Characterizing Pb mobilization from upland soils to streams using (206)Pb/(207)Pb isotopic ratios

Anthropogenically deposited lead (Pb) binds efficiently to soil organic matter, which can be mobilized through hydrologically mediated mechanisms, with implications for ecological and potable quality of receiving waters. Lead isotopic ((206)Pb/(207)Pb) ratios change down peat profiles as a consequence of long-term temporal variation in depositional sources, each with distinctive isotopic signatures. This study characterizes differential Pb transport mechanisms from deposition to streams at two small catchments with contrasting soil types in upland Wales, U.K., by determining Pb concentrations and (206)Pb/(207)Pb ratios from soil core profiles, interstitial pore waters, and stream water. Hydrological characteristics of soils are instrumental in determining the location in soil profiles of exported Pb and hence concentration and (206)Pb/(207)Pb ratios in surface waters. The highest Pb concentrations from near-surface soils are mobilized, concomitant with high dissolved organic carbon (DOC) exports, from hydrologically responsive peat soils with preferential shallow subsurface flows, leading to increased Pb concentrations in stream water and isotopic signatures more closely resembling recently deposited Pb. In more minerogenic soils, percolation of water allows Pb, bound to DOC, to be retained in mineral horizons and combined with other groundwater sources, resulting in Pb being transported from throughout the profile with a more geogenic isotopic signature. This study shows that (206)Pb/(207)Pb ratios can enhance our understanding of the provenances and transport mechanisms of Pb and potentially organic matter within upland soils.

Sr-Nd-Pb Isotope Evidence for Ice-Sheet Presence on Southern Greenland During the Last Interglacial

To ascertain the response of the southern Greenland Ice Sheet (GIS) to a boreal summer climate warmer than at present, we explored whether southern Greenland was deglaciated during the Last Interglacial (LIG), using the Sr-Nd-Pb isotope ratios of silt-sized sediment discharged from southern Greenland. Our isotope data indicate that no single southern Greenland geologic terrane was completely deglaciated during the LIG, similar to the Holocene. Differences in sediment sources during the LIG relative to the early Holocene denote, however, greater southern GIS retreat during the LIG. These results allow the evaluation of a suite of GIS models and are consistent with a GIS contribution of 1.6 to 2.2 meters to the =4-meter LIG sea-level highstand, requiring a significant sea-level contribution from the Antarctic Ice Sheet.

Room-temperature single phase multiferroic magnetoelectrics: Pb(Fe,M)x(Zr,Ti)(1−x)O3 [M=Ta, Nb]

We describe extensive studies on a family of perovskite oxides that are ferroelectric and ferromagnetic at ambient temperatures. The data include x-ray diffraction, Raman spectroscopy, measurements of ferroelectric and magnetic hysteresis, dielectric constants, Curie temperatures, electron microscopy
(both scanning electron microscope and transmission electron microscopy (TEM)) studies, and both longitudinal and transverse magnetoelectric constants a33 and a31. The study extends earlier work to lower Fe, Ta, and Nb concentrations at the B-site (from 15%–20% down to 5%). The magnetoelectric
constants increase supralinearly with Fe concentrations, supporting the earlier conclusions of a key role for Fe spin clustering. The room-temperature orthorhombic C2v point group symmetry inferred from earlier x-ray diffraction studies is confirmed via TEM, and the primitive unit cell size is found to be the basic perovskite Z¼1 structure of BaTiO3, also the sequence of phase transitions with increasing temperature from rhombohedral to orthorhombic to tetragonal to cubic mimics barium titanate.

Giant energy density in [001]-textured Pb(Mg1/3Nb2/3)O-3-PbZrO3-PbTiO3 piezoelectric ceramics

Pb(Zr,Ti)O-3 (PZT) based compositions have been challenging to texture or grow in a single crystal form due to the incongruent melting point of ZrO2. Here we demonstrate the method for achieving 90% textured PZT-based ceramics and further show that it can provide highest known energy density in piezoelectric materials through enhancement of piezoelectric charge and voltage coefficients (d and g). Our method provides more than similar to 5x increase in the ratio d(textured)/d(random). A giant magnitude of d.g coefficient with value of 59 000 x 10(-15) m(2) N-1 (comparable to that of the single crystal counterpart and 359% higher than that of the best commercial compositions) was obtained. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4789854]

Rapid and nondestructive measurement of labile Mn, Cu, Zn, Pb and As in DGT by using field portable-XRF

