Interactions between short-term and long-term plasticity: shooting for a moving target

Far from being static transmission units, synapses are highly dynamical elements that change over multiple time scales depending on the history of the neural activity of both the pre- and postsynaptic neuron. Moreover, synaptic changes on different time scales interact: long-term plasticity (LTP) can modify the properties of short-term plasticity (STP) in the same synapse. Most existing theories of synaptic plasticity focus on only one of these time scales (either STP or LTP or late-LTP) and the theoretical principles underlying their interactions are thus largely unknown. Here we develop a normative model of synaptic plasticity that combines both STP and LTP and predicts specific patterns for their interactions. Recently, it has been proposed that STP arranges for the local postsynaptic membrane potential at a synapse to behave as an optimal estimator of the presynaptic membrane potential based on the incoming spikes. Here we generalize this approach by considering an optimal estimator of a non-linear function of the membrane potential and the long-term synaptic efficacy—which itself may be subject to change on a slower time scale. We find that an increase in the long-term synaptic efficacy necessitates changes in the dynamics of STP. More precisely, for a realistic non-linear function to be estimated, our model predicts that after the induction of LTP, causing long-term synaptic efficacy to increase, a depressing synapse should become even more depressing. That is, in a protocol using trains of presynaptic stimuli, as the initial EPSP becomes stronger due to LTP, subsequent EPSPs should become weakened and this weakening should be more pronounced with LTP. This form of redistribution of synaptic efficacies agrees well with electrophysiological data on synapses connecting layer 5 pyramidal neurons.

Diffusion-driven transport in clayrock formations

Clay mineral-rich sedimentary formations are currently under investigation to evaluate their potential use as host formations for installation of deep underground disposal facilities for radioactive waste (e.g. Boom Clay (BE), Opalinus Clay (CH), Callovo-Oxfordian argillite (FR)). The ultimate safety of the corresponding repository concepts depends largely on the capacity of the host formation to limit the flux towards the biosphere of radionuclides (RN) contained in the waste to acceptably low levels. Data for diffusion-driven transfer in these formations shows extreme differences in the measured or modelled behaviour for various radionuclides, e. g. between halogen RN (Cl-36, I-129) and actinides (U-238,U-235, Np-237, Th-232, etc.), which result from major differences between RN of the effects on transport of two phenomena: diffusion and sorption. This paper describes recent research aimed at improving understanding of these two phenomena, focusing on the results of studies carried out during the EC Funmig IP on clayrocks from the above three formations and from the Boda formation (HU). Project results regarding phenomena governing water, cation and anion distribution and mobility in the pore volumes influenced by the negatively-charged surfaces of clay minerals show a convergence of the modelling results for behaviour at the molecular scale and descriptions based on electrical double layer models. Transport models exist which couple ion distribution relative to the clay-solution interface and differentiated diffusive characteristics. These codes are able to reproduce the main trends in behaviour observed experimentally, e.g. D-e(anion) < D-e(HTO) < D-e(cation) and D-e(anion) variations as a function of ionic strength and material density. These trends are also well-explained by models of transport through ideal porous matrices made up of a charged surface material. Experimental validation of these models is good as regards monovalent alkaline cations, in progress for divalent electrostatically-interacting cations (e.g. Sr2+) and still relatively poor for 'strongly sorbing', high K-d cations. Funmig results have clarified understanding of how clayrock mineral composition, and the corresponding organisation of mineral grain assemblages and their associated porosity, can affect mobile solute (anions, HTO) diffusion at different scales (mm to geological formation). In particular, advances made in the capacity to map clayrock mineral grain-porosity organisation at high resolution provide additional elements for understanding diffusion anisotropy and for relating diffusion characteristics measured at different scales. On the other hand, the results of studies focusing on evaluating the potential effects of heterogeneity on mobile species diffusion at the formation scale tend to show that there is a minimal effect when compared to a homogeneous property model. Finally, the results of a natural tracer-based study carried out on the Opalinus Clay formation increase confidence in the use of diffusion parameters measured on laboratory scale samples for predicting diffusion over geological time-space scales. Much effort was placed on improving understanding of coupled sorption-diffusion phenomena for sorbing cations in clayrocks. Results regarding sorption equilibrium in dispersed and compacted materials for weakly to moderately sorbing cations (Sr2+, Cs+, Co2+) tend to show that the same sorption model probably holds in both systems. It was not possible to demonstrate this for highly sorbing elements such as Eu(III) because of the extremely long times needed to reach equilibrium conditions, but there does not seem to be any clear reason why such elements should not have similar behaviour. Diffusion experiments carried out with Sr2+, Cs+ and Eu(III) on all of the clayrocks gave mixed results and tend to show that coupled diffusion-sorption migration is much more complex than expected, leading generally to greater mobility than that predicted by coupling a batch-determined K-d and Ficks law based on the diffusion behaviour of HTO. If the K-d measured on equivalent dispersed systems holds as was shown to be the case for Sr, Cs (and probably Co) for Opalinus Clay, these results indicate that these cations have a D-e value higher than HTO (up to a factor of 10 for Cs+). Results are as yet very limited for very moderate to strongly sorbing species (e.g. Co(II), Eu(III), Cu(II)) because of their very slow transfer characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

