Parsimonious methodology for synthesis of silver and copper functionalized cellulose.

Metal nanomaterials, such as silver and copper, are often incorporated into commercial textiles to take advantage of their Antibacterial and antiviral properties. The goal of this study was to identify the most parsimonious method for the synthesis of silver, copper, or silver/copper bimetallic treated textiles. To accomplish this eight different methods were employed to synthesize silver, copper, and silver/copper functionalized cotton batting textiles. Using silver and copper nitrate as precursors, different reagents were used to initiate/catalyze the deposition of metal, including: (1) no additive, (2) sodium bicarbonate, (3) green tea, (4) sodium hydroxide, (5) ammonia, (6, 7) sodium hydroxide/ammonia at a 1:2 and 1:4 ratio, and (8) sodium borohydride. The use of sodium bicarbonate as a reagent to reduce silver onto cotton has not been used previously in literature and was compared to established methods. All synthesis methods were performed at 80 °C for one hour following textile addition to the solutions. The products were characterized by x-ray fluorescence (XRF) analysis for quantitative determination of the metal content and x-ray absorption near edge structure (XANES) analysis for silver and copper speciation on the textile. Scanning electron microscopy (SEM) with energy dispersive x-ray (EDX) and size distribution inductively coupled plasma mass spectrometry (ICP-MS) were used to further characterize the products of the sodium bicarbonate, sodium hydroxide, and sodium borohydride synthesis methods following ashing of the textile. For the silver treatment methods (1 mM Ag +), sodium bicarbonate and sodium hydroxide resulted in the highest amounts of silver on the textile (8900 mg Ag/kg textile and 7600 mg Ag/kg textile) and for copper treatment (1 mM Cu +) the sodium hydroxide and sodium hydroxide/ammonium hydroxide resulted in the highest amounts of copper on the textile (3800 mg Ag/kg textile and 2500 mg Ag/kg textile). Formation of copper oxide was dependent on the pH of the solution, with 4 mM ammonia and other high pH solutions resulting in majority of the copper on the textile existing as copper oxide, with smaller amounts of ionic-bound copper. The identified parsimonious methods will lend themselves to the efficient manufacturing of antibacterial and antiviral textiles, or the development of multifunctionalized smart textiles. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-023-05099-7.

Gauge invariant and gauge dependent aspects of topological walking colloidal bipeds.

Paramagnetic colloidal spheres assemble to colloidal bipeds of various length in an external magnetic field. When the bipeds reside above a magnetic pattern and we modulate the direction of the external magnetic field, the rods perform topologically distinct classes of protected motion above the pattern. The topological protection allows each class to be robust against small continuous deformations of the driving loop of the external field. We observe motion of the rod from a passive central sliding and rolling motion for short bipeds toward a walking motion with both ends of the rod alternately touching down on the pattern for long bipeds. The change of character of the motion occurs in form of discrete topological transitions. The topological protection makes walking a form of motion robust against the breaking of the non symmorphic symmetry. In patterns with non symmorphic symmetry walking is reversible. In symmorphic patterns lacking a glide plane the walking can be irreversible or reversible involving or not involving ratchet jumps. Using different gauges allows us to unravel the active and passive aspects of the topological walks.

CRISPR/Cas9-mediated ELANE knockout enables neutrophilic maturation of primary hematopoietic stem and progenitor cells and induced pluripotent stem cells of severe congenital neutropenia patients.

A Autosomal-dominant ELANE mutations are the most common cause of severe congenital neutropenia. Although the majority of congenital neutropenia patients respond to daily granulocyte colony stimulating factor, approximately 15 % do not respond to this cytokine at doses up to 50 µg/kg/day and approximately 15 % of patients will develop myelodysplasia or acute myeloid leukemia. "Maturation arrest," the failure of the marrow myeloid progenitors to form mature neutrophils, is a consistent feature of ELANE associated congenital neutropenia. As mutant neutrophil elastase is the cause of this abnormality, we hypothesized that ELANE associated neutropenia could be treated and "maturation arrest" corrected by a CRISPR/Cas9-sgRNA ribonucleoprotein mediated ELANE knockout. To examine this hypothesis, we used induced pluripotent stem cells from two congenital neutropenia patients and primary hematopoietic stem and progenitor cells from four congenital neutropenia patients harboring ELANE mutations as well as HL60 cells expressing mutant ELANE We observed that granulocytic differentiation of ELANE knockout induced pluripotent stem cells and primary hematopoietic stem and progenitor cells were comparable to healthy individuals. Phagocytic functions, ROS production, and chemotaxis of the ELANE KO (knockout) neutrophils were also normal. Knockdown of ELANE in the mutant ELANE expressing HL60 cells also allowed full maturation and formation of abundant neutrophils. These observations suggest that ex vivo CRISPR/Cas9 RNP based ELANE knockout of patients' primary hematopoietic stem and progenitor cells followed by autologous transplantation may be an alternative therapy for congenital neutropenia.

Colloidal trains.

Single and double paramagnetic colloidal particles are placed above a magnetic square pattern and are driven with an external magnetic field processing around a high symmetry direction of the pattern. The external magnetic field and that of the pattern confine the colloids into lanes parallel to a lattice vector of the pattern. The precession of the external field causes traveling minima of the magnetic potential along the direction of the lanes. At sufficiently high frequencies of modulation, only the doublets respond to the external field and move in direction of the traveling minima along the lanes, while the single colloids cannot follow and remain static. We show how the doublets can induce a coordinated motion of the single colloids building colloidal trains made of a chain of several single colloids transported by doublets.

Arsenic speciation in the bracket fungus Fomitopsis betulina from contaminated and pristine sites.

Uptake, distribution and speciation of arsenic (As) were determined in the bracket fungus Fomitopsis betulina (previously Piptoporus betulinus), commonly known as the birch polypore, collected from a woodland adjacent to a highly contaminated former mine in the Southwest UK and at an uncontaminated site in Quebec, Canada, with no past or present mining activity. The fruiting body was divided into cap, centre and pores representing the top, middle and underside to identify trends in the distribution and transformation of As. Total As, determined by inductively coupled plasma-mass spectrometry (ICP-MS), was approximately tenfold higher in the mushroom from the contaminated compared to the uncontaminated site. Overall, accumulation of As was low relative to values reported for some soil-dwelling species, with maximum levels of 1.6 mg/kg at the contaminated site. Arsenic speciation was performed on aqueous extracts via both anion and cation high-performance liquid chromatography-ICP-MS (HPLC-ICP-MS) and on whole dried samples using X-ray absorption near edge structure (XANES) analysis. Seven As species were detected in F. betulina from the contaminated site by HPLC-ICP-MS: arsenite (AsIII), arsenate (AsV), dimethylarsinate (DMAV), methylarsonate (MAV), trimethylarsine oxide (TMAO), tetramethylarsonium ion (Tetra) and trace levels of arsenobetaine (AB). The same As species were observed at the uncontaminated site with the exception of TMAO and Tetra. Arsenic species were localized throughout the fruiting body at the contaminated site, with the cap and pores containing a majority of AsV, only the cap containing TMAO, and the pores containing higher concentrations of DMAV and MAV as well as tetra and a trace of AB. XANES analysis demonstrated that the predominant form of As at the contaminated site was inorganic AsIII coordinated with sulphur or oxygen and AsV coordinated with oxygen. This is the first account of arsenic speciation in F. betulina or any fungi of the family Fomitopsidaceae.

Edge transport at the boundary between topologically equivalent lattices.

Edge currents of paramagnetic colloidal particles propagate at the edge between two topologically equivalent magnetic lattices of different lattice constant when the system is driven with periodic modulation loops of an external magnetic field. The number of topologically protected particle edge transport modes is not determined by a bulk-boundary correspondence. Instead, we find a rich variety of edge transport modes that depend on the symmetry of both the edge and the modulation loop. The edge transport can be ratchet-like or adiabatic, time or non-time reversal symmetric. The topological nature of the edge transport is classified by a set of winding numbers around bulk fence points extended by winding numbers around edge specific bifurcation points that cannot be deduced from the two bulk lattices.

Estimating the number of airports potentially contaminated with perfluoroalkyl and polyfluoroalkyl substances from aqueous film forming foam: A Canadian example.

Assessing the extent to which emerging contaminants (ECs) such as perfluoroalkyl and polyfluoroalkyl substances (PFAS) have been released into the environment is one of the foundations for developing effective management and remediation strategies for impacted sites. PFAS are known to have caused the contamination of soil, groundwater, and surface water as a result of aqueous film forming foam (AFFF) being accidentally or intentionally released into the environment. To date, the scope of the issue has not been evaluated in Canada. In this study we developed a framework, in the form of a decision tree, to estimate the number of potentially PFAS impacted airport sites in Canada as a result of AFFF releases. The screening process was completed using publicly available resources including airport websites, the Canadian Owners and Pilots Association website, Sky Vector, Transport Safety Board of Canada aviation investigation reports, the Aviation Safety Network website, and Google maps. The methodology presented in this study could be used to identify additional PFAS impacted sites in Canada or other jurisdictions worldwide. 2071 airport/heliport sites in Canada were investigated with indications that 152 (7%) of these sites likely have PFAS contamination as a result of the use of AFFF at firefighter training areas (FFTAs) and/or accidents where fires occurred. In addition, another 268 sites (13%) were identified as possibly impacted with PFASs primarily as a result of the location having the ability to store and dispense petroleum products, and therefore having AFFF systems onsite. Surficial geology was also identified for all sites determined to likely have PFAS contamination. An estimated 42.8% had surficial geology composed of sand, 27% had clay, 19.7% organic-based, with the remaining sites found on cryosols or rock. Methodological validation was also completed. The procedure used in this study successfully predicted occurrences of PFAS contamination at 25 sites where contamination, as a result of AFFF use, was confirmed by Canadian governmental departments. For these 25 sites, the distance from potential release areas to the nearest surface water was calculated. Five of the sites were within 200 meters of surface water, 19 were within one kilometer, and all 25 were within 2.5 kilometers. This suggests that surface water may have been historically impacted by PFAS at as many as 152 to 420 different airport locations in Canada.

Lattice symmetries and the topologically protected transport of colloidal particles.

The topologically protected transport of colloidal particles on top of periodic magnetic patterns is studied experimentally, theoretically, and with computer simulations. To uncover the interplay between topology and symmetry we use patterns of all possible two dimensional magnetic point group symmetries with equal lengths lattice vectors. Transport of colloids is achieved by modulating the potential with external, homogeneous but time dependent magnetic fields. The modulation loops can be classified into topologically distinct classes. All loops falling into the same class cause motion in the same direction, making the transport robust against internal and external perturbations. We show that the lattice symmetry has a profound influence on the transport modes, the accessibility of transport networks, and the individual transport directions of paramagnetic and diamagnetic colloidal particles. We show how the transport of colloidal particles above a two fold symmetric stripe pattern changes from universal adiabatic transport at large elevations via a topologically protected ratchet motion at intermediate elevations toward a non-transport regime at low elevations. Transport above four-fold symmetric patterns is closely related to the two-fold symmetric case. The three-fold symmetric case however consists of a whole family of patterns that continuously vary with a phase variable. We show how this family can be divided into two topologically distinct classes supporting different transport modes and being protected by proper and improper six fold symmetries. We discuss and experimentally demonstrate the topological transition between both classes. All three-fold symmetric patterns support independent transport directions of paramagnetic and diamagnetic particles. The similarities and the differences in the lattice symmetry protected transport of classical over-damped colloidal particles versus the topologically protected transport in quantum mechanical systems are emphasized.

Sporozoite Route of Infection Influences In Vitro var Gene Transcription of Plasmodium falciparum Parasites From Controlled Human Infections.

BACKGROUND: Antigenