Iron-manganese concretions are common in upper sola of Alfisols in the Inner Bluegrass Region of Kentucky. Their nature and quantities appear to be related to the fluctuation of seasonal perched water tables above clayey argillic horizons. This study was conducted to examine changes in the macro-and micromorphology, chemistry and mineralogy of concretions as a function of size, color and soil depth. Total Mn and Fe contents increased, while SiO2 decreased with concretion size. Black concretions contained higher Mn, while brown concretions were higher in Fe. Crystalline Mn- and Fe-oxides fractionated with a sequential extraction procedure increased, but amorphous Mn and Fe decreased with concretion size. Goethite was the only crystalline Fe oxide mineral identified by X-ray diffraction (XRD) analysis. Manganese oxide minerals were very difficult to detect due to the diffuse nature of their XRD peaks and poor crystallinity. Examination of soil thin sections showed concretions of soil horizons overlying restrictive clayey layers to exhibit differentiated fabrics, sharp external boundaries and generally spherical shapes. Concretions found within clayey restrictive layers or above lithic interfaces usually had less structural organization, softer matrices and diffuse external boundaries due to longer term saturated conditions. Scanning electron microscopy (SEM) examinations suggested that the concretionary matrix, in spite of its density, has numerous cavities and an extensive micropore system within which dissolved plasmic Fe and Mn can diffuse and precipitate.

Freshwater reservoir ages and a potential freshwater diet effect are examined for Manitoba (Canada), using paired samples of contemporaneous terrestrial, freshwater, and omnivore-diet species (Homo sapiens, Gavia sp.). The freshwater diet effect (n=4) varies from 220 to 370 14C years. The FRE (n=12) is temporally variable, with a median of 230 14C years and values up to 880 14C years (or more). Understanding the FRE is important for geologists who reconstruct the postglacial history of an area. It is also important for archaeologists who rely on 14C dating to develop cultural histories, as inhabitants of the Canadian boreal forest have relied upon freshwater resources as a part of their diet. An analysis of the δ13C on 93 freshwater mollusk samples from 11 species demonstrates significant variability, which highlights the difficulty in assigning an “assumed” fractionation correction.

Smoke-derived seed germination is an important trait for plants to colonize postfire habitats. The well-characterized smoke-derived chemicals of karrikins germinate seeds of species not known to occur after fires in nature. Hence, the ecologically relevant germination cues in smoke remain to be explored for native postfire plants. With the fire-chaser, Nicotiana attenuata, we revisit a bioassay-driven fractionation of liquid smoke to identify ecologically relevant germination cues. By combining bioassay-guided fractionation and comparative unbiased metabolomics, we developed a robust and efficient method to identify germination cues in smoke. Syringaldehyde (SAL) was re-identified as a germination cue in fractions of liquid smoke that promote seed germination. SAL was found to be produced during wildfires in the plant's native habitat, efficiently adsorbed to N. attenuata seeds from aqueous solutions and not readily leached from soil and accurately predicted the boundaries of natural fire events that reflect the occurrence of native postfire N. attenuata populations. We propose that SAL is an ecologically relevant germination cue in smoke for this species.

Stable isotope ratios (δ18O and δD) in Antarctic snow and ice are basic proxy indices of climate in ice core studies. The relation between the ratios has important indicative significance for moisture sources. In general, the fractionation characteristics of the two isotopes vary with different meteorological and topographical conditions. This paper presents the spatial and temporal distribution of meteoric water line (MWL) slopes along a traverse from the Zhongshan Station (ZSS) to Dome A in East Antarctica. It is found that the slopes decrease with the increasing distance inland from the coast and the lowest slope occurred at Dome A, where the long-range transported moisture dominates and clear sky snowing have an influence. The slopes in different layers of the snowpack showed a decreasing trend with depth and this is attributed to the fractionation during the interstitial sublimation and re-condensation processes of the water vapor. Frost flower development on the interior plateau surface can greatly alter the depth evolution of the MWL slope. The coastal snow pits also go through the post-depositional smoothing effect, but their influences are not so significant as the inland regions.

Globally, there is an increased demand for sustainable protein sources for animal feed. Grass and forage legumes have the yield potential to become such alternatives, but the protein needs to be separated from the fibres. Red clover, white clover, lucerne and perennial ryegrass were fractionated into a green juice and a fibrous pulp in a screw-press and protein was subsequently precipitated. The nitrogen (N) and amino acid composition of the produced fractions was analysed and the digestibility of dry matter (DM) and N was evaluated using a rat digestibility trial. The aim was to determine the effect of fractionation on composition and digestibility in order to evaluate the four plants as potential protein sources for monogastrics. Protein concentrates with CP concentrations of 240 to 388 g/kg DM and fibrous pulps with CP concentrations of 111 to 216 g/kg DM were produced. The sum of all analysed amino acids was highest in the protein concentrates corresponding to a low concentration of non-protein nitrogen ranging from 4.9% to 10.4%. Only small variations were seen in the amino acid compositions of the different plants and fractions. The concentration of the essential lysine and methionine in the protein concentrate ranged from 6.27 to 6.67 g/16 g N and 1.54 to 2.09 g/16 g N for lysine and methionine, respectively. For all plants species, total tract digestibility of DM and standardised N digestibility was significantly higher in the protein concentrates (60.8% to 76.5% and 75.4% to 85.0% for DM and N, respectively) compared to pulp (21.2% to 43.4% and 52.1% to 72.5% for DM and N, respectively). Digestibility of lucerne protein concentrate (76.5% and 85.0% for DM and N, respectively) was higher than of the unprocessed plant (39.6% and 74.9% for DM and N, respectively), whereas for red and white clover no difference was found. The amino acids methionine and cysteine were limiting for pigs and broilers in all fractions regardless of plant origin, and low scores were also found for lysine. The study demonstrated great potential of using green plants as a protein source for monogastrics because of high protein content, balanced amino acid composition and high digestibility of DM and N. The effects of processing and protein precipitation were pronounced in lucerne where significantly improved digestibility was observed in the protein concentrate. The results from the study provide valuable and enhanced knowledge to the production of alternative and sustainable protein sources for monogastric feed.

Relative concentrations of elements in the minerals of fine-grained sediments can be inferred from element-mineral correlation coefficients. The technique is applied to the distribution of REE in Middle Ordovician shales from South Wales analysed by ICPAES, Leco C/S125 and XRD. Phosphate and chlorite show mid-REE enrichment; muscovite + biotite shows mid-REE depletion. The complementarity of the chlorite and muscovite + biotite patterns may be due to fractionation during diagenetic recrystallisation. Partial correlation analysis is used to infer the presence of zircon.

Ferrihydrite and goethite are amongst the most important substrates for the sorption of contaminants in soil and other environmental media. Isotopic studies of the transition elements, particularly those that exhibit more than one oxidation state and show pH- and/or redox-sensitive behaviour at low temperatures, have been shown to be potentially useful present-day and past proxies for redox (or palaeoredox) conditions. We have made preliminary investigations of Fe isotope fractionation that take place during the formation of FeIII (oxy)hydroxides (FeIIIox) from an aqueous FeIII(NO3)3 solution (FeIIIaq) under laboratory conditions. We have attempted to keep the chemical system simple by excluding 'vital effects' and major changes in redox through the maintenance of abiotic conditions and use of FeIIIaq. Isotopic measurements (56Fe/54Fe, 57Fe/54Fe) of the FeIII(NO3)3 stock solution, the original ferrihydrite and the mixed ferrihydrite/goethite-supernatant FeIIIaq 'pairs' were carried out using a double focusing multicollector inductively coupled plasma mass spectrometer. The results reveal an apparent systematic variation indicating larger ΔFeIIIaq—FeIIIox with decrease in the ferrihydrite:goethite ratio, which reflects the time allowed for isotopic exchange. These values range from virtually zero (0.03%) after 24 h to 0.30% after 70 h. In each FeIIIox-FeIIIaq 'pair' the lighter Fe isotope is partitioned into the FeIIIox, leaving the FeIIIaq isotopically heavier. The observed fractionation reflects isotopic exchange of Fe between the FeIIIox and FeIIIaq upon at least a two step transition of ferrihydrite to goethite.

