Heavy Metals in Crop Plants: Transport and Redistribution Processes on the Whole Plant Level

Copper, zinc, manganese, iron, nickel and molybdenum are essential micronutrients for plants. However, when present in excess they may damage the plant or decrease the quality of harvested plant products. Some other heavy metals such as cadmium, lead or mercury are not needed by plants and represent pollutants. The uptake into the roots, the loading into the xylem, the acropetal transport to the shoot with the transpiration stream and the further redistribution in the phloem are crucial for the distribution in aerial plant parts. This review is focused on long-distance transport of heavy metals via xylem and phloem and on interactions between the two transport systems. Phloem transport is the basis for the redistribution within the shoot and for the accumulation in fruits and seeds. Solutes may be transferred from the xylem to the phloem (e.g., in the small bundles in stems of cereals, in minor leaf veins). Nickel is highly phloem-mobile and directed to expanding plant parts. Zinc and to a lesser degree also cadmium are also mobile in the phloem and accumulate in meristems (root tips, shoot apex, axillary buds). Iron and manganese are characterized by poor phloem mobility and are retained in older leaves.

Solvation-Driven Charge Transfer and Localization in Metal Complexes

In any physicochemical process in liquids, the dynamical response of the solvent to the solutes out of equilibrium plays a crucial role in the rates and products: the solvent molecules react to the changes in volume and electron density of the solutes to minimize the free energy of the solution, thus modulating the activation barriers and stabilizing (or destabilizing) intermediate states. In charge transfer (CT) processes in polar solvents, the response of the solvent always assists the formation of charge separation states by stabilizing the energy of the localized charges. A deep understanding of the solvation mechanisms and time scales is therefore essential for a correct description of any photochemical process in dense phase and for designing molecular devices based on photosensitizers with CT excited states. In the last two decades, with the advent of ultrafast time-resolved spectroscopies, microscopic models describing the relevant case of polar solvation (where both the solvent and the solute molecules have a permanent electric dipole and the mutual interaction is mainly dipole−dipole) have dramatically progressed. Regardless of the details of each model, they all assume that the effect of the electrostatic fields of the solvent molecules on the internal electronic dynamics of the solute are perturbative and that the solvent−solute coupling is mainly an electrostatic interaction between the constant permanent dipoles of the solute and the solvent molecules. This well-established picture has proven to quantitatively rationalize spectroscopic effects of environmental and electric dynamics (time-resolved Stokes shifts, inhomogeneous broadening, etc.). However, recent computational and experimental studies, including ours, have shown that further improvement is required. Indeed, in the last years we investigated several molecular complexes exhibiting photoexcited CT states, and we found that the current description of the formation and stabilization of CT states in an important group of molecules such as transition metal complexes is inaccurate. In particular, we proved that the solvent molecules are not just spectators of intramolecular electron density redistribution but significantly modulate it. Our results solicit further development of quantum mechanics computational methods to treat the solute and (at least) the closest solvent molecules including the nonperturbative treatment of the effects of local electrostatics and direct solvent−solute interactions to describe the dynamical changes of the solute excited states during the solvent response.

Mode of action of claudin peptidomimetics in the transient opening of cellular tight junction barriers

In epithelial/endothelial barriers, claudins form tight junctions, seal the paracellular cleft, and limit the uptake of solutes and drugs. The peptidomimetic C1C2 from the C-terminal half of claudin-1's first extracellular loop increases drug delivery through epithelial claudin-1 barriers. However, its molecular and structural mode of action remains unknown. In the present study, >100 μM C1C2 caused paracellular opening of various barriers with different claudin compositions, ranging from epithelial to endothelial cells, preferentially modulating claudin-1 and claudin-5. After 6 h incubation, C1C2 reversibly increased the permeability to molecules of different sizes; this was accompanied by redistribution of claudins and occludin from junctions to cytosol. Internalization of C1C2 in epithelial cells depended on claudin-1 expression and clathrin pathway, whereby most C1C2 was retained in recyclosomes >2 h. In freeze-fracture electron microscopy, C1C2 changed claudin-1 tight junction strands to a more parallel arrangement and claudin-5 strands from E-face to P-face association - drastic and novel effects. In conclusion, C1C2 is largely recycled in the presence of a claudin, which explains the delayed onset of barrier and junction loss, the high peptide concentration required and the long-lasting effect. Epithelial/endothelial barriers are specifically modulated via claudin-1/claudin-5, which can be targeted to improve drug delivery.

