Formation and Characteristics of Coastal Internal Boundary Layers During Onshore Flows

The development and characteristics of coastal internal boundary layers were investigated in 28 tests. These were made at all seasons and in both gradient and sea-breeze flows but only during mid-day periods. Measurements of turbulence and temperature were taken from a light aircraft which flew traverses across Long Island at successive altitudes parallel to the wind direction. These were used to locate the boundary between modified and unmodified air as a function of height and distance from the coast. The same measurements plus tower measurements of wind, turbulence and temperature, pilot balloon soundings and measurements of land and water surface temperatures by a remote sensing IR thermometer were used to quantify the characteristics of the modified and unmodified air. The boundary layer slope was steep close to the land-water interface and became shallower with downwind distance. Growth of the boundary layer was initially slower with stable lapse rates upwind than with neutral or unstable conditions over the water. An equilibrium height was found in many tests except under conditions of free convection when the internal boundary layer merged into the mixed layer inland and with sea-breeze conditions. The equilibrium height depended on downwind conditions and was greater with low wind speeds and strong land surface heating than with stronger winds and small land-water temperature differences. Current theoretical models are not adequate to predict the height of the boundary layer at the altitudes and distances studied but reasonably good predictions were given by an empirical model developed earlier. Wind speed in the modified air averaged about 70% of that at the coast but turbulence levels were several times higher both near the surface and aloft. These findings have important implications for diffusion from coastal sites.     

A Synthetic Haematite Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Application to Iron Oxide‐Cu‐Au Systems

In both nature and synthetic experiments, the common iron oxide haematite (α‐Fe₂O₃) can incorporate significant amounts of U into its crystal structure and retain radiogenic Pb over geological time. Haematite is a ubiquitous component of many ore deposit types and, therefore, represents a valuable hydrothermal mineral geochronometer, allowing direct constraints to be placed on the timing of ore formation and upgrading. However, to date, no suitable natural haematite reference material has been identified. Here, a synthetic haematite U‐Pb reference material (MR‐HFO) is characterised using LA‐ICP‐MS and ID‐TIMS. Centimetre‐scale ‘chips’ of synthesised α‐Fe₂O₃ were randomly microsampled via laser ablation‐extraction and analysed using ID‐TIMS. Reproducible U/Pb and Pb/Pb measurements were obtained across four separate chips (n = 13). Subsequently, an evaluation of the suitability MR‐HFO in constraining U‐Pb data via LA‐ICP‐MS is presented using a selection of natural samples ranging from Cenozoic to Proterozoic in age. The MR‐HFO normalised U‐Pb ratios are more concordant and ages more accurate versus the same LA‐ICP‐MS spot analyses normalised to zircon reference material, when compared with independently acquired ID‐TIMS data from the same natural haematite grains. Results establish MR‐HFO as a suitable reference material for LA‐ICP‐MS haematite U‐Pb geochronology.     

Prediction of the effects of size and morphology on the structure of water around hematite nanoparticles

Compared with macroscopic surfaces, the structure of water around nanoparticles is difficult to probe directly. We used molecular dynamics simulations to investigate the effects of particle size and morphology on the time-averaged structure and the dynamics of water molecules around two sizes of hematite (α-Fe₂O₃) nanoparticles. Interrogation of the simulations via atomic density maps, radial distribution functions and bound water residence times provide insight into the relationships between particle size and morphology and the behavior of interfacial water. Both 1.6 and 2.7 nm particles are predicted to cause the formation of ordered water regions close to the nanoparticle surface, but the extent of localization and ordering, the connectivity between regions of bound water, and the rates of molecular exchange between inner and outer regions are all affected by particle size and morphology. These findings are anticipated to be relevant to understanding the rates of interfacial processes involving water exchange and the transport of aqueous ions to surface sites.     

Sea-Level Changes and δO Record for the Past 34,000 yr from Mayotte Reef, Indian Ocean

New sea-level and δ¹⁸O curves for the past 34,000 yr, based on uranium–thorium chronology, are proposed for the southwestern part of the Indian Ocean. The archives include cores drilled from onshore coral reefs and submersed samples from foreslope corals of Mayotte in the Comoro Islands. The Mayotte sea-level curve shows a lowstand of 145 ± 5 m below the present level during the last glacial maximum dated at 18,400 yr. This lowstand is supported by the maximum¹⁸O enrichment in the coral colonies. The residual signal (Δδ¹⁸O), controlled by sea-surface temperature changes, indicates that surface waters 18,400 yr ago were approximately 5°C cooler than present. The deglacial sea-level rise is clearly recorded, with a mean rate of about 1.7 cm yr⁻¹between 18,400 and 10,000 yr ago. The deglaciation phase is characterized by a strong¹⁸O depletion marked by two pulses related to meltwater discharges into the North Atlantic Ocean but also characterized by responses specific to the tropical Indian Ocean.     

Terrace reconstruction and long profile projection: a case study from the Solent river system near Southampton,England

River terrace sequences are important frameworks for archaeological evidence and as such it is important to produce robust correlations between what are often fragmentary remnants of ancient terraces. This paper examines both conceptual and practical issues related to such correlations, using a case study from the eastern part of the former Solent River system near Southampton, England. In this region two recent terrace schemes have been constructed using different data to describe the terrace deposits: one based mainly on terrace surfaces; the other on gravel thicknesses, often not recording the terrace surface itself. The utility of each of these types of data in terrace correlation is discussed in relation to the complexity of the record, the probability of post-depositional alteration of surface sediments and comparison of straight-line projections with modern river long profiles. Correlation using age estimates is also discussed, in relation to optically stimulated luminescence dating of sand lenses within terrace gravels in this region during the PASHCC project. It is concluded that the need for replication at single sites means that this approach has limited use for correlative purposes, although dating of sediments is important for understanding wider landscape evolution and patterns of human occupation.     

Intermobility of barium,strontium, and lead in chloride and sulfate leach solutions

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t_50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t_50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.

     

Mantle heterogeneity and crustal recycling in Archean granite-greenstone belts: Evidence from Nd isotopes and trace elements in the Rainy Lake area, Superior Province, Ontario, Canada

The 2685–2752 Ma old granite-greenstone crust in the Rainy Lake area, Ontario, consists of metaigneous and metasedimentary rocks that range in composition from tholeiite to monzogranite and include anorthosite, trachyandesite, monzodiorite and high-silica rhyodacite. Major element, rare earth and other trace element data are the basis for modelling the formation of the crust by melting of large-ionlithophile element enriched and unenriched mantle, by melting of basalt at mantle to crustal levels and by melting of monzodiorite and tonalite at crustal levels.

All metaigneous rocks lie on a ¹⁴³Nd/¹⁴⁴Nd vs. ¹⁴⁷Sm/¹⁴⁴Nd isochron with an age of 2737 ±42 Ma and an initial ¹⁴³Nd/¹⁴⁴Nd of 0.509178 ±33 (ε_Nd = +1.9). This age is consistent with U-Pb zircon ages, which suggests the Nd isotopic system has been unaffected since the crust-forming events. The positive initial ε_Nd's are further evidence for time-averaged depletion in Sm/Nd relative to CHUR for the Archean mantle. The similarity of the initial Nd isotopic composition for both mantle-derived and crustally-derived rocks suggests rapid recycling of crustal components, which were previously derived from depleted mantle sources.

Initial ¹⁴³Nd/¹⁴⁴Nd ratios on individual rocks range from ε_Nd = +3.3 to ε_Nd = −0.4. Younger granitoids have lower ε_Nd values (+1.5 to −0.1) relative to tholeiites and monzodiorites crystallized from mantle-derived melts (+3.3 to +1.0). Thus, incorporation of slightly older crust (ca. 100–200 Ma) in some of the granitoid source areas is possible. Mantle-derived rocks form an isochron of 2764 ±58 Ma that represents a minimum age for enrichment processes in the mantle sources for the Rainy Lake area. Consideration of data from the Abitibi belt suggests such enrichment processes in the mantle may have preceded crust-forming events in a wide area of the Superior Province, perhaps by as much as 50–70 Ma.     

Late Quaternary barrier and fringing reef development of Bora Bora (Society Islands,south Pacific): First subsurface data from the Darwin‐type barrier‐reef system

The universally known subsidence theory of Darwin, based on Bora Bora as a model, was developed without information from the subsurface. To evaluate the influence of environmental factors on reef development, two traverses with three cores, each on the barrier and the fringing reefs of Bora Bora, were drilled and 34 uranium‐series dates obtained and subsequently analysed. Sea‐level rise and, to a lesser degree, subsidence were crucial for Holocene reef development in that they have created accommodation space and controlled reef architecture. Antecedent topography played a role as well, because the Holocene barrier reef is located on a Pleistocene barrier reef forming a topographic high. The pedestal of the fringing reef was Pleistocene soil and basalt. Barrier and fringing reefs developed contemporaneously during the Holocene. The occurrence of five coralgal assemblages indicates an upcore increase in wave energy. Age–depth plots suggest that barrier and fringing reefs have prograded during the Holocene. The Holocene fringing reef is up to 20 m thick and comprises coralgal and microbial reef sections and abundant unconsolidated sediment. Fringing reef growth started 8780 ± 50 yr bp ; accretion rates average 5·65 m kyr^?1. The barrier reef consists of >30 m thick Holocene coralgal and microbial successions. Holocene barrier‐reef growth began 10 030 ± 50 yr bp and accretion rates average 6·15 m kyr^?1. The underlying Pleistocene reef formed 116 900 ± 1100 yr bp , i.e. during marine isotope stage 5e. Based on Pleistocene age, depth and coralgal palaeobathymetry, the subsidence rate of Bora Bora was estimated to be 0·05 to 0·14 m kyr^?1. In addition to subsidence, reef development on shorter timescales like in the late Pleistocene and Holocene has been driven by glacioeustatic sea‐level changes causing alternations of periods of flooding and subaerial exposure. Comparisons with other oceanic barrier‐reef systems in Tahiti and Mayotte exhibit more differences than similarities.     

Testing Nano-Powder and Fused-Glass Mineral Reference Materials for In Situ Rb-Sr Dating of Glauconite,Phlogopite, Biotite and Feldspar via LA-ICP-MS/MS

Reference materials (RMs) with well-characterised composition are necessary for reliable quantification and quality control of isotopic analyses of geological samples. For in situ Rb-Sr analysis of silicate minerals via laser ablation inductively coupled plasma tandem mass spectrometry (LA-ICP-MS/MS) with a collision/reaction cell, there is a general lack of mineral-specific and matrix-matched RMs, which limits wider application of this new laser-based dating technique to certain minerals. In this work, pressed nano-powder pellets (NP) of four RMs, GL-O (glauconite), Mica-Mg (phlogopite), Mica-Fe (biotite) and FK-N (K-feldspar), were analysed and tested for in situ Rb-Sr dating, complemented by isotope dilution (ID) MC-ICP-MS Rb-Sr analyses of GL-O and Mica-Mg. In addition, we attempted to develop alternative flux-free and fused ‘mineral glasses’ from the above RMs for in situ Rb-Sr dating applications. Overall, the results of this study showed that among the above RMs only two NP (Mica-Mg-NP and GL-O-NP) were suitable and robust for in situ dating applications. These two nano-powder reference materials, Mica-Mg-NP and GL-O-NP, were thus used as primary RMs to normalise and determine Rb-Sr ages for three natural minerals: MDC phlogopite and GL-O glauconite grains, and also Mica-Fe-NP (biotite). Our in situ analyses of the above RMs yielded Rb-Sr ages that are in good agreement (within 8%) of published ages, which suggests that both Mica-Mg-NP and GL-O-NP are suitable RMs for in situ Rb-Sr dating of phlogopite, glauconite and biotite. However, using secondary RMs is recommended to monitor the quality of the obtained ages.     

Breaking recent global temperature records

Global surface temperature was a record in 1988. What is the probability that this record will be surpassed in the next few years? Answers are provided given a variety of simple statistical models for temperature. The answers illustrate how record breaking is influenced by alternative model specifications. Estimates for the probability of a record are shown to range widely. If annual temperature is independent and identically distributed then a new record is unlikely. But probabilities increase rapidly if there is a trend or autocorrelation. Estimates of the probability of a record using data on global temperature suggest that another record in the next few years would not be a rare event.