We present a study on major and trace element geochemistry of some intermediate lithologies from the predominantly basaltic Tibbit Hill volcanic suite in the Humber Zone of the Quebec Appalachians. The intermediate rocks probably formed as lava flows in the volcanic sequence. Their presence shows that this rift-related, c. 554 Ma volcanic sequence is not bimodal (basaltic-comenditic) as previously thought, but consists of a spectrum of compositions ranging from mafic through intermediate to felsic lithologies. The entire volcanic sequence is poly-deformed and generally metamorphosed to greenschist facies conditions.

The intermediate rocks of the Tibbit Hill Formation are trachyandesitic, trachytic and comenditic in composition, and exhibit a wide range of SiO2 content (52 to 68 wt.%). Mg is highly depleted in most samples. Variations of silica versus the alkalis show that most of the samples are alkaline in nature. The rocks display a tholeiitic trend on a standard AFM diagram.

In general, the examined rocks also exhibit a wide range of Sr (15 to 174 ppm), Rb (0 to 156 ppm), Zr (155 to 899 ppm), Nb (18 to 123 ppm), and Y (18 to 94 ppm). The concentration of Hf and Ta are generally low (6.6–14.8 ppm, and 3.3–6.6 ppm, respectively), compared to those of Zr and Nb. Nevertheless, these rocks contain relatively high concentrations of the HFS elements, thus reflecting an enriched source. The suite is also relatively enriched in the rare earth elements (REE), and exhibits fractionated, subparallel REE pattems; the latter are generally uniform and conformable.

Chemical features of these volcanic rocks are typical of those of anorogenic A1 type suites, related to hotspots, mantle plumes, or continental rift zones. This is consistent with earlier interpretation of volcanism associated with an Iapetan RRR triple junction, occurring shortly before the onset of seafloor spreading. At that stage of crustal evolution, alkaline to transitional basaltic magma pierced into the crust, and experienced fractionation to produce the liquids of intermediate composition. Rare earth element geochemical modelling supports the hypothesis that the most evolved composition for which REE data are available (comendite; 67.9 wt.% SiO2) was produced by 20% fractional crystallization of the least evolved trachyandesite (56.7 wt.% SiO2) of this intermediate volcanic assemblage.

Djerfisherite [K6(Cu,Fe,Ni)25S26Cl] has been found as a daughter mineral in melt inclusions in melilite from a Kugda melilitolite. The inclusion mineral assemblage includes pyrrhotite, pentlandite, forsterite, diopside, monticellite, phlogopite, wollastonite, nepheline, sodalite, combeite, calcite, Na-K-Ca carbonate, and hydrated calcium silicates. The djerfisherite is Ni-rich rather than Cu-rich consistent with an ultimate upper mantle magma source. The djerfisherite-bearing assemblage formed from primary carbonate/alkali-rich, melilititic melt inclusions which underwent extreme, closed-system, magmatic to postmagmatic fractionation over a temperature range of >1000° to <500 °C.

Zirconium and Hf are nearly identical geochemically, and therefore most of the crust maintains near-chondritic Zr/Hf ratios of ∼35–40. By contrast, many high-silica rhyolites and granites have anomalously low Zr/Hf (15–30). As zircon is the primary reservoir for both Zr and Hf and preferentially incorporates Zr, crystallization of zircon controls Zr/Hf, imprinting low Zr/Hf on coexisting melt. Thus, low Zr/Hf is a unique fingerprint of effective magmatic fractionation in the crust. Age and compositional zonation in zircons themselves provide a record of the thermal and compositional histories of magmatic systems. High Hf (low Zr/Hf) in zircon zones demonstrates growth from fractionated melt, and Ti provides an estimate of temperature of crystallization (TTiZ) (Watson and Harrison, 2005). Whole-rock Zr/Hf and zircon zonation in the Spirit Mountain batholith, Nevada, document repeated fractionation and thermal fluctuations. Ratios of Zr/Hf are ∼307–40 for cumulates and 18–30 for high-SiO2 granites. In zircons, Hf (and U) are inversely correlated with Ti, and concentrations indicate large fluctuations in melt composition and TTiZ (>100°C) for individual zircons. Such variations are consistent with field relations and ion-probe zircon geochronology that indicate a >1 million year history of repeated replenishment, fractionation, and extraction of melt from crystal mush to form the low Zr/Hf high-SiO2 zone.

A detailed geochemical study is presented of the uppermost Critical Zone, especially of the footwall and hanging wall to the Merensky Reef, at Impala Platinum Mines in the Bushveld Complex. The approximately 100 m-thick sequence below the Merensky Reef consists of 13 distinct layers which have sharp boundaries. They are adcumulates with varying proportions of cumulus plagioclase, orthopyroxene and chromite.

Experimental studies on the composition of coexisting orthopyroxene liquid indicate that the magma which produced this sequence contained between 4 and 6% MgO. The magma from which the Merensky Reef formed was more evolved than the footwall magma.

Significant variations exist for both the En content of orthopyroxene and mg# number of whole-rock analyses in short vertical sections. Pyroxenite and norite always have higher values than anorthosite. Extremely sharp breaks in these values correlate with changes in modal proportions, and argue against both significant fractionation within the studied interval, and infiltration metasomatism. Quantitative modelling shows that the entire footwall section could have contained pyroxene with a uniform primary composition of En82, and that all the variation now observed reflects the effect of reaction with trapped magma.

Two independent methods for determining the proportion of trapped liquid are presented, based on mg# number and incompatible element abundances. Both yield a uniform proportion in all samples of approximately 10%. Immiscible sulphide liquid from the Merensky Reef can be shown to have infiltrated downwards for <5 m, despite its high density contrast with silicate magma, very low viscosity and low crystallization temperature. Residual silicate magma would have had even more restricted mobility. The migration of residual liquid or fluid through pothole structures in the floor of the Merensky Reef is not supported by the present data.

Single crystals of magnetite and of hematite have been dissolved at atmospheric pressure in superheated melts in the systems CaO-MgO-Al2O3-SiO2 and CaO-Al2O3-SiO2, and in a basalt. The crystals were suspended in alumina crucibles containing ca 3.5 cm 3 of melt. Quenched run products were examined optically and by electron probe analysis to establish the distribution of Fe in the glassy charges. There is usually a concentration of Fe at the base of a run product, consistent with flow of dissolved matter from the crystal to the floor. One or more columns of brown, Fe-rich glass may extend from the underside of a relic crystal towards the floor. In CMAS run products, such columns typically extend this entire distance, whereas in the CAS and basalt run products, the columns are either detached from the crystal or do not reach the floor. In the CMAS melt (viscosity ~1 poise) there is apparently continuous release of Fe-bearing melt from around a dissolving crystal, whereas in the CAS and basalt melts (viscosities 7000 and 300 poise, respectively) release is intermittent. In CMAS run products the Fe content is usually greatest, in glass, at the base, and declines gradually upwards; in CAS and basalt runs the bottom of a crucible is occupied by discrete, sharply bounded pillows of Fetich glass, with only slight, or no, gradation in composition. Rising gas bubbles can elevate small blobs of the denser, Fe-bearing melt from around a dissolving crystal, and trains of bubbles in the CAS melt may guide this Fe-bearing melt, against gravity, to the surface of the charge. When the bubbles burst at the surface, this dense melt is left in an unstable location and releases diapirs which descend to the bottom of the crucible. In spite of the evidence that convective fractionation occurs in these haplomagmas and in the basalt, it remains to be demonstrated that it will occur during sidewall crystallization or during the growth of minerals in a cumulus mush to cause magmatic differentiation.

Analysis of stable isotopes in coexisting minerals has found wide application in the study of hydrothermal mineral deposits, particularly for elucidating the temperature and source of the fluid phase involved in mineralisation. For these purposes the temperature dependence of isotopic fractionation in several mineral-water systems has already been established (e.g. Friedman and O'Neil, 1977; O'Neil, 1986). Unfortunately, the oxygen isotope fractionation between cassiterite (SnO2) and water has not been adequately characterized, and this has hindered a full utilization of oxygen isotope data derived from studies of tin deposits (e.g. Harzer, 1970; Patterson et al., 1981; Kelly and Rye, 1979). Because of this situation, an attempt is made here to derive a relationship between temperature and the fractionation of oxygen isotopes (Δ) between quartz and cassiterite, based on the fractionations observed in naturally-occurring assemblages and independent temperature estimates.

Contamination of foods with extrinsic (soil) Fe is common in developing countries. However, the bioavailability of this extrinsic Fe and the extent to which it contributes to Fe nutrition remains unknown. The present study compared the bioavailability of laboratory- and field-threshed teff (Eragrostisis tef (Zucc) Trotter) to evaluate the bioavailablity of extrinsic soil Fe that resulted from the traditional threshing of the staple grain. Using sequential extraction, Fe was fractionated and its solubility was evaluated. The contribution of the additional extrinsic (soil) Fe to the Hb regeneration of Fe-depleted rats was evaluated using a rat Hb depletion–repletion assay. Weanling male Wistar rats (n 24) were fed Fe-deficient diet for 21 d, and were then repleted for 14 d with diets: either laboratory-threshed teff (35 mg Fe/kg; n 8), field-threshed teff (35 mg intrinsic Fe/kg+ 120 mg soil Fe/kg; n 8), or FeSO4 (control; n 8). Fe content of field-threshed teff (29·4 mg/100 g) was four times greater than that of the laboratory-threshed (6·7 mg/100 g) teff (P<0·05). Soil contamination significantly increased the exchangeable, acid-soluble and reducible fractions obtained after sequential extraction. The relative biological value of the field-threshed teff (88 %) was higher than that of the laboratory-threshed (68 %) teff (P<0·05). Soil Fe can contribute to Hb regeneration in Fe-deficient rats. Considering that contamination of foods with soil is common in Ethiopia and other developing countries, it needs to be accounted for in the design and implementation of fortification programmes to prevent excessive intakes. Human studies are needed to confirm the present findings.

A new radiocarbon preparation facility was set up in 2010 at the Godwin Laboratory for Palaeoclimate Research, at the University of Cambridge. Samples are graphitized via hydrogen reduction on an iron powder catalyst before being sent to the Chrono Centre, Belfast, or the Australian National University for accelerator mass spectrometry (AMS) analysis. The experimental setup and procedure have recently been developed to investigate the potential for running small samples of foraminiferal carbonate. By analyzing background values of samples ranging from 0.04 to 0.6 mg C along with similar sized secondary standards, the setup and experimental procedures were optimized for small samples. “Background” modern 14C contamination has been minimized through careful selection of iron powder, and graphitization has been optimized through the use of “small volume” reactors, allowing samples containing as little as 0.08 mg C to be graphitized and accurately dated. Graphitization efficiency/fractionation is found not to be the main limitation on the analysis of samples smaller than 0.07 mg C, which rather depends primarily on AMS ion beam optics, suggesting further improvements in small sample analysis might yet be achieved with our methodology.

Polar regions represent a unique environment for the study of mercury cycling in the global ecosystem. Our research was focused on the assessment of the origin and mobility of mercury in the geochemical cycle in Maritime Antarctic (James Ross Island) by means of atomic absorption spectrometry. Mercury content in a set of extrusive (subaerial, subaqueous) and intrusive (dyke) alkaline basalts ranged between 1.6 µg kg-1 (for samples without xenoliths) and 8 µg kg-1 (for samples containing crustal xenoliths). The mercury content in alkaline basalts indicates a very low concentration of mercury in peridotitic mantle sources. Samples of regolith from James Ross Island were subjected to a comprehensive analytical procedure proposed for ultra-trace mercury concentrations involving fractionation and thermal analysis. Total mercury contents in regolith (2.7–11.3 µg kg-1) did not deviate from the natural background in this part of Antarctica. Additionally, the obtained results are about two orders of magnitude smaller than values formerly assumed for primary mercury contents in basaltic lavas. Our results from Antarctica were compared with mercury contents in basaltic rocks from Greenland and the findings were confirmed. It seems that the input of mercury of geological origin into the polar ecosystem is apparently lower than expected.

To go further in the optimization of treatment planning in selective internal radiationtherapy (SIRT), radiobiological aspects can be accounted for with the OEDIPE software andused to design fractionation protocols. Dosimetry was performed using data from99mTc-MAAevaluations of 10 patients treated for hepatic metastases with SIRT. The maximalinjectable activity (MIA) was calculated, using a tolerance criterion onBEDmean,healthyliver equal to 54 Gy2.5, for different fractionationprotocols, varying the number of fractions, the repartition of activity and the time delaybetween fractions. OEDIPE was also used to calculate BEDmean and the EUD to the tumoralliver (TL) that would be delivered with those MIAs. Compared with a single-injectionprotocol, the MIA is increased on average by 23% ± 3%, 36% ± 5% and 45% ± 7% for fractionation protocols with 2, 3and 4 equal fractions, respectively, while BEDmean,TL is increased by 15% ± 2%, 23% ± 4% and 29% ± 5%. EUDTL, calculated for oneevaluation, is increased by 51%, 115% and 159% using 2, 3 and 4 equal fractions,respectively. For this evaluation, the optimal activity repartition for two-fractionprotocols is (3/4 − 1/4) fortime delays of less than 4 days, (2/3 − 1/3) for time delays between 4 and 6 days and (1/2 − 1/2) for time delays superior to 6 days.Finally, this study confirmed that OEDIPE can be regarded as a tool for treatment planningoptimization and fractionation protocol design in SIRT.

Many continental flood basalt provinces contain rhyolites with ‘A-type’ compositions and many studies have concluded that these higher silica rocks are crustal melts from metapelitic or tonalitic country rock. However, although many of the low-Ti continental flood basalt sequences exhibit a marked a silica gap from ∼55–65 wt. SiO2, many incompatible element ratios, and the calculated eruption temperatures (950–1100°C) are strikingly similar between the rhyolites and associated basalts. Using experimental evidence, derivation of the low-Ti rhyolites from a basaltic parent is shown to be a viable alternative to local crustal melting. Comparison of liquid compositions from experimental melting of both crustal and mantle-derived (basaltic) source materials allows the two to be distinguished on the basis of Al2O3 and FeO content. The basalt experiments are reversible, such that the same melts can be produced by melting or crystallisation. The effect of increased water content in the source is also detectable in the liquid composition. The majority of rhyolites from continental flood basalt provinces fall along the experimental trend for basalt melting/ crystallisation at relatively low water content. The onset of the silica gap in the rhyolites is accompanied by an abrupt decrease in TiO2 and FeO*, marking the start of Fe–Ti oxide crystallisation. Differentiation from 55–65 wt. SiO2 requires ∼30 fractional crystallisation in which magnetite is an important phase, sometimes accompanied by limited crustal contamination. The rapid increase in silica occurs over a small temperature interval and for relatively small changes in the amount of fractional crystallisation, thus intermediate compositions are less likely to be sampled. It is argued that the presence of a silica gap is not diagnostic of a crustal melting origin for either A-type granites or rhyolites in continental flood basalt provinces. The volume of these rhyolites erupted over the Phanerozoic is significant and models for crustal growth should take this substantial contribution from the mantle into account.