Sodium Polytungstate Research Articles

Evaluation of the Adsorption of Mono- and Polytungstates onto Different Types of Clay Minerals and Pahokee Peat

Detailed knowledge about the fate and transport of tungsten in soils is critical to understanding and effectively addressing tungsten behavior in the environment. Recent studies have shown that tungsten anions may polymerize (depending upon concentration, pH, and aquatic geochemistry) in aquatic and soil systems. However, to date, of all soluble tungstate species only monotungstates have been scrutinized to a fair extent in adsorption studies. There is a lack of information evaluating adsorption mechanisms of mono- and polytungstates onto clay minerals. The objective of this work is to investigate the adsorption behavior of monotungstates (sodium tungstate, Na2WO4) and polytungstates (sodium metatungstate, 3Na2WO4·9WO3) onto different types of clay minerals (montmorillonite, kaolinite, illite) and an organic adsorbent (Pahokee peat). Batch equilibrium experiments as a function of concentration (adsorption isotherms) and pH (adsorption envelopes) were performed to provide information about mono- and polytungstate adsorption onto clays and Pahokee peat. Adsorption equilibrium data for mono- and polytungstates onto different types of clay minerals and Pahokee peat were modeled with Freundlich and Langmuir isotherms. The adsorption affinity of clays and Pahokee peat for monotungstates follows the order: Pahokee peat>kaolinite>montmorillonite>illite; for polytungstates, the order is as follows: kaolinite>Pahokee peat>montmorillonite>illite. Results of this study suggest that the charges of the clay mineral surface, tungsten species, and solution pH are the main factors controlling tungsten adsorption. Moreover, polymeric tungsten species (i.e., metatungstate) appear to be more mobile in the environment than monomeric tungstate.

Controls on soil carbon storage and turnover in German landscapes

Soil organic carbon (OC) storage across regions is influenced by climate and parent materials, which determine soil properties like clay content and mineralogy. Within homogeneous soil regions, land use and management practices are further important controls for soil OC contents and turnover. Here, we studied the impact of study region, land use (forest, grassland), forest management (spruce and beech forest under age-class management, unmanaged beech forest), and grassland management (meadow, mown pasture, unmown pasture) on stocks and turnover (based on Δ14C values) of soil OC in density frations of topsoil horizons. Samples were taken from 36 plots in the regions Hainich–Dun (HAI) and the Schwabische Alb (ALB) in Germany. They were separated into two light fractions (free light fraction (LF1), occluded light fraction (LF2)) and the mineral-associated organic matter (MOM) fraction using sodium polytungstate with a density of 1.6 g cm−3. Overall most soil OC was stored in the MOM fraction (73%). Soil OC concentrations and stocks in the MOM fraction differed between study regions, probably due to larger amounts of pedogenic Al- and Fe-oxides in the ALB than in the HAI region. Within each region, forest soils stored significantly higher proportions of total OC in the two LF (33±1.9 %) than grassland soils (20±2.3 %). Different management of forests and grasslands affected the C:N ratio of density fractions, but not OC storage. While modelled soil OC turnover in the MOM was longest of all fractions, all fractions had average Δ14C values above atmospheric values, suggesting a significant fast-cycling component in all of them. Different from stocks, turnover of OC in the MOM fraction were not affected by study region or contents of pedogenic oxides. Radiocarbon contents in the LF were higher for forest than for grassland sites, indicating faster turnover of OC at grassland sites. However, some of the observed difference could originate from different average lifetimes of roots in forests and grasslands. Applying different lag-times for OC input for forests and grasslands significantly reduced the differences in modelled turnover times. Lower Δ14C values of mown pastures than pasture soils in both regions suggest a management effect on soil C turnover in grasslands.We conclude that OC storage in the MOM of topsoil layers is more affected by regional differences in soil texture and mineralogy than by land use and management, while its turnover could not be explained with the studied soil properties. Soil OC storage and turnover in the two LFs is influenced by land use (forest or grassland) and management, but ecosystem specific lag-times have to be considered for modelling OC turnover in these fractions.