The technique of diffusive gradients in thin films (DGT) is often employed to quantify labile metals in situ; however, it is a challenge to perform the measurements in-field. This study evaluated the capability of field-portable X-ray fluorescence (FP-XRF) to swiftly generate elemental speciation information with DGT. Biologically available metal ions in environmental samples passively preconcentrate in the thin films of DGT devices, providing an ideal and uniform matrix for XRF nondestructive detection. Strong correlation coefficients (r > 0.992 for Mn, Cu, Zn, Pb and As) were obtained for all elements during calibration. The limits of quantitation (LOQ) for the investigated elements of FP-XRF on DGT devices are 2.74 for Mn, 4.89 for Cu, 2.89 for Zn, 2.55 for Pb, and 0.48 for As (unit: µg cm(-2)). When Pb and As co-existed in the solution trials, As did not interfere with Pb detection when using Chelex-DGT. However, there was a significant enhancement of the Pb reading attributed to As when ferrihydrite binding gels were tested, consistent with Fe-oxyhydroxide surfaces absorbing large quantities of As. This study demonstrates the value of the FP-XRF technique to rapidly and nondestructively detect the metals accumulated in DGT devices, providing a new and simple diagnostic tool for on-site environmental monitoring of labile metals/metalloids

Carrefours de la sociocritique. E´ dite´ par ANTHONY GLINOER. (¼ Texte: revue de critique et de the´orie litte´raire, 45/46). Toronto: E´ ditions Trintexte, 2009. 227 pp. Pb CAD $35.00

French Studies (2012) 66 (1): 125-126 doi:10.1093/fs/knr208

Switching ferroelectric domain configurations using both electric and magnetic fields in Pb(Zr,Ti)O3–Pb(Fe,Ta)O3 single-crystal lamellae

Thin single-crystal lamellae cut from Pb(Zr,Ti)O3–Pb(Fe,Ta)O3 ceramic samples have been integrated into simple coplanar capacitor devices. The influence of applied electric and magnetic fields on ferroelectric domain configurations has been mapped, using piezoresponse force microscopy. The extent to which magnetic fields alter the ferroelectric domains was found to be strongly history dependent: after switching had been induced by applying electric fields, the susceptibility of the domains to change under a magnetic field (the effective magnetoelectric coupling parameter) was large. Such large, magnetic field-induced changes resulted in a remanent domain state very similar to the remanent state induced by an electric field. Subsequent magnetic field reversal induced more modest ferroelectric switching.

Studies of the Room-Temperature Multiferroic Pb(Fe0.5Ta0.5)0.4(Zr0.53Ti0.47)0.6O3: Resonant Ultrasound Spectroscopy, Dielectric, and Magnetic Phenomena

Recently, lead iron tantalate/lead zirconium titanate (PZTFT) was demonstrated to possess large, but unreliable, magnetoelectric coupling at room temperature. Such large coupling would be desirable for device applications but reproducibility would also be critical. To better understand the coupling, the properties of all 3 ferroic order parameters, elastic, electric, and magnetic, believed to be present in the material across a range of temperatures, are investigated. In high temperature elastic data, an anomaly is observed at the orthorhombic mm2 to tetragonal 4mm transition, Tot = 475 K, and a softening trend is observed as the temperature is increased toward 1300 K, where the material is known to become cubic. Thermal degradation makes it impos- sible to measure elastic behavior up to this temperature, however. In the low temperature region, there are elastic anomalies near ≈40 K and in the range 160–245 K. The former is interpreted as being due to a magnetic ordering transition and the latter is interpreted as a hysteretic regime of mixed rhom- bohedral and orthorhombic structures. Electrical and magnetic data collected below room temperature show anomalies at remarkably similar temperature ranges to the elastic data. These observations are used to suggest that the three order parameters in PZTFT are strongly coupled.

Epitaxial ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films on La0.7Sr0.3MnO3 bottom electrode

Epitaxial (001)-oriented 0.7Pb(Mg_0.33Nb_0.67)O₃-0.3PbTiO₃ (PMN-PT) thin films were deposited by pulsed laser deposition on vicinal SrTiO₃ (001) substrates using La_0.7Sr_0.3MnO₃ as bottom electrode. Detailed microstructural investigations of these films were carried out using X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM). Polarization-field hysteresis curves were measured at room temperature. Spontaneous polarization P s , remnant polarization P r and coercive voltage V c were found to be 25 μC/cm², 15 μC/cm² and 0.81 V, respectively. Field dependent dielectric constant measurements exhibited butterfly shaped curves, indicating the true ferroelectric nature of these films at room temperature. The dielectric constant and the dielectric loss at 100 kHz were found to be 238 and 0.14, respectively. The local piezoelectric properties of PMN-PT films were investigated by piezoelectric force microscopy and were found to exhibit a local piezoelectric coefficient of 7.8 pm/V.

Clamping-induced changes of domain morphology in 88%Pb(Zn1/3Nb2/3)O3-12%PbTiO3 (invited)

Domain microstructures in single crystal lamellae of 88%Pb(Zn1/3Nb2/3)O3-12%PbTiO3 (cut from bulk using focused ion beam milling) have been mapped using both piezoresponse force microscopy and transmission electron microscopy. Dramatic changes from mottled microstructures typical of relaxors to larger scale domains typical of ferroelectrics have been noted. Stresses associated with substrate clamping are suspected as the cause for the transition from short- to long-range polar order, akin to effects induced by cation ordering achieved by thermal quenching.

