contribute enough bioavailable iron to regulate interannual and interglacial variability in biological productivity downstream in the high-nitrate low-chlorophyll upwelling zone of the eastern equatorial Pacific. We investigated the advection and first-order biogeochemical impact of an imposed, data-based iron maximum in the western Pacific EUC using an ecosystem model forced by a global dynamical model. We imposed two source profiles of iron constrained by total acid-soluble iron measurements. Though the data for total acid-soluble iron included both dissolved and acid-soluble particulate iron species, we treated all of the total acid-soluble iron as if it was dissolved and bioavailable. A deeper (270 m) source was centered in the density horizon of the observed iron maximum and a shallower (180 m) source was located in the core of our model's EUC, where a dissolved iron maximum has been frequently postulated. These source runs were compared with a control run that contained no specific source of iron associated with the EUC. In the source runs elevated iron concentrations were simulated in the EUC across its entire zonal span, evident as a subsurface plume of dissolved iron slightly below the core of the EUC. In the control run there was no iron maximum associated with the EUC. Upwelling of iron-replete water in the central and eastern equatorial Pacific increased integrated primary productivity in the Wyrtki box (180°W:90°W, 5°S:5°N, 0:200 m) by 41% and 66% for the deeper and shallower iron perturbation, respectively. The source runs increased the realism of the zonal extent of HNLC conditions and the meridional distributions of biological productivity, relative to the control run. However, in the source simulations surface chlorophyll concentrations were too high by a factor of two and maximum surface nitrate concentrations were too low, relative to climatologies. The relative abundance of diatoms roughly doubled upon the input of additional iron, exceeding field observations. Though biogeochemical data are limited and we did not adjust parameters to optimize the model fits to observations, these results suggest that acid-soluble particulate iron supplied to the EUC in the western equatorial Pacific is unlikely to be entirely bioavailable.     

Stability of methane clathrate hydrates under pressure: Influence on outgassing processes of methane on Titan

We have conducted high-pressure experiments in the H₂O-CH₄ and H₂O-CH₄-NH₃ systems in order to investigate the stability of methane clathrate hydrates, with an optical sapphire-anvil cell coupled to a Raman spectrometer for sample characterization. The results obtained confirm that three factors determine the stability of methane clathrate hydrates: (1) the bulk methane content of the samples; (2) the presence of additional gas compounds such as nitrogen; (3) the concentration of ammonia in the aqueous solution. We show that ammonia has a strong effect on the stability of methane clathrates. For example, a 10 wt.% NH₃ solution decreases the dissociation temperature of methane clathrates by 14-25 K at pressures above 5 MPa. Then, we apply these new results to Titan’s conditions. Dissociation of methane clathrate hydrates and subsequent outgassing can only occur in Titan’s icy crust, in presence of locally large amounts of ammonia and in a warm context. We propose a model of cryomagma chamber within the crust that provides the required conditions for methane outgassing: emplacement of an ice plume triggers the melting (if solid) or heating (if liquid) of large ammonia-water pockets trapped at shallow depth, and the generated cryomagmas dissociate surrounding methane clathrate hydrates. We show that this model may allow for the outgassing of significant amounts of methane, which would be sufficient to maintain the presence of methane in Titan’s atmosphere for several tens of thousands of years after a large cryovolcanic event.     

The recording of floods and earthquakes in Lake Chichój,Guatemala during the twentieth century

Laguna Chichój (Lake Chichój) is the only deep permanent lake in the central highlands of Guatemala. The lake is located in the boundary zone between the North American and Caribbean plates. The lake has been struck by devastating earthquakes and tropical cyclones in historical times. We investigated the imprint of twentieth century extreme events on the sedimentary record of this tropical lake using a bathymetric survey of the lake, coring the lake floor, and providing a chronology of sediment accumulation. The lake occupies a series of circular depressions likely formed by the rapid dissolution of a buried body of gypsum. ²¹⁰Pb and ¹³⁷Cs inventories and varve counting indicate high rates of sedimentation (1–2 cm year^?1). The annually layered sediment is interrupted by turbidites of two types: a darker-colored turbidite, enriched in lake-derived biogenic constituents, and interpreted as a seismite, and a lighter-colored type, enriched in catchment-derived constituents, interpreted as a flood layer. Comparison of our ¹³⁷Cs-determined layer ages with a catalog of twentieth century earthquakes shows that an earthquake on the Motagua fault in 1976 generated a conspicuous darker-colored turbidite and slumped deposits in separate parts of the lake. The entire earthquake inventory further reveals that mass movements in the lake are triggered at Modified Mercalli Intensities higher than V. Tropical cyclonic depressions known to have affected the lake area had limited effect on the lake, including Hurricane Mitch in 1998. One storm however produced a significantly thicker flood layer in the 1940s. This storm is reportedly the only event to have generated widespread slope failures in the lake catchment. It is thus inferred that abundant landsliding provided large amounts of concentrated sediment to the lake, through hyperpycnal flows.     

Warm‐temperate,marine, carbonate sedimentation in an Early Miocene,tide‐influenced,incised valley; Provence,south‐east France

The Saumane‐Venasque compound palaeovalley succession accumulated in a strongly tide‐influenced embayment or estuary. Warm‐temperate normal marine to brackish conditions led to deposition of extensive cross‐bedded biofragmental calcarenites. Echinoids, bryozoans, coralline algae, barnacles and benthic foraminifera were produced in seagrass meadows, on rocky substrates colonized by macroalgae and within subaqueous dune fields. There are two sequences, S1 and S2, the first of which contains three high‐frequency sequences (S1a, S1b and S1c). Sequence 1 is largely confined to the palaeovalley with its upper part covering interfluves. Each of these has a similar upward succession of deposits that includes: (i) a basal erosional surface that is bored and glauconitized; (ii) a discontinuous lagoonal lime mudstone or wackestone; (iii) a thin conglomerate generated by tidal ravinement; (iv) a transgressive systems tract series of cross‐bedded calcarenites; (v) a maximum flooding interval of argillaceous, muddy quartzose, open‐marine limestones; and (vi) a thin highstand systems tract of fine‐grained calcarenite. Tidal currents during stages S1a, S1b and S1c were accentuated by the constricted valley topography, whereas basin‐scale factors enhanced tidal currents during the deposition of S2. The upper part of the succession in all but S1c has been removed by later erosion. There is an overall upward temporal change with quartz, barnacles, encrusting corallines and epifaunal echinoids decreasing but bryozoans, articulated corallines and infaunal echinoids increasing. This trend is interpreted to be the result of changing oceanographic conditions as the valley was filled, bathymetric relief was reduced, rocky substrates were replaced as carbonate factories by seagrass meadows and subaqueous dunes, and the setting became progressively less confined and more open marine. These limestones are characteristic of a suite of similar cool‐water calcareous sand bodies in environments with little siliciclastic or fresh water input during times of high‐amplitude sea‐level change wherein complex inboard antecedent topography was flooded by a rising ocean.     

A helping hand: artificial nest site provisioning increases breeding success of a tropical seabird

Common white terns Gygis alba lay a single egg balanced on rocks or branches and consequently are at risk of low nesting success. A novel technique of hollowing out coconut husks and providing artificial nest sites was developed on Cousine Island, Seychelles. Our study aimed to critically assess whether common white tern nesting success differed between artificial and natural nest sites. For natural nest sites, nesting success and the stage of nest failure were also compared between seasons, nest heights, and tree species. Finally, we compared results from our study to those of a study conducted 10 years ago on the same island. Nesting success differed significantly between artificial nests and natural nests, with the success of artificial nests nearly double that of natural nests. Hatching success was similar for artificial and natural nests (65% and 52% respectively), suggesting coconut husks do not reduce egg losses, but rather provide secure perches for young chicks. Most natural nest failures occurred during the egg phase (70%), followed by the youngest chick phase (21%). Of the eggs that hatched in natural nests, 61% fledged successfully. Tree species and season significantly influenced nesting success for natural nests and nest height varied significantly between tree species. Higher nesting success was observed during the mixed seasonal period (50%) followed by the cooler, windier and drier South-East Monsoon season (33%). The hotter and more humid North-West Monsoon period had the lowest nesting success (20%). Comparisons of nesting success at natural and artificial nest sites with the earlier study did not differ significantly, despite a smaller population of common white terns being present on the island at that stage. Our results support the use of artificial nest sites to improve nesting success for this species and serve as a model for similar species currently under threat.     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

Building zoned ignimbrites by recycling silicic cumulates: insight from the 1,000 km<Superscript>3</Superscript> Carpenter Ridge Tuff,CO

The ~1,000 km³ Carpenter Ridge Tuff (CRT), erupted at 27.55 Ma during the mid-tertiary ignimbrite flare-up in the western USA, is among the largest known strongly zoned ash-flow tuffs. It consists primarily of densely welded crystal-poor rhyolite with a pronounced, highly evolved chemical signature (high Rb/Sr, low Ba, Zr, Eu), but thickly ponded intracaldera CRT is capped by a more crystal-rich, less silicic facies. In the outflow ignimbrite, this upper zone is defined mainly by densely welded crystal-rich juvenile clasts of trachydacite composition, with higher Fe–Ti oxide temperatures, and is characterized by extremely high Ba (to 7,500 ppm), Zr, Sr, and positive Eu anomalies. Rare mafic clasts (51–53 wt% SiO₂) with Ba contents to 4,000–5,000 ppm and positive Eu anomalies are also present. Much of the major and trace-element variations in the CRT juvenile clasts can be reproduced via in situ differentiation by interstitial melt extraction from a crystal-rich, upper-crustal mush zone, with the trachydacite, crystal-rich clasts representing the remobilized crystal cumulate left behind by the melt extraction process. Late recharge events, represented by the rare mafic clasts and high-Al amphiboles in some samples, mixed in with parts of the crystal cumulate and generated additional scatter in the whole-rock data. Recharge was important in thermally remobilizing the silicic crystal cumulate by partially melting the near-solidus phases, as supported by: (1) ubiquitous wormy/sieve textures and reverse zoning patterns in feldspars and biotites, (2) absence of quartz in this very silicic unit stored at depths of >4–5 km, and (3) heterogeneous melt compositions in the trachydacite fiamme and mafic clasts, particularly in Ba, indicating local enrichment of this element due mostly to sanidine and biotite melting. The injection of hot, juvenile magma into the upper-crustal cumulate also imparted the observed thermal gradient to the deposits and the mixing overprint that partly masks the in situ differentiation process. The CRT provides a particularly clear perspective on processes of in situ crystal-liquid separation into a lower crystal-rich zone and an upper eruptible cap, which appears common in incrementally built upper-crustal magma reservoirs of high-flux magmatic provinces.     

A case study of using Raman lidar measurements in high-accuracy GPS applications

This paper investigates the impact of rapid small-scale water vapor fluctuations on GPS height determination. Water vapor measurements from a Raman lidar are used for documenting the water vapor heterogeneities and correcting GPS signal propagation delays in clear sky conditions. We use data from four short observing sessions (6 h) during the VAPIC experiment (15 May–15 June 2004). The retrieval of wet delays from our Raman lidar is shown to agree well with radiosonde retrievals (bias and standard deviation (SD) were smaller than 1 and 2.8 mm, respectively) and microwave radiometers (from two different instruments, bias was 6.0/−6.6 mm and SD 1.3/3.8 mm). A standard GPS data analysis is shown to fail in accurately reproducing fast zenith wet delay (ZWD) variations. The ZWD estimates could be improved when mean post-fit phase residuals were removed. Several methodologies for integrating zenith lidar observations into the GPS data processing are also presented. The final method consists in using lidar wet delays for correcting a priori the GPS phase observations and estimating a scale factor for the lidar wet delays jointly with the GPS station position. The estimation of this scale factor allows correcting for a mis-calibration in the lidar data and provides in the same way an estimate of the Raman lidar instrument constant. The agreement of this constant with an independent determination using radiosonde data is at the level of 1–4%. The lidar wet delays were derived by ray-tracing from zenith pointing measurements: further improvement in GPS positioning is expected from slant path lidar measurements that would properly account for water vapor anisotropy.     

Contribution of climatic and anthropogenic effects to the hydric deficit of peatlands

The present study makes use of a detailed water balance to investigate the hydrological status of a peatland with a basal clay‐rich layer overlying an aquifer exploited for drinking water. The aim is to determine the influence of climate and groundwater extraction on the water balance and water levels in the peatland. During the two‐year period of monitoring, the hydrological functioning of the wetland showed a hydric deficit, associated with a permanent unsaturated layer and a deep water table. At the same time, a stream was observed serving as a recharge inflow instead of draining the peatland, as usually described in natural systems. Such conditions are not favourable for peat accumulation. Field investigations show that the clay layer has a high hydraulic conductivity (from 1·10^?7 to 3·10^?9 m.s^?1) and does not form a hydraulic barrier. Moreover, the vertical hydraulic gradients are downward between the peat and the sand aquifer, leading to high flows of groundwater through the clay layer (20–48% of the precipitation). The observed hydric deficit of the peatland results from a combination of dry climatic conditions during the study period and groundwater extraction. The climatic effect is mainly expressed through drying out of the peatland, while the anthropogenic effect leads to an enhancement of the climatic effect on a global scale, and a modification of fluxes at a local scale. The drying out of the peatland can lead to its mineralisation, which thus gives rise to environmental impacts. The protection of such wetlands in the context of climate change should take account of anthropogenic pressures by considering the wetland‐aquifer interaction. Copyright © 2011 John Wiley & Sons, Ltd.     

Magnetic horizons of UHECR sources and the GZK feature

We study the effect of random extra-galactic magnetic fields on the propagation of protons of energy larger than 10¹⁹ eV. We show that for reasonable field values (in the 100 nG range) the transition between diffusive and ballistic regimes occurs in the same energy range as the GZK cutoff (a few 10¹⁹ eV). The usual interpretation of the flux reduction above the GZK energy in terms of a sudden reduction of the visible horizon is modified. Moreover, since the size of the diffusion sphere of a continuous source of cosmic rays is of the order of 10 Mpc, the local structure of the Universe and, therefore, of potential local astrophysical sources plays a dominant role in the expected spectrum. Under reasonable assumptions on the sources configurations the expected GZK cutoff is reduced.