Dissolution-Precipitation in Porous Media: Experiments and Modelling

The evolution of porosity due to dissolution/precipitation processes of minerals and the associated change of transport parameters are of major interest for natural geological environments and engineered underground structures. We designed a reproducible and fast to conduct 2D experiment, which is flexible enough to investigate several process couplings implemented in the numerical code OpenGeosys-GEM (OGS-GEM). We investigated advective-diffusive transport of solutes, effect of liquid phase density on advective transport, and kinetically controlled dissolution/precipitation reactions causing porosity changes. In addition, the system allowed to investigate the influence of microscopic (pore scale) processes on macroscopic (continuum scale) transport. A Plexiglas tank of dimension 10 × 10 cm was filled with a 1 cm thick reactive layer consisting of a bimodal grain size distribution of celestite (SrSO4) crystals, sandwiched between two layers of sand. A barium chloride solution was injected into the tank causing an asymmetric flow field to develop. As the barium chloride reached the celestite region, dissolution of celestite was initiated and barite precipitated. Due to the higher molar volume of barite, its precipitation caused a porosity decrease and thus also a decrease in the permeability of the porous medium. The change of flow in space and time was observed via injection of conservative tracers and analysis of effluents. In addition, an extensive post-mortem analysis of the reacted medium was conducted. We could successfully model the flow (with and without fluid density effects) and the transport of conservative tracers with a (continuum scale) reactive transport model. The prediction of the reactive experiments initially failed. Only the inclusion of information from post-mortem analysis gave a satisfactory match for the case where the flow field changed due to dissolution/precipitation reactions. We concentrated on the refinement of post-mortem analysis and the investigation of the dissolution/precipitation mechanisms at the pore scale. Our analytical techniques combined scanning electron microscopy (SEM) and synchrotron X-ray micro-diffraction/micro-fluorescence performed at the XAS beamline (Swiss Light Source). The newly formed phases include an epitaxial growth of barite micro-crystals on large celestite crystals (epitaxial growth) and a nano-crystalline barite phase (resulting from the dissolution of small celestite crystals) with residues of celestite crystals in the pore interstices. Classical nucleation theory, using well-established and estimated parameters describing barite precipitation, was applied to explain the mineralogical changes occurring in our system. Our pore scale investigation showed limits of the continuum scale reactive transport model. Although kinetic effects were implemented by fixing two distinct rates for the dissolution of large and small celestite crystals, instantaneous precipitation of barite was assumed as soon as oversaturation occurred. Precipitation kinetics, passivation of large celestite crystals and metastability of supersaturated solutions, i.e. the conditions under which nucleation cannot occur despite high supersaturation, were neglected. These results will be used to develop a pore scale model that describes precipitation and dissolution of crystals at the pore scale for various transport and chemical conditions. Pore scale modelling can be used to parameterize constitutive equations to introduce pore-scale corrections into macroscopic (continuum) reactive transport models. Microscopic understanding of the system is fundamental for modelling from the pore to the continuum scale.

Geological and hydrological histories of the Argyre province, Mars

The geologic history of the multi-ringed Argyre impact basin and surroundings has been reconstructed on the basis of geologic mapping and relative-age dating of rock materials and structures. The impact formed a primary basin, rim materials, and a complex basement structural fabric including faults and valleys that are radial and concentric about the primary basin, as well as structurally-controlled local basins. Since its formation, the basin has been a regional catchment for volatiles and sedimentary materials as well as a dominant influence on the flow of surface ice, debris flows, and groundwater through and over its basement structures. The basin is interpreted to have been occupied by lakes, including a possible Mediterranean-sized sea that formed in the aftermath of the Argyre impact event The hypothesized lakes froze and diminished through time, though liquid water may have remained beneath the ice cover and sedimentation may have continued for some time. At its deepest, the main Argyre lake may have taken more than a hundred thousand years to freeze to the bottom even absent any heat source besides the Sun, but with impact-induced hydrothermal heat, geothermal heat flow due to long-lived radioactivities in early martian history, and concentration of solutes in sub-ice brine, liquid water may have persisted beneath thick ice for many millions of years. Existence of an ice-covered sea perhaps was long enough for life to originate and evolve with gradually colder and more hypersaline conditions. The Argyre rock materials, diverse in origin and emplacement mechanisms, have been modified by impact, magmatic, eolian, fluvial, lacustrine, glacial, periglacial, alluvial, colluvial, and tectonic processes. Post-impact adjustment of part of the impact-generated basement structural fabric such as concentric faults is apparent. Distinct basin-stratigraphic units are interpreted to be linked to large-scale geologic activity far from the basin, including growth of the Tharsis magmatic-tectonic complex and the growth into southern middle latitudes of south polar ice sheets. Along with the migration of surface and sub-surface volatiles towards the central part of the primaiy basin, the substantial difference in elevation with respect to the surrounding highlands and Tharsis and the Thaumasia highlands result in the trapping of atmospheric volatiles within the basin in the form of fog and regional or local precipitation, even today. In addition, the impact event caused long-term (millions of years) hydrothermal activity, as well as deep-seated basement structures that have tapped the internal heat of Mars, as conduits, for far greater time, possibly even today. This possibility is raised by the observation of putative open-system pingos and nearby gullies that occur in linear depressions with accompanying systems of faults and fractures. Long-term water and heat energy enrichment, complemented by the interaction of the nutrient-enriched primordial crustal and mantle materials favorable to life excavated to the surface and near-surface environs through the Argyre impact event, has not only resulted in distinct geomorphology, but also makes the Argyre basin a potential site of exceptional astrobiological significance. (C) 2015 Elsevier Inc. All rights reserved.