The Nature of Magnetoelectric Coupling in Pb(Zr,Ti)O3-Pb(Fe,Ta)O3

The coupling between magnetization and polarization in a room temperature multiferroic (Pb(Zr,Ti)O3–Pb(Fe,Ta)O3) is explored by monitoring changes in capacitance that occur when a magnetic field is applied in each of three orthogonal directions. Magnetocapacitance effects, consistent with P2M2 coupling, are strongest when fields are applied in the plane of the single crystal sheet investigated.

Availability and transfer to grain of As, Cd, Cu, Ni, Pb and Zn in a barley agri-system: Impact of biochar, organic and mineral fertilizers

With biochar becoming an emerging soil amendment and a tool to mitigate climate change, there are only a few studies documenting its effects on trace element cycling in agriculture. Zn and Cu are deficient in many human diets, whilst exposures to As, Pb and Cd need to be decreased. Biochar has been shown to affect many of them mainly at a bench or greenhouse scale, but field research is not available. In our experiment we studied the impact of biochar, as well as its interactions with organic (compost and sewage sludge) and mineral fertilisers (NPK and nitrosulfate), on trace element mobility in a Mediterranean agricultural field (east of Madrid, Spain) cropped with barley. At harvesting time, we analysed the soluble fraction, the available fraction (assessed with the diffusive gradients in thin gels technique, DGT) and the concentration of trace elements in barley grain. No treatment was able to significantly increase Zn, Cu or Ni concentration in barley grain, limiting the application for cereal fortification. Biochar helped to reduce Cd and Pb in grain, whereas As concentration slightly increased. Overall biochar amendments demonstrated a potential to decrease Cd uptake in cereals, a substantial pathway of exposure in the Spanish population, whereas mineral fertilisation and sewage sludge increased grain Cd and Pb. In the soil, biochar helped to stabilise Pb and Cd, while marginally increasing As release/mobilisation. Some of the fertilisation practises or treatments increased toxic metals and As solubility in soil, but never to an extent high enough to be considered an environmental risk. Future research may try to fortify Zn, Cu and Ni using other combinations of organic amendments and different parent biomass to produce enriched biochars.

Geoquímica de superfície na área envolvente da mineralização do Salgadinho: contribuição para o estudo das fases - suporte do Cu Pb e Zn e para a optimização dos métodos de prospecção geoquímica

Resumo indisponível

Genotoxicity and cytotoxicity of Cr(VI) and Pb²+ in Pisum sativum

A toxicidade dos metais é uma problemática que envolve a saúde humana e o ambiente, sendo necessária uma vigilância constante e uma avaliação dos danos precisa e robusta. As plantas, como principal fonte alimentar e de produtos, são de vital importância à sociedade humana. Devido a serem seres sesseis, este grupo é um dos mais afectados por poluentes, tornandoos objectos de estudo extremamente interessantes. O objectivo desta tese foi avaliar os efeitos genotóxicos e citotóxicos do Cr(VI) e Pb2+ na espécie modelo Pisum sativum L. No capitulo I é introduzida a problemática da toxicidade de ambos os metais, com especial relevo nas plantas, bem como as abordagens mais actuais no estudo da geno e citotoxicidade. No capitulo II são apresentados os resultados dos estudos da genotoxicidade do Pb2+ (II-1) e Cr(VI) (II-2 e II-3), tendo sido realizados analises de dano ao DNA a vários níveis e alterações do ciclo celular (II-1 e II-2), bem como a detecção de instabilidade de microssatelites (II-1 e II-3), que é um indicador do estado funcional do mecanismo de reparação do DNA. O capítulo III aborda o efeito de stresses abióticos na capacidade fotossintética da espécie modelo. No capítulo III-1, realizou-se um estudo pioneiro de avaliação da aplicabilidade da citometria de fluxo no estudo da fotossíntese, mais concretamente no estado funcional e estrutural dos cloroplastos, quando expostos a um inibidor da fotossíntese (Paraquat). Os dados obtidos neste estudo encorajaram a aplicação da técnica nos capítulos III-2 e III-3, nos quais se analisaram os efeitos dos metais Pb2+ (III- 2) e Cr(VI) (III-3) na capacidade fotossintética de plantas expostas a este metal; em estudos que envolveram vários marcadores clássicos, para alem dos da citometria de fluxo. Finalmente, no capítulo IV são apresentadas as conclusões finais do trabalho, uma comparativa entre os efeitos e níveis de toxicidade dos dois metais em estudo e são apontadas algumas perspectivas para futuros estudos, levantadas pelos dados obtidos.