The abundance and isotopic composition of Cd in iron meteorites

Cadmium is a highly volatile element and its abundance in meteorites may help better understand volatility-controlled processes in the solar nebula and on meteorite parent bodies. The large thermal neutron capture cross section of 113Cd suggests that Cd isotopes might be well suited to quantify neutron fluences in extraterrestrial materials. The aims of this study were (1) to evaluate the range and magnitude of Cd concentrations in magmatic iron meteorites, and (2) to assess the potential of Cd isotopes as a neutron dosimeter for iron meteorites. Our new Cd concentration data determined by isotope dilution demonstrate that Cd concentrations in iron meteorites are significantly lower than in some previous studies. In contrast to large systematic variations in the concentration of moderately volatile elements like Ga and Ge, there is neither systematic variation in Cd concentration amongst troilites, nor amongst metal phases of different iron meteorite groups. Instead, Cd is strongly depleted in all iron meteorite groups, implying that the parent bodies accreted well above the condensation temperature of Cd (i.e., ≈650 K) and thus incorporated only minimal amounts of highly volatile elements. No Cd isotope anomalies were found, whereas Pt and W isotope anomalies for the same iron meteorite samples indicate a significant fluence of epithermal and higher energetic neutrons. This observation demonstrates that owing to the high Fe concentrations in iron meteorites, neutron capture mainly occurs at epithermal and higher energies. The combined Cd-Pt-W isotope results from this study thus demonstrate that the relative magnitude of neutron capture-induced isotope anomalies is strongly affected by the chemical composition of the irradiated material. The resulting low fluence of thermal neutrons in iron meteorites and their very low Cd concentrations make Cd isotopes unsuitable as a neutron dosimeter for iron meteorites.

Correlated cosmogenic W and Os isotopic variations in Carbo and implications for Hf-W chronology

An obstacle for establishing the chronology of iron meteorite formation using 182Hf-182W systematics (t1/2 = 8.9 Myr) is to find proper neutron fluence monitors to correct for cosmic ray modification of W isotopic composition. Recent studies showed that siderophile elements such as Pt and Os could serve such a purpose. To test and calibrate these neutron dosimeters, the isotopic compositions of W and Os were measured in a slab of the IID iron meteorite Carbo. This slab has a well-characterized noble gas depth profile reflecting different degrees of shielding to cosmic rays. The results show that W and Os isotopic ratios correlate with distance from the pre-atmospheric center. Negative correlations, barely resolved within error, were found between epsilo190Os-epsilo189Os and epsilo186Os-epsilo189Os with slopes of -0.64 ± 0.45 and -1.8(+1.9/-2.1), respectively. These Os isotope correlations broadly agree with model predictions for capture of secondary neutrons produced by cosmic ray irradiation and results reported previously for other groups of iron meteorites. Correlations were also found between epsilo182W-epsilo189Os (slope = 1.02 ± 0.37) and epsilo182W-epsilo190Os (slope = -1.38 ± 0.58). Intercepts of these two correlations yield pre-exposure epsilo182W values of -3.32 ± 0.51 and -3.62 ± 0.23, respectively (weighted average epsilo182W = -3.57 ± 0.21). This value relies on a large extrapolation leading to a large uncertainty but gives a metal-silicate segregation age of -0.5 ± 2.4 Myr after formation of the solar system. Combining the iron meteorite measurements with simulations of cosmogenic effects in iron meteorites, equations are presented to calculate and correct for cosmogenic effects on 182W using Os isotopes.

Geochemistry and petrology of ODP Leg 121 basalts

Basement lavas from Sites 756, 757, and 758 on Ninetyeast Ridge are tholeiitic basalts. Lavas from Sites 756 and 757 appear to be subaerial eruptives, but the lowermost flows from Hole 758A are pillow lavas. In contrast to the compositional variation during the waning stages of Hawaiian volcanism, no alkalic lavas have been recovered from Ninetyeast Ridge and highly evolved lavas were recovered from only one of seven drill sites (DSDP Site 214). All lavas from Site 758 have relatively high MgO contents (8-10 wt%), and they are less evolved than lavas from Sites 756 and 757. Although abundances of alkali metals in these Ninetyeast Ridge basalts were significantly modified by postmagmatic alteration, abundances of other elements reflect magmatic processes. At Site 757 most of the lavas are Plagioclase cumulates, but lava compositions require two compositionally distinct, AhCb-rich parental magmas, perhaps segregated at relatively low mantle pressures. In addition, at both Sites 756 and 758 more than one compositionally distinct parental magma is required. The compositions of these Ninetyeast Ridge lavas, especially those from Site 758, require a source component with a depleted composition; specifically, the abundance ratios Th/Ta, Th/La, Ba/Nb, Ba/La, and La/Ce in these lavas are generally less than the ratios inferred for primitive mantle. Lavas from Ninetyeast Ridge and the Kerguelen Archipelago have very different chondrite-normalized REE patterns, with lower light REE/heavy REE (LREE/HREE) ratios in lavas from Ninetyeast Ridge. However, lavas from Sites 757 and 758 have Pb isotope ratios that overlap with the field defined by lavas from the Kerguelen Archipelago (Weis and Frey, this volume). Therefore, these Ninetyeast Ridge lavas contain more of a component that is relatively depleted in LREE and other highly incompatible elements, but have similar amounts of the component that controls radiogenic Pb isotopes. A model involving mixing between components related to a depleted source and an enriched plume source has been proposed for the oldest Kerguelen Archipelago basalts and Ninetyeast Ridge lavas. Although the incompatible element characteristics of the Ninetyeast Ridge lavas are intermediate between depleted MORB and Kerguelen Archipelago basalts, these data are not consistent with a simple two-component mixing process. A more complex model is required.

Geochemistry of the lower sheeted dike complex of ODP Holes 137-504B and 140-504B

Sixty-three samples representing 379 m of sheeted dikes from Deep Sea Drilling Project/Ocean Drilling Program Site 504B have been analyzed for major and selected trace elements by X-ray fluorescence. The samples range from microcrystalline aphyric basalts to moderately phyric (2%-10% phenocrysts) diabase that are typically multiply saturated with plagioclase, olivine, and clinopyroxene, in order of relative abundance. All analyzed samples are classified as Group D compositions with moderate to slightly elevated compatible elements (MgÆ-value = 0.65% ± 0.03%; Al2O3 = 15.5% ± 0.8%; CaO = 13.0% ± 0.3%; Ni = 114 ± 29 ppm), and unusually depleted levels of moderate to highly incompatible elements (Nb < 1 ppm; Zr = 44 ± 7 ppm; Rb < 0.5 ppm; Ba ~ 1 ppm; P2O5 = 0.07% ± 0.02%). These compositions are consistent with a multistage melting of a normal ocean ridge basaltic mantle source followed by extensive fractionation of olivine, plagioclase, and clinopyroxene. Leg 140 aphyric to sparsely phyric (0%-2% phenocrysts) basalts and diabases are compositionally indistinguishable from similarly phyric samples at higher levels in the hole. An examination of the entire crustal section, from the overlying volcanics through the sheeted dikes observed in Leg 140, reveals no significant trends indicating the enrichment or depletion of Costa Rica Rift Zone source magmas over time. Similarly, significant trends toward increased or decreased differentiation cannot be identified, although compositional patterns reflecting variable amounts of phenocryst addition are apparent at various depths. Below ? 1700 mbsf to the bottom of the Leg 140 section, there is a broadly systematic pattern of Zn depletion with depth, the result of high-temperature hydrothermal leaching. This zone of depletion is thought to be a significant source of Zn for the hydrothermal fluids depositing metal sulfides at ridge-crest hydrothermal vents and the sulfide-mineralization zone, located in the transition between pillow lavas and sheeted dikes. Localized zones of intense alteration (60%-95% recrystallization) are present on a centimeter to meter scale in many lithologic units. Within these zones, normally immobile elements Ti, Zr, Y, and rare-earth elements are strongly depleted compared with "fresher" samples centimeters away. The extent of compositional variability of these elements tends to obscure primary igneous trends if the highly altered samples are not identified or removed. At levels up to 40% (or possibly 60%) recrystallization, Ti, Zr, and Y retain their primary signatures. Although the mechanisms are unclear, it is possible that these intense alteration zones are a source of Y and rare-earth elements for the typically rare-earth-element-enriched hydrothermal vent fluids of mid-ocean ridges.

Element concentrations and isotopic composition of tholeiite and whole rocks samples from the east Mariana Basin

Studies of seafloor magnetic anomaly patterns suggest the presence of Jurassic oceanic crust in a large area in the western Pacific that includes the East Mariana, Nauru and Pigafetta Basins. Sampling of the igneous crust in this area by the Deep Sea Drilling Program (DSDP) and the Ocean Drilling Program (ODP) allows direct evaluation of the age and petrogenesis of this crust. ODP Leg 129 drilled a 51 m sequence of basalt pillows and massive flows in the central East Mariana Basin. 40Ar/39Ar ages determined in this study for two Leg 129 basalts average 114.6 +/- 3.2 Ma. This age is in agreement with the Albian-late Aptian paleontologic age of the overlying sediments, but is distinctively younger than the Jurassic age predicted by magnetic anomaly patterns in the basin. Compositionally, the East Mariana Basin basalts are uniformly low-K tholeiites that are depleted in highly incompatible elements compared to moderately incompatible ones, which is typical of mid-ocean ridge basalts (MORB) erupted near hotspots. The Sr, Nd and Pb isotopic compositions of the tholeiites (87Sr/86Sr init = 0.70360-0.70374; 143Nd/144Nd init = 0.512769-0.512790; 206Pb/204Pb meas = 18.355-18.386) also overlap with some Indian Ocean Ridge MORB, although they are distinct from the isotopic compositions of Jurassic basalts drilled in the Pigafetta Basin, the oldest Pacific MORB. The isotopic compositions of the East Mariana Basin tholeiites are also similar to those of intraplate basalts, and in particular, to the isotopic signature of basalts from the nearby Ontong Java and Manihiki Plateaus. The East Mariana Basin tholeiites also share many petrologic and isotopic characteristics with the oceanic basement drilled in the Nauru Basin at DSDP Site 462. In addition, the new 110.8 +/- 1.0 Ma 40Ar/39Ar age for two flows from the bottom of Site 462 in the Nauru Basin is indistinguishable from the age of the East Mariana Basin flows. Thus, while magnetic anomaly patterns predict that the igneous basement in the Nauru and East Mariana Basins is Jurassic in age, the geochemical and chronological results discussed here suggest that the basement formed during a Cretaceous rifting event within the Jurassic crust. This magmatic and tectonic event was created by the widespread volcanism responsible for the genesis of the large oceanic plateaus of the western Pacific.

Mineralogy and stable oxygen isotope ratios of the Cretaceous-Tertiary boundary

Results of detailed mineralogical, chemical, and oxygen isotope analyses of the clay minerals and zeolites from two Cretaceous-Tertiary (K/T) boundary regions, Stevns Klint, Denmark, and Deep Sea Drilling Project (DSDP) Hole 465A in the north central Pacific Ocean, are presented. In the central part of the Stevns Klint K/T boundary layer, the only clay mineral detected by x-ray diffraction is a pure smectite with > 95 percent expandable layers. No detrital clay minerals or quartz were observed in the clay size fraction in these beds, whereas the clay minerals above and below the boundary layer are illite and mixed-layer smectite-illite of detrital origin as well as quartz. The mineralogical purity of the clay fraction, the presence of smectite only at the boundary, and the d18O value of the smectite (27.2 ± 0.2 per mil) suggest that it formed in situ by alteration of glass. Formation from impact rather than from volcanic glass is supported by its major element chemistry. The high content of iridium and other siderophile elements is not due to the cessation of calcium carbonate deposition and resulting slow sedimentation rates. At DSDP Hole 465A, the principal clay mineral in the boundary zone (80 to 143 centimeters) is a mixed-layer smectite-illite with >=90 percent expandable layers, accompanied by some detrital quartz and small amounts of a euhedral authigenic zeolite (clinoptilolite). The mixed-layer smectite-illite from the interval 118 to 120 centimeters in the zone of high iridium abundance has a very low rare earth element content; the negative cerium anomaly indicates formation in the marine environment. This conclusion is corroborated by the d18O value of this clay mineral (27.1 ± 0.2 per mil). Thus, this mixed-layer smectite-illite formed possibly from the same glass as the K/T boundary smectite at Stevns Klint, Denmark.