Fracionamento físico da matéria orgânica e índice de manejo de carbono de um Argissolo submetido a sistemas conservacionistas de manejo

O fracionamento físico da matéria orgânica (MO) do solo é uma alternativa para a obtenção de frações lábeis utilizadas no cálculo do índice de manejo de carbono (IMC). O objetivo deste trabalho foi avaliar a eficiência do fracionamento físico granulométrico (53µm) e densimétrico, com soluções de iodeto de sódio 1,8Mg m-3 (NaI) ou politungstato de sódio 2,0Mg m-3 (PTS), na separação das frações lábeis (particulada e leve, respectivamente) da MO e o seu uso na estimativa do IMC. Amostras da camada de 0-20cm de um Argissolo Vermelho sob preparo convencional (PC) e plantio direto (PD), combinados com dois sistemas de culturas (aveia/milho e aveia+ervilhaca/milho+caupi), foram avaliadas quanto ao estoque de carbono orgânico total (COT), e nas frações particulada (COP) e leve (C-FL) da MO. No fracionamento físico densimétrico, com a utilização de NaI, foi recuperado menos C-FL em relação ao uso de PTS. A recuperação de COP no fracionamento granulométrico foi intermediária entre a recuperação de FL-NaI e de FL-PTS. O IMC com os dados do fracionamento granulométrico apresentou elevada correlação com o IMC dos dados de fracionamento densimétrico (NaI e PTS), havendo porém uma subestimação dos resultados com o uso de NaI. Os sistemas de manejo sem revolvimento do solo e com maior aporte de resíduos vegetais resultaram em maior IMC, tanto pelo aumento do índice de labilidade quanto do índice de estoque de carbono. O IMC a partir de frações físicas densimétricas da MO demonstra ser um índice eficiente na discriminação de sistemas de manejo, podendo ser utilizado na avaliação das práticas de manejo do solo.

Soil carbon and nitrogen sequestration over an age sequence of Pinus patula plantations in Zimbabwean Eastern Highlands

Forests play a major role in regulating the rate of increase of global atmospheric carbon dioxide (CO2) concentrations creating a need to investigate the ability of exotic plantations to sequester atmospheric CO2. This study examined pine plantations located in the Eastern Highlands of Zimbabwe relative to carbon (C) and nitrogen (N) storage along an age series. Samples of stand characteristics, forest floor (L, F and H) and 0–10, 10–30 and 30–60cm soil depth were randomly taken from replicated stands in Pinus patula Schiede & Deppe of 1, 10, 20, 25, and 30years plus two natural forests. Sodium polytungstate (density 1.6gcm−3) was used to isolate organic matter into free light fraction (fLF), occluded light fraction (oLF) and mineral associated heavy fraction (MaHF). In both natural and planted forests, above ground tree biomass was the major ecosystem C pool followed by forest floor’s humus (H) layer in addition to the 45%, 31% and 24% of SOC contributed by the 0–10, 10–30 and 30–60cm soil depths respectively. Stand age caused significant differences in total organic C and N stocks. Carbon and N declined initially soon after establishment but recovered rapidly at 10years, after which it declined following silvicultural operations (thinning and pruning) and recovered again by 25years. Soil C and N stocks were highest in moist forest (18.3kgCm−2 and 0.66kg of Nm−2) and lowest in the miombo (8.5kgm−2 of C and 0.22kg of Nm−2). Average soil C among Pinus stands was 11.4kg of Cm−2, being highest at 10years (13.7 of Ckgm−2) and lowest at 1year (9.9kg of Cm−2). Some inputs of charcoal through bioturbation over the 25year period contributed to stabilisation of soil organic carbon (SOC) and its depth distribution compared to the one year old stands. Nitrogen was highest at 10years (0.85kg of Nm−2) and least at 30years (0.22kg of Nm−2). Carbon and N in density fractions showed the 20year old stand having similar proportions of fLF and oLF while the rest had significantly higher fLF than oLF. The contribution of fLF C, oLF C and MaHF C to SOC was 8–13%, 1–7% and 90–91% respectively. Carbon and N in all fractions decreased with depth. The mineral associated C was significantly affected by stand age whilst the fLF and oLF were not. Conversion of depleted miombo woodlands to pine plantations yield better C gains in the short and long run whilst moist forest provide both carbon and biodiversity. Our results highlight the importance of considering forestry age based C pools in estimating C sink potential over a rotation and the possibility of considering conservation of existing natural forests as part of future REDD+projects.

The use of sodium polytungstate as an X-ray contrast agent to reduce the beam hardening artifact in hydrological laboratory experiments

Abstract Iodine is conventionally used as a contrast agent in hydrological laboratory experiments using polychromatic X-ray computed tomography (CT) to monitor two-phase Darcy flow in porous geological media. Undesirable beam hardening artifacts, however, render the quantitative analysis of the obtained CT images difficult. CT imaging of porous sand/bead packs saturated with iodine and tungsten-bearing aqueous solutions, respectively, was performed using a medical CT scanner. We found that sodium polytungstate (Na6H2W12O40) significantly reduced the beam hardening compared with potassium iodide (KI). This result is attributable to the location of the K absorption edge of tungsten, which is nearer to the peak of the polychromatic X-ray source spectrum than that of iodine. As sodium polytungstate is chemically stable and less toxic than other heavy element bearing compounds, we recommend it as a promising contrast agent for hydrological CT experiments.

Development of a method for sequential Si extraction from soils

In this paper, we introduce a new method for sequential extraction of different silicon (Si) fractions from soils. The method has been developed based on several series of extraction experiments on well-characterized isolated soil compounds and selected soil samples. Results and implications of these test series are presented, and reasons for the choice of methods for the single steps of the sequential extraction procedure are given.The sequential extraction method separates seven Si fractions. The first four extraction steps are performed on four replicates, which are then split into two by two replicates subjected to two different treatments in the following step. 1) The mobile Si fraction is obtained by extraction by weak electrolyte solution of CaCl2. 2) Si in adsorbed silicic acid is extracted by acetic acid through anion exchange. 3) Si in soil organic matter (SOM) is released by SOM oxidation with H2O2. 4) Si in pedogenic oxides and hydroxides is obtained by treatment with ammonium oxalate and oxalic acid solution under UV-light. 5) In step 5 amorphous silica of biogenic and minerogenic origin is specified. This separation is done in three sub-steps: 5.1) Two samples are directly subjected to NaOH extraction to obtain the total amorphous silica fraction; 5.2) the two other samples are first subjected to bio-opal separation with sodium polytungstate; 5.3) NaOH extraction is then applied to the bio-opal samples to obtain their Si content. The difference between the amounts of Si in the extracts of sub-steps 5.1 and 5.3 is interpreted as Si from minerogenic amorphous silica forming precipitates on surfaces of mineral grains. 6) In addition, total Si concentration is either determined by fusion of sub-samples with lithium borate, dissolution in nitric acid and ICP-OES analysis or by X-ray fluorescence analysis. The share of crystalline silicates is calculated as the difference between total Si and the sum of the Si fractions obtained in extraction steps 1 to 5.Potential drawbacks of the method include i) varying efficiency of the second extraction step, strongly depending on soil composition, ii) overestimation of Si in soil organic matter due to partial dissolution of clay minerals, pedogenic oxides and amorphous silica by H2O2, iii) underestimation of Si in pedogenic oxides and hydroxides due to incomplete destruction of highly crystalline pedogenic oxides or nodules.

An improved cell separation technique for marine subsurface sediments: applications for high-throughput analysis using flow cytometry and cell sorting.

SummaryDevelopment of an improved technique for separating microbial cells from marine sediments and standardization of a high-throughput and discriminative cell enumeration method were conducted. We separated microbial cells from various types of marine sediment and then recovered the cells using multilayer density gradients of sodium polytungstate and/or Nycodenz, resulting in a notably higher percent recovery of cells than previous methods. The efficiency of cell extraction generally depends on the sediment depth; using the new technique we developed, more than 80% of the total cells were recovered from shallow sediment samples (down to 100 meters in depth), whereas ∼ 50% of cells were recovered from deep samples (100–365 m in depth). The separated cells could be rapidly enumerated using flow cytometry (FCM). The data were in good agreement with those obtained from manual microscopic direct counts over the range 104–108 cells cm−3. We also demonstrated that sedimentary microbial cells can be efficiently collected using a cell sorter. The combined use of our new cell separation and FCM/cell sorting techniques facilitates high-throughput and precise enumeration of microbial cells in sediments and is amenable to various types of single-cell analyses, thereby enhancing our understanding of microbial life in the largely uncharacterized deep subseafloor biosphere.

The role of nanominerals and mineral nanoparticles in the transport of toxic trace metals: Field-flow fractionation and analytical TEM analyses after nanoparticle isolation and density separation

Nanominerals and mineral nanoparticles from a mining-contaminated river system were examined to determine their potential to co-transport toxic trace metals. A recent large-scale dam removal project on the Clark Fork River in western Montana (USA) has released reservoir and upstream sediments contaminated with toxic trace metals (Pb, As, Cu and Zn), which had accumulated there as a consequence of more than a century and a half of mining activity proximal to the river’s headwaters near the cities of Butte and Anaconda. To isolate the high-density nanoparticle fractions from riverbed and bank sediments, a density separation with sodium polytungstate (2.8g/cm3) was employed prior to a standard nanoparticle extraction procedure. The stable, dispersed nanoparticulate fraction was then analyzed by analytical transmission electron microscopy (aTEM) and flow field-flow fractionation (FlFFF) coupled to both multi-angle laser light scattering (MALLS) and high-resolution, inductively coupled plasma mass spectrometry (HR-ICPMS). FlFFF analysis revealed a size distribution in the nano range and that the elution profiles of the trace metals matched most closely to that for Fe and Ti. aTEM confirmed these results as the majority of the Fe and Ti oxides analyzed were associated with one or more of the trace metals of interest. The main mineral phases hosting trace metals are goethite, ferrihydrite and brookite. This demonstrates that they are likely playing a significant role in dictating the transport and distribution of trace metals in this river system, which could affect the bioavailability and toxicity of these metals.

Krásnoite, the fluorophosphate analogue of perhamite, from the Huber open pit, Czech Republic and the Silver Coin mine, Nevada, USA

AbstractKrásnoite is a new mineral (IMA2011-040) from the Huber open pit, Krásno ore district, Czech Republic and the Silver Coin mine, Nevada, USA. Krásnoite is the fluorophosphate analogue of perhamite. Krásnoite occurs as compact to finely crystalline aggregates, balls and rosette-like clusters up to 1 mm across. Individual crystals are platy, show a hexagonal outline and can reach 0.1 mm on edge at Krásno and 0.4 mm at Silver Coin. At both localities, krásnoite occurs very late in phosphaterich paragenetic sequences. Krásnoite crystals are partly transparent with a typically pearly lustre, but can also appear greasy (Krásno) or dull (Silver Coin). The streak is white and the hardness is 5 on the Mohs scale. Crystals are brittle, have an irregular fracture, one imperfect cleavage on {001} and are not fluorescent under SW and LW ultraviolet light. Penetration twinning ⊥ {001} is common. The density for both Krásno and Silver Coin material is 2.48(4) g cm–3, measured by the sink–float method in an aqueous solution of sodium polytungstate. The calculated density is 2.476 g cm–3 (Krásno). Krásnoite crystals are uniaxial (+), with ω = 1.548(2) and ε = 1.549(2) (Krásno) and ω = 1.541(1) and ε = 1.543(1) (Silver Coin). The simplified formula of krásnoite is: Ca3Al7.7Si3P4O23.5(OH)12.1F2·8H2O. Krásnoite is trigonal, space group Pm1, with a = 6.9956(4), c = 20.200(2) Å, V = 856.09(9) Å3 and Z = 3. Raman and infrared spectroscopy, coupled with magic-angle spinning nuclear magnetic resonance (MAS–NMR) spectrometry, confirmed the presence of PO3F, PO4, SiO4, H2O and OH in the crystal structure of krásnoite.

Density fractionation and 13C reveal changes in soil carbon following woody encroachment in a desert ecosystem

Woody encroachment has dramatically changed land cover patterns in arid and semiarid systems (drylands) worldwide over the past 150 years. This change is known to influence bulk soil carbon (C) pools, but the implications for dynamics and stability of these pools are not well understood. Working in a Chihuahuan Desert C4 grassland encroached by C3 creosote bush (Larrea tridentata), we used two density fractionation techniques (2 and 7 pool density fractionations) and isotopic analysis to quantify changes in C pools and dynamics among vegetation microsites typical of an encroachment scenario (remnant intact grassland, shrub subcanopies, and in shrub intercanopy spaces within a shrub-encroached area). The C concentration of bulk soils varied with microsite, with almost twice the C in shrub subcanopies as in intercanopy spaces or remnant grasslands. Estimated SOC accumulation rates from Larrea encroachment (4.79 g C m−2 year−1 under canopies and 1.75 g C m−2 year−1 when intercanopy losses were taken into account) were lower than reported for higher productivity Prosopis systems, but still represent a potentially large regional C sink. The composition of soil C varied among microsites, with the shrub subcanopy C composed of proportionally more light fraction C (<1.85 g cm−3) and C that was soluble in sodium polytungstate. Grassland soils contained very little carbonate C compared to shrub subcanopies or shrub intercanopy spaces. Stable isotope analyses indicate that inputs from C3 shrubs were incorporated into all density fractions, even in heavy fractions in which shrub inputs did not change overall C concentration. The seven density fractionation yielded unexpected δ13C patterns, where the two heaviest fractions were strongly depleted in 13C, indicating strong fractionation following organic matter inputs. These results suggest that the utility of isotope mixing models for determining input sources may be limited in systems with similar fractionation patterns. We propose a five pool model for dryland soil C that includes a relatively dynamic light fraction, aggregate and heavy fractions that are stable in size but that reflect dynamic inputs and outputs, a potentially large and seasonally dynamic pool of soluble C, and a large pool of carbonate C. Combined, these results suggest that dryland soil C pools may be more dynamic than previously recognized.

Tungsten-Induced Denaturation and Aggregation of Epoetin Alfa During Primary Packaging as a Cause of Immunogenicity

PurposeFollowing two cases of neutralizing antibodies to epoetin alfa in an investigational clinical study, a small number of individual syringes of two drug product batches were found to contain unusually high levels of aggregation at the end of the clinical trial.MethodsWe undertook an extensive analytical approach to determine the root-cause of the increased aggregation in the affected batches.ResultsSoluble tungsten was found in the syringes, most likely derived from the pins used to manufacture the syringes. Spiking of epoetin alfa with sodium polytungstate or an extract of tungsten pins used to manufacture the syringes induced the formation of aggregates, both dimers that appeared to be covalently linked by disulphide bonds as well as higher-order aggregates. Sodium polytungstate had also a strong denaturing effect on the protein.ConclusionsWe propose tungsten-mediated unfolding and aggregation of epoetin alfa in pre-filled syringes as a potential root cause for increased immunogenicity. This finding may be more broadly applicable to this and other classes of therapeutic proteins.

INCREASES IN SEED DENSITY CAN IMPROVE PLANT STAND AND INCREASE SEEDLING VIGOUR FROM SMALL SEEDS OF WHEAT (TRITICUM AESTIVUM)

SUMMARYEarly vigour in wheat (Triticum aestivum) is an important physiological trait to improve water-use efficiency and grain yield, especially on light soils in Mediterranean-type climates. Potential interactions for plant stand and seedling vigour between seed density and various seed quality treatments were examined for wheat grown in two experiments, conducted under controlled and field environments in Western Australia. Seed lots were graded into seed size classes and seed density fractions using saturated solutions of ammonium sulphate or sodium polytungstate. Dense seed improved plant stands or produced seedlings with greater early seedling vigour than their low-density counterparts in all three field environments. Artificial ageing reduced germination and emergence in the controlled environment. When grown in the field at Merredin, Western Australia, on the sandy soil, plant development was delayed with aged seed, and total leaf area and dry weight of plants were reduced. Fungicide application diminished total plant dry weight in sandy soils, but had a much larger detrimental effect when applied to aged and low-density seeds than normal seeds, retarding development, total leaf area and total plant dry weight. Our results indicate that an increase in seed density, particularly in small seed, can potentially improve plant stand and seedling vigour independently of seed size, and may be especially important for wheat grown on sandy soils of poor fertility and low water-holding capacity. The results also suggest consistency in seedling vigour may benefit from combined screening against small seed size and low seed density, which may also reduce the likelihood of adverse reactions to seed-applied fungicides. More attention should be paid to seed density as a valuable trait for improved reliability in plant stand and seedling vigour.

Use of sodium polytungstate in the granulo-densimetric fractionation of soil material

A solution of sodium polytungstate (SPT) is used as a heavy liquid in global soil studies. This reagent has found wide use because it is nontoxic, incombustible, well soluble, environmentally safe, and of low viscosity. There is a relatively simple and accessible method for its regeneration. The reagent contains no carbon compounds, which is important for studying organic matter with the use of carbon isotopes. However, some chemical properties of SPT should be taken into consideration to ensure the obtainment of incoherent and sorbed solid-phase forms of organic matter. A modification of granulodensimetric fractionation is described that allows separating the solid-phase fractions of soils without changes in the content and isotope composition of the organic carbon and organic nitrogen in the separated material.

Iangreyite: a new secondary phosphate mineral closely related to perhamite

AbstractIangreyite, ideally Ca2Al7(PO4)2(PO3OH)2(OH,F)15·8H2O, is a new mineral (IMA2009-087) from the Silver Coin mine, Nevada, USA and the Krásno ore district, Horní Slavkov, Czech Republic. At Silver Coin, iangreyite occurs as thin, colourless to white or cream, hexagonal tablets up to 0.4 mm in diameter and 0.02 mm thick associated with meurigite-Na, plumbogummite, kidwellite, lipscombite. strengite, chalcosiderite, wardite, leucophosphite, wavellite, goethite, barite, quartz and F-rich perhamite. At Krásno, white, yellowish or light pink iangreyite coatings consist of 0.3 mm wide clusters of minute and very thin intergrown tabular crystals with a maximum diameter of 0.2 mm. Individual iangreyite crystals are transparent with a vitreous lustre, while iangreyite clusters tend to be pearly and translucent. The estimated hardness is 3 on the Mohs scale, the fracture is irregular and the mineral is non-fluorescent under SW and LW ultraviolet light. Individual crystals are somewhat flexible and there is perfect cleavage on ﹛001﹜. The density (Silver Coin), measured by the sink-float method in an aqueous solution of sodium polytungstate, is 2.46(3) g/cm3, while the calculated density is 2.451 g/cm3. Crystals from Silver Coin are uniaxial (+), with the indices of refraction: ε = 1.544(2) and s = 1.554(2), measured in white light, and are non-pleochroic. The empirical formula for iangreyite from Silver Coin (calculated on the basis of 39 anions per formula unit) is: Ca1.42K0.22Na0.09Ba0.03 Sr0.01Al6.51Mg0.09Fe0.02Cu0.01Zn0.01P3.81F5.24H30.21O33.76, while the empirical formula from Krásno is: Ca2.15K0.10Na0.01Ba0.02Sr0.12Al6.28Mg0.01Fe0.12Cu0.08Zn0.01P3.64Si0.43F4.65H29.62O34.35. Iangreyite is trigonal, space group P321 and Z = 1, with the unit-cell parameters (Silver Coin): a = 6.988(1), c = 16.707(3) Å and V= 706.5(2) Å3 and (Krasno): a = 6.989(1), c = 16.782(4) Å and V = 709.8(2) Å3. The structure of iangreyite, modelled from powder data, consists of blocks of the crandallite-type structure that are interconnected along c via corner-sharing of crandallite-block PO4 tetrahedra with A1O2(OH)3 bipyramids. This linkage generates large channels along [110] bounded by 10-member rings of octahedra, tetrahedra and trigonal biyramids, that are occupied by Ca and water molecules.

Evaluation of potentially labile soil organic carbon and nitrogen fractionation procedures

Abstract Particulate organic matter (POM) and light fraction (LF) organic matter are potentially labile (active) fractions of soil organic matter (SOM) that have been shown to be indicators of short-term changes in soil management practices (e.g. tillage, manure and fertilizer applications, and crop rotation). These two fractions consist mainly of partially decomposed plant residues, microbial residues, seeds, and spores forming organo-mineral complexes with soil mineral particles; however, they cannot be used as synonyms because of their different chemical composition and structure. Particulate-OM is recovered by size-based procedures while LF is generally recovered in two distinct fractions [free-LF (FLF) and occluded-LF (OLF)] using density-based solutions in conjunction with soil-aggregate disruption. Solutions used in these density-based separations have most commonly varied in density from 1.6 to 2.0 g cm −3 . Sodium iodide (NaI) and sodium polytungstate (SPT) are the chemicals most often used to prepare the density solutions in LF recovery but comparisons of the effectiveness of two solutions have not been conducted. The objectives of this research were: (1) compare the efficiency of similar density solutions of NaI and SPT in recovering FLF; and (2) compare POM, FLF, and OLF as possible sensitive indices of short-term soil changes due to tillage management. Soil samples were collected at 0–15 cm depth from a cropping system experiment conducted on a silt loam Ultisol. Plots selected for sampling had received either reduced till (RT) or no-till (NT), and cropping was continuous corn silage for a period of 3 years prior to sampling. Solutions of NaI and SPT at densities of 1.6 and 1.8 g cm −3 were used to recover FLF, and OLF was recovered with SPT solution at a density of 2.0 g cm −3 from the soil pellet remaining after FLF recovery with SPT 1.6 g cm −3 . The average total soil organic carbon (SOC) content of these samples was of 12.7 g kg −1 , and carbon-POM (C-POM), carbon-FLF (C-FLF), and carbon-OLF (C-OLF) represented 22.4, 5.5, and 5.2% of it, respectively. In general, C-FLF and nitrogen-FLF (N-FLF) contents recovered did not differ significantly between chemical solutions (NaI or SPT) adjusted to the same density (1.6 or 1.8 g cm −3 ). Increasing the density within a specific solution (NaI or SPT) resulted in significantly higher C-FLF and N-FLF recovery. For instance, C-FLF recovery averaged 637 and 954 mg kg −1 at 1.6 and 1.8 g cm −3 , respectively. For both chemicals increasing density from 1.6 to 1.8 g cm −3 reduced the variability in recovering C-FLF and N-FLF with coefficient of variation values decreasing from a range of 14.9–19.1% for densities of 1.6 g cm −3 to 6.7–10.4% when densities increased to 1.8 g cm −3 . In the present work, POM and OLF were more sensitive than FLF to changes in tillage management, with significantly greater amounts of the sensitive fractions in RT samples. A better sensitivity of FLF would be expected if treatments dealing with residue input (e.g. crop rotation and cover crop) were evaluated.

An experimental study of the stability of liquid bridges subject to shear-induced closed-flow

This paper shows via experiments, the effect of closed-flows on the stability of a liquid bridge. Experiments were conducted with a 3M™ HFE-7500 liquid as the liquid bridge and a mixture of sodium polytungstate solution and glycerine as the outer liquid, which is encapsulated in a cylindrical cavity. Depending on the glycerine content, the Bond number ranged from 0.04 to 0.25. It was shown that a closed-flow in both the encapsulating liquid and the bridge would increase the stability of a non-cylindrical bridge depending on the direction of shear, the Bond number and the bridge volume. It was also shown that, for a given bridge volume and Bond number, there is a capillary number that gives the maximum percentage stabilization. Any further increase in the capillary number flips the direction of the bulge from top to bottom or vice versa thereby decreasing the stabilization and at some capillary number even destabilizing the bridge. The scaling of the problem was analyzed through experimental data.

Silica content in soil solution and its relation with phytolith weathering and silica biogeochemical cycle in Typical Argiudolls of the Pampean Plain, Argentina—a preliminary study

Little is known on the silica biogeochemical cycle in terrestrial environments. The aim of this work is to assess phytolith’s role on the biogeochemical cycle of Si in Typical Argiudolls under different vegetation of the Pampean Plain, Argentina. The work has been developed in three plots with different vegetal cover: grasses and shelter-belt plantations of Acacia melanoxylon–Celtis tala and Eucalyptus globulus–C. tala. The heavy liquid separation in the soil samples was realized with sodium polytungstate. The silica concentration of the soil solution and groundwaters was determined by UV-VIS spectrophotometry. Acacia and eucalyptus do not produce phytoliths; instead, Dactylis glomerata (grass) is a silica-accumulating species, and their phytolith assemblage is composed basically by oblong and crenate, smooth elongate, rectangular and prickles within isolated phytoliths, and smooth long cells articulated. Phytolith content in soils decreases with depth. Total stock of phytoliths represents 5.9 to 12.9 wt.% and is higher in the arboreal plots. In the A horizons, phytolith fraction represents about 59.6 × 103 to 103.5 × 103 kg/ha. In these horizons, 90.7–94.4% of the phytolith content constitutes the labile pool and 9.3–5.6% the stable pool. In the arboreal plots, SiO2 content in soil solution is higher (406–1,106 μmol/L) and decreases with depth, while in the grass plot, SiO2 content is lesser (421–777 μmol/L) and increases with depth; probably because of differences in the nutritional requirements and root design between vegetal species, therefore, in the different depth uptake from the soil solution. In groundwaters, silica content is very high (932 μmol/L). Phytoliths are very representative in Typical Argiudolls and show a great degree of weathering so they could be into account in the biogeochemical studies since they could contribute with silica content in the soil solution, affecting the terrestrial silica biogeochemical cycle.

Pedogenic, mineralogical and land-use controls on organic carbon stabilization in two contrasting soils

Organo-mineral complexation in soils is strongly controlled by pedogenesis, but the mechanisms controlling it and its interaction with cultivation are not yet well understood. We compared the mineralogy and quality of organic carbon (C) among organo-mineral fractions from two soils with contrasting pedogenic origin. Sequential density fractionation (SDF; using 1.6, 1.8, 2.1, 2.4 and 2.6 g mL-1 sodium polytungstate solutions) followed by thermal analysis was applied to a Chernozem from Ellerslie, Alberta, and a Luvisol from Breton, Alberta, each under native and cultivated land uses. Similar clay mineralogy suggested that pedogenic controls on organic C stabilization were related to long-term vegetation cover. In addition to large differences in total organic C quantities, bulk soil and isolated fractions showed significant differences in organic C quality. Samples under native vegetation revealed greater organo-mineral complexation at Ellerslie compared with Breton, as expressed by less solubilisation, more organic C recovered in intermediate-density fractions, and exothermic differential scanning calorimetry peak signals associated with more stable forms of organic C. Long-term cultivation resulted in an overall shift to more stable organo-mineral complexes. The proportion of soil C in the 2.1-2.4 g mL-1 fraction increased under cultivation from 21 to 32% in Breton samples, and from 6 to 16% in Ellerslie samples. The quality of inherited pedogenic soil organic C stored in a soil thus appears to determine its response to long-term cultivation.Key words: Cultivation, sequential density fractionation, organic carbon, organic matter, thermal analysis

Tungsten speciation and toxicity: Acute toxicity of mono- and poly-tungstates to fish

Tungsten is a widely used transition metal for which very limited information on environmental and toxicological effects is available. Of particular interest is the lack of information linking tungsten speciation and environmental effects. Tungsten anions may polymerize (depending upon concentration, pH, and aquatic geochemistry) in aquatic and soil systems. However, to this date, of all soluble tungstate species only monotungstates have been scrutinized to a fair extent in toxicological studies. The objective of this work is a comparative assessment of the acute toxicity of monotungstates (sodium tungstate, Na 2WO 4) and polytungstates (sodium metatungstate, 3Na 2WO 4·9WO 3) to Poecilia reticulate. The experiments have been performed according to the OEDC protocols 203 and 204. LD50 values for 1–14 days show that sodium metatungstate is significantly more toxic to fish than sodium tungstate. Based on LD50 (0.86–3.88 g L −1 or 4.67–21.1×10 −3 mol Na 2WO 4 L −1), sodium tungstate may be classified as a chemical of low toxicity to fish. Sodium metatungstate caused similar fish mortality to sodium tungstate when it was introduced in 55–80 times lower concentrations (in terms of mol L −1) than sodium tungstate. LD50 values for sodium metatungstate range from 0.13 to 0.85 g W L −1 or 5.69 to 38.71×10 −5 mol 3Na 2WO 4·9WO 3 L −1. Based on these values sodium metatungstate can be classified as a moderate toxic agent to fish.

Influence of speciation on tungsten toxicity

Information on tungsten ecotoxicology is very limited. Moreover, it is an even larger lack of information linking tungsten environmental speciation and environmental effects. Soluble tungsten compounds can be released into the environment after corrosion and dissolution of tungsten containing alloys and minerals. Tungsten aquatic chemistry is quite complicated; tungsten anions may polymerize (depending upon concentration and aquatic geochemistry) in aquatic systems at environmentally relevant pHs. However, our present knowledge of tungsten toxicological effects is entirely based on the data obtained in experiments with monotungstates. Here we report experimental results demonstrating that polytungstates are significantly more toxic than monotungstates. Toxicological effects of sodium tungstate and metatungstate have been examined in the standard OECD toxicological tests for Daphnia, algae and earthworms. LD50 and EC50 values for sodium tungstate are more than 10 times larger than those for sodium metatungstate, when expressed in terms of tungsten concentration. This difference increases 12-fold more when LD50 and EC50 are expressed in terms of molecular concentrations. These toxicity patterns have also been observed in the experiment with laboratory aquatic ecosystems. At the ecosystem level, mono- and polytungstates also affect the nitrogen cycle. These findings stress the need for further studies of both environmental speciation of tungsten and toxicity of different tungsten compounds.