Chemical, and Sr and Li isotopic composition of pore fluids and sediments from ODP Leg 170 and Leg 205 sites

Pore fluid and sediment chemical and isotopic data were obtained for samples from Ocean Drilling Program (ODP) Leg 205 Sites 1253, 1254, and 1255 in the Costa Rica subduction zone. The chemical and isotopic data reported here were generated in our shore-based laboratories to complement shipboard inorganic geochemical data. Li isotopic analyses were carried out by L.-H. Chan at Louisiana State University (USA). The data reported herein include fluoride, bromide, rubidium, cesium, and barium concentrations; Li and Sr isotopic compositions in pore fluids; and Rb, Cs, and Ba concentrations in representative bulk sediments. The data also include new pore fluid fluoride and bromide concentrations from corresponding ODP Leg 170 Sites 1039, 1040, and 1043. O.M. Saether's Site 1039 and 1040 fluoride concentration data are shown for comparison. Basal sediment fluoride concentrations and Li and Sr isotope ratios at both Sites 1253 and 1039 show reversals that approach modern seawater values. Br/Cl ratios are, however, conservative throughout the sediment section at Sites 1039 and 1253. The observed sharp F and Br concentration maxima, Rb and K concentration minima, the most radiogenic 87Sr/86Sr ratios, and highest 7Li values along the décollement and fracture zone (Sites 1040, 1043, 1254, and 1255) strengthen the evidence obtained during Leg 170 that a deeply sourced fluid, originating from fluid-rock reactions at ~150°C and corresponding to between 10 and 15 km depth, is transporting solutes to the ocean.

Cloride and bromide concentrations and Br-/Cl- molar ratios in pore fluids at ODP Site 134-833

Other than halite diagenesis and organic matter degradation, Cl- and Br- are considered to be conservative in marine pore fluids. Consequently, Br-/Cl- ratios should remain constant during most diagenetic reactions. Nonetheless, Br-/Cl- molar ratios decrease to 0.00127 (~18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl- and Br-. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br-/Cl- ratio. Some Cl- may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br-/Cl- ratio. The limited source of Cl- suggests that proportionately more Br- than Cl- is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl- and Br- may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust.

Respuestas fisiológicas a la suplementación con calcio de plántulas de vinal (Prosopis ruscifolia G.) estresadas con NaCl

Vinal (Prosopis ruscifolia G.) es una especie de importancia forestal, nativa de la Región Fitogeográfica del Chaco Occidental, altamente tolerante al estrés salino. El objetivo de este trabajo fue poner a prueba la hipótesis de que la suplementación con CaSO4 disminuye la concentración de iones tóxicos en plántulas de vinal, e incrementa la concentración de prolina, permitiendo un ajuste osmótico. Las plántulas se cultivaron en solución nutritiva de Hoagland al 25%, con o sin la adición de 0,4 mol L-1 de NaCl, y con o sin suplementación de 5 ó 10 mmol L-1 de CaSO4. Se determinó la materia seca, composición mineral, contenido relativo de agua y concentraciones de prolina y azúcares solubles. Se utilizó un diseño experimental completamente aleatorizado con cinco repeticiones, y los resultados se analizaron con ANOVA y test de Tukey. Los resultados obtenidos en este trabajo confirman el rol protector del Ca+2, a través de la manutención de las concentraciones de Ca+2, K+ y Mg+2 en los tejidos, la inhibición de la absorción de Na+ y el ajuste osmótico mediante la síntesis de solutos osmocompatibles.

Interstitial-water chemistry and stable isotope record of Prydz Bay sediments

Leg 119 of the Ocean Drilling Program (ODP) provided the first opportunity to study the interstitial-water chemistry of the eastern Antarctic continental margin. Five sites were cored in a northwest-southeast transect of Prydz Bay that extended from the top of the continental slope to within 30 km of the coastline. Geological studies of the cores reveal a continental margin that has evolved through terrestrial, glacial, and glacial-marine environments. Chemical and stable isotopic analyses of the interstitial-waters were performed to determine the types of depositional environments and the diagenetic and hydrologic processes that are operating in this unusual marine environment. Highly compacted glacial sediments provide an effective barrier to the vertical diffusion of interstitial-water solutes. Meteoric water from the Antarctic continent appears to be flowing into Prydz Bay sediments through the sequence of terrestrial sediments that lie underneath the glacial sediments. The large amounts of erosion associated with glacial advances appear to have had the effect of limiting the amount of marine organic matter that is incorporated into the sediments on the continental shelf. Although all of the sites cored in Prydz Bay exhibit depletions in dissolved sulfate with increasing depth, the greatest bacterial activity is associated with a thin layer of diatom ooze that coats the seafloor of the inner bay. Results of alkalinity modeling, thermodynamic calculations, and strontium analyses indicate that (1) ocean bottom waters seaward of Site 740 are undersaturated with respect to both calcite and aragonite, (2) interstitial waters at each site become saturated or supersaturated with respect to calcite and aragonite with increasing depth, (3) precipitation of calcium carbonate reduces the alkalinity of the pore waters with increasing depth, and (4) recrystallization of aragonite to calcite accounts for 24% of the pore-water strontium. Weathering of unstable terrestrial debris and cation exchange between clay minerals and pore fluids are the most probable chemical processes affecting interstitial water cation gradients.

Direct visualization of solute locations in laboratory ice samples, links to videos

Many important chemical reactions occur in polar snow, where solutes may be present in several reservoirs, including at the air-ice interface and in liquid-like regions within the ice matrix. Some recent laboratory studies suggest chemical reaction rates may differ in these two reservoirs. While investigations have examined where solutes are found in natural snow and ice, similar research has not identified solute locations in laboratory samples, nor the possible factors controlling solute segregation. To address this, we examined solute locations in ice samples prepared from either aqueous cesium chloride (CsCl) or Rose Bengal solutions that were frozen using several different methods. Samples frozen in a laboratory freezer had the largest liquid-like inclusions and air bubbles, while samples frozen in a custom freeze chamber had somewhat smaller air bubbles and inclusions; in contrast, samples frozen in liquid nitrogen showed much smaller concentrated inclusions and air bubbles, only slightly larger than the resolution limit of our images (~2 µm). Freezing solutions in plastic versus glass vials had significant impacts on the sample structure, perhaps because the poor heat conductivity of plastic vials changes how heat is removed from the sample as it cools. Similarly, the choice of solute had a significant impact on sample structure, with Rose Bengal solutions yielding smaller inclusions and air bubbles compared to CsCl solutions frozen using the same method. Additional experiments using higher-resolution imaging of an ice sample show that CsCl moves in a thermal gradient, supporting the idea that the solutes in ice are present in liquid-like regions. Our work shows that the structure of laboratory ice samples, including the location of solutes, is sensitive to freezing method, sample container, and solute characteristics, requiring careful experimental design and interpretation of results.

Chemical and isotope compositions of bottom sediments from ODP Leg 168, Eastern Flank of the Juan de Fuca Ridge

Ten sites were drilled in the eastern flank of the Juan de Fuca Ridge (North East Pacific) along a 100 km-long east-west transect during Leg ODP 168. This study focuses on the mineralogical and chemical study of sediments that overly basaltic basement through which seawater circulates. Silicate authigenesis was observed in the sediment layer just above basement at sites located more than 30 km from the ridge axis. This sediment alteration is particularly abundant at ODP Sites 1031 and 1029 where authigenic formation of Fe-Mg rich smectite and zeolite and the dissolution of biogenic calcite are observed. Comparison of the distribution of the alteration in the basal sediment collected along this transect suggests that diffusional transport of aqueous solutes from the basement into the overlying sediment cannot produce the mineralogical and chemical changes in the basal sediments at Sites 1031 located on a basement topographic high, and at Site 1029 located at about 50 km from the ridge axis on a buried basement area. Vertical advection of basement fluid though the sediment section is required to produce this alteration. These processes are still active at Site 1031, based on systematic variations in pore-water profiles and temperatures obtained from stable isotopic data on calcium carbonates and the nature of authigenic minerals. At Site 1029, there is no present-day advection of basement fluids though the sediment section, suggesting that this is a relic site for fluid flow.

(Table 2) Composition of the deapest pore fluids from ODP Holes 168-1030B and 168-1031A

On the eastern flank of the Juan de Fuca Ridge, reaction between upwelling basement fluid and sediment alters hydrothermal fluxes of Ca, SiO2(aq), SO4, PO4, NH4, and alkalinity. We used the Global Implicit Multicomponent Reactive Transport (GIMRT) code to model the processes occurring in the sediment column (diagenesis, sediment burial, fluid advection, and multicomponent diffusion) and to estimate net seafloor fluxes of solutes. Within the sediment section, the reactions controlling the concentrations of the solutes listed above are organic matter degradation via SO4 reduction, dissolution of amorphous silica, reductive dissolution of amorphous Fe(III)-(hydr)oxide, and precipitation of calcite, carbonate fluorapatite, and amorphous Fe(II)-sulfide. Rates of specific discharge estimated from pore-water Mg profiles are 2 to 3 mm/yr. At this site the basement hydrothermal system is a source of NH4, SiO2(aq), and Ca, and a sink of SO4, PO4, and alkalinity. Reaction within the sediment column increases the hydrothermal sources of NH4 and SiO2(aq), increases the hydrothermal sinks of SO4 and PO4, and decreases the hydrothermal source of Ca. Reaction within the sediment column has a spatially variable effect on the hydrothermal flux of alkalinity. Because the model we used was capable of simulating the observed pore-water chemistry by using mechanistic descriptions of the biogeochemical processes occurring in the sediment column, it could be used to examine the physical controls on hydrothermal fluxes of solutes in this setting. Two series of simulations in which we varied fluid flow rate (1 to 100 mm/yr) and sediment thickness (10 to 100 m) predict that given the reactions modeled in this study, the sediment section will contribute most significantly to fluxes of SO4 and NH4 at slow flow rates and intermediate sediment thickness and to fluxes of SiO2(aq) at slow flow rates and large sediment thickness. Reaction within the sediment section could approximately double the hydrothermal sink of PO4 over a range of flow rates and sediment thickness, and could slightly decrease (by

The formation of a subsurface anticyclonic eddy in the Peru-Chile Undercurrent and its impact on the near-coastal salinity, oxygen and nutrient distributions

The formation of a subsurface anticyclonic eddy in the Peru-Chile Undercurrent (PCUC) in January and February 2013 is investigated using a multi-platform four-dimensional observational approach. Research vessel, multiple glider and mooring-based measurements were conducted in the Peruvian upwelling regime near 12°30'S. The dataset consists of more than 10000 glider profiles and repeated vessel-based hydrography and velocity transects. It allows a detailed description of the eddy formation and its impact on the near-coastal salinity, oxygen and nutrient distributions. In early January, a strong PCUC with maximum poleward velocities of ca. 0.25 m/s at 100 to 200 m depth was observed. Starting on January 20 a subsurface anticyclonic eddy developed in the PCUC downstream of a topographic bend, suggesting flow separation as the eddy formation mechanism. The eddy core waters exhibited oxygen concentrations less than 1mol/kg, an elevated nitrogen-deficit of ca. 17µmol/l and potential vorticity close to zero, which seemed to originate from the bottom boundary layer of the continental slope. The eddy-induced across-shelf velocities resulted in an elevated exchange of water masses between the upper continental slope and the open ocean. Small scale salinity and oxygen structures were formed by along-isopycnal stirring and indications of eddy-driven oxygen ventilation of the upper oxygen minimum zone were observed. It is concluded that mesoscale stirring of solutes and the offshore transport of eddy core properties could provide an important coastal open-ocean exchange mechanism with potentially large implications for nutrient budgets and biogeochemical cycling in the oxygen minimum zone off Peru.