Composition of minerals from peridotides at the Mid-Atlantic Ridge, 13°N

Peridotites (diopside-bearing harzburgites) found at 13°N of the Mid-Atlantic Ridge fall into two compositional groups. Peridotites P1 are plagioclase-free rocks with minerals of uniform composition and Ca-pyroxene strongly depleted in highly incompatible elements. Peridotites P2 bear evidence of interaction with basic melt: mafic veinlets; wide variations in mineral composition; enrichment of minerals in highly incompatible elements (Na, Zr, and LREE); enrichment of minerals in moderately incompatible elements (Ti, Y, and HREE) from P1 level to abundances 4-10 times higher toward the contacts with mafic aggregates; and exotic mineral assemblages Cr-spinel + rutile and Cr-spinel + ilmenite in peridotite and pentlandite + rutile in mafic veinlets. Anomalous incompatible-element enrichment of minerals from peridotites P2 occurred at the spinel-plagioclase facies boundary, which corresponds to pressure of about 0.8-0.9 GPa. Temperature and oxygen fugacity were estimated from spinel-orthopyroxene-olivine equilibria. Peridotites P1 with uniform mineral composition record temperature of the last complete recrystallization at 940-1050°C and FMQ buffer oxygen fugacity within the calculation error. In peridotites P2, local assemblages have different compositions of coexisting minerals, which reflects repeated partial recrystallization during heating to magmatic temperatures (above 1200°C) and subsequent reequilibration at temperatures decreasing to 910°C and oxygen fugacity significantly higher than FMQ buffer (delta log fO2 = 1.3-1.9). Mafic veins are considered to be a crystallization product from basic melt enriched in Mg and Ni via interaction with peridotite. The geochemical type of melt reconstructed by the equilibrium with Ca-pyroxene is defined as T-MORB: (La/Sm)_N~1.6 and (Ce/Yb) )_N~2.3 that is well consistent with compositional variations of modern basaltic lavas in this segment of the Mid-Atlantic Ridge, including new data on quenched basaltic glasses.

Element concentrations and Osmium, Platinum and Rhenium isotope ratios of ODP Site 153-920 abyssal peridotites

Abyssal peridotites are normally thought to be residues of melting of the mid-ocean ridge basalt (MORB) source and are presumably a record of processes affecting the upper mantle. Samples from a single section of abyssal peridotite from the Kane Transform area in the Atlantic Ocean were examined for 190Pt-186Os and 187Re-187Os systematics. They have uniform 186Os/188Os ratios with a mean of 0.1198353 +/- 7, identical to the mean of 0.1198340 +/-12 for Os-Ir alloys and chromitites believed to be representative of the upper mantle. While the Pt/Os ratios of the upper mantle may be affected locally by magmatic processes, these data show that the Pt/Os ratio for the bulk upper mantle has not deviated by more than about +/- 30% from a chondritic Pt/Os ratio over 4.5 billion years. These observations are consistent with the addition of a chondritic late veneer after core separation as the primary control on the highly siderophile element budget of the terrestrial upper mantle. The 187Os/188Os of the samples range from 0.12267 to 0.12760 and correlate well with Pt and Pt/Os, but not Re/Os. These relationships may be explained by variable amounts of partial melting with changing D(Re), reflecting in part garnet in the residue, with a model-dependent melting age between about 600 and 1700 Ma. A model where the correlation between Pt/Os and 187Os/188Os results from multiple ancient melting events, in mantle peridotites that were later juxtaposed by convection, is also consistent with these data. This melting event or events are evidently unrelated to recent melting under mid-ocean ridges, because recent melting would have disturbed the relationship between Pt/Os and 187Os/188Os. Instead, this section of abyssal peridotite may be a block of refractory mantle that remained isolated from the convecting portions of the upper mantle for 600 Ma to >1 Ga. Alternatively, Pt and Os may have been sequestered during more recent melting and possibly melt/rock reaction processes, thereby preserving an ancient melting history. If representative of other abyssal peridotites, then the rocks from this suite with subchondritic 187Os/188Os are not simple residues of recent MORB source melting at ridges, but instead have a more complex history. This suite of variably depleted samples projects to an undepleted present-day Pt/Os of about 2.2 and 187Os/188Os of about 0.128-0.129, consistent with estimates for the primitive upper mantle.

Geochemistry of Ninetyeast Ridge basaltic glasses

The Ninetyeast Ridge (NER), a north-south striking, 5,000 km long, 77 to 43 Ma chain of basaltic submarine volcanoes in the eastern Indian Ocean formed as a hotspot track created by rapid northward migration of the Indian Plate over the Kerguelen hotspot. Based on the major and trace element contents of unaltered basaltic glasses from six locations along the NER, we show that the NER was constructed by basaltic magma derived from at least three geochemically distinct mantle sources: (1) a source enriched in highly incompatible elements relative to primitive mantle like the source of the 29-24 Ma flood basalts in the Kerguelen Archipelago; (2) an incompatible element-depleted source similar to the source of Mid-Ocean Ridge Basalt (MORB) erupted along the currently active Southeast Indian Ridge (SEIR); and (3) an incompatible element-depleted source that is compositionally and mineralogically distinct from the source of SEIR MORB. Specifically, this depleted mantle source was garnet-bearing and had higher Y/Dy and Nb/Zr, but lower Zr/Sm, than the SEIR MORB source. We infer that this third source formed as a garnet-bearing residue created during a previous melting event, perhaps an initial partial melting of the mantle hotspot. Subsequently, this residue partially melted over a large pressure range, from slightly over 3 GPa to less than 1 GPa, and to a high extent (~ 30%) thereby creating relatively high SiO2 and FeO contents in some NER basalts relative to SEIR MORB.

Geochemistry and provenance of basaltic clasts within volcaniclastic debris flows at DSDP Site 89-585

Pebble-sized basaltic and glassy clasts were extracted from seamount-derived volcaniclastic debris flows and analyzed for various trace elements, including the rare earths, to determine their genetic relationships and provenance. All the clasts were originally derived from relatively shallow submarine lava flows prior to sedimentary reworking, and have undergone minor low-grade alteration. They are classified into three petrographic groups (A, B, and C) characterized by different phenocryst assemblages and variable abundances and ratios of incompatible elements. Group A (clast from Hole 585) is a hyaloclastite fragment which is olivine-normative and distinct from the other clasts, with incompatibleelement ratios characteristic of transitional or alkali basalts. Groups B and C (clasts from Hole 585A) are quartz-normative, variably plagioclase-clinopyroxene-olivine phyric tholeiites, all with essentially similar ratios of highly incompatible elements and patterns of enrichment in light rare earth elements (chrondrite-normalized). Variation within Groups B and C was governed by low-pressure fractionation of the observed phenocryst phases, whereas the most primitive compositions of each group may be related by variable partial melting of a common source. The clasts have intraplate chemical characteristics, although relative to oceanic hot-spot-related volcanics (e.g., Hawaiian tholeiites) they are marginally depleted in most incompatible elements. The source region was enriched in all incompatible elements, compared with a depleted mid-ocean-ridge basalt source.

Geochemistry of ODP Hole 111-504B basalts (Table 2)

Fifty samples of basalt recovered during ODP Leg 111 from the dikes (Layer 2C) of Hole 504B (1350.0-1562.3 m below seafloor) were analyzed by X-ray-fluorescence techniques. All of the samples are highly depleted in magmaphile elements relative to other mid-ocean ridge basalts, with TiO2 = 0.75-1.24 wt%, Na2O = 1.59-2.22 wt%, Zr = 38-64 ppm, Nb = 0.3-1.5 ppm, and Y = 20-30 ppm (for samples containing 0%-2% phenocrysts), but have ratios of highly incompatible elements similar to normal Type I mid-ocean ridge basalts (e.g., Zr/Nb > 30). Abundances of compatible elements are similar to those of typical mid-ocean ridge basalts, with MgO = 7.2-9.2 wt%, Fe2O3* = 9.3-12.5 wt%, Ni = 55-164 ppm, and Cr = 26-388 ppm. Approximately 2% of the samples recovered from the top part of Hole 504B are similar to normal Type I or Type II ocean floor basalts. However, all of the analyzed Leg 111 samples from Hole 504B are depleted basalts. Aphyric dike rocks from Leg 111 are virtually identical to the depleted aphyric samples recovered from the pillow lavas and dikes in the upper 1075 m of Hole 504B during DSDP Legs 69, 70, and 83, with the exception of elements readily altered by seawater (Sr, Rb, and K). These elements reach a maximum in both abundance and variability in the pillow lavas of the upper 571.5 m of Hole 504B and decline to more constant values in the dike system sampled on Legs 83 and 111, apparently as a result of a decrease in porosity and increase in alteration temperatures relative to the pillow lavas. Based on compositional similarities to the vast majority of the pillows and flows, the dikes sampled on Leg 111 appear to be the feeder system for the pillow lavas in the upper part of Hole 504B. The incompatible-element-depleted compositions of the Costa Rica Rift Zone basalts are consistent with multistage melting of a normal mid-ocean ridge source.

Composition of sediments samples spanning the Cretaceous-Tertiary boundary at ODP Site 207-1259

Ocean Drilling Program (ODP) Leg 207, on the Demerara Rise in the western tropical North Atlantic, recovered multiple Cretaceous-Paleogene boundary sections containing an ejecta layer. Sedimentological, geochemical, and paleontological changes across the boundary closely match patterns expected for a mass extinction caused by a single impact. A normally graded, ~2-cm-thick bed of spherules that is interpreted as a primary air-fall deposit of impact ejecta occurs between sediments of the highest Cretaceous Plummerita hantkeninoides foraminiferal zone and the lowest Paleogene P0 foraminiferal zone. There are no other spherule layers in the section. In addition to extinction of Cretaceous taxa, foraminiferal abundance drops from abundant to rare across the boundary. Ir concentrations reach a maximum of ~1.5 ppb at the top of the spherule bed, and the Ir anomaly is associated with enrichment in other siderophile elements. We attribute the unusually well-preserved and relatively simple stratigraphy to the fact that Demerara Rise was close enough (~4500 km) to the Chicxulub impact site to receive ~2 cm of ejecta, yet was far enough away (and perhaps sheltered by the curve of northern South America) to have been relatively unaffected by impact-induced waves.

Kerb and urban increment of highly time-resolved trace elements in PM10, PM2.5 and PM1.0 winter aerosol in London during ClearfLo 2012

Ambient concentrations of trace elements with 2 h time resolution were measured in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 size ranges at kerbside, urban background and rural sites in London during winter 2012. Samples were collected using rotating drum impactors (RDIs) and subsequently analysed with synchrotron radiation-induced X-ray fluorescence spectrometry (SR-XRF). Quantification of kerb and urban increments (defined as kerb-to-urban and urban-to-rural concentration ratios, respectively), and assessment of diurnal and weekly variability provided insight into sources governing urban air quality and the effects of urban micro-environments on human exposure. Traffic-related elements yielded the highest kerb increments, with values in the range of 10.4 to 16.6 for SW winds (3.3–6.9 for NE) observed for elements influenced by brake wear (e.g. Cu, Sb, Ba) and 5.7 to 8.2 for SW (2.6–3.0 for NE) for other traffic-related processes (e.g. Cr, Fe, Zn). Kerb increments for these elements were highest in the PM10–2.5 mass fraction, roughly twice that of the PM1.0–0.3 fraction. These elements also showed the highest urban increments (~ 3.0), although no difference was observed between brake wear and other traffic-related elements. All elements influenced by traffic exhibited higher concentrations during morning and evening rush hours, and on weekdays compared to weekends, with the strongest trends observed at the kerbside site, and additionally enhanced by winds coming directly from the road, consistent with street canyon effects. Elements related to mineral dust (e.g. Al, Si, Ca, Sr) showed significant influences from traffic-induced resuspension, as evidenced by moderate kerb (3.4–5.4 for SW, 1.7–2.3 for NE) and urban (~ 2) increments and increased concentrations during peak traffic flow. Elements related to regional transport showed no significant enhancement at kerb or urban sites, with the exception of PM10–2.5 sea salt (factor of up to 2), which may be influenced by traffic-induced resuspension of sea and/or road salt. Heavy-duty vehicles appeared to have a larger effect than passenger vehicles on the concentrations of all elements influenced by resuspension (including sea salt) and wearing processes. Trace element concentrations in London were influenced by both local and regional sources, with coarse and intermediate fractions dominated by traffic-induced resuspension and wearing processes and fine particles influenced by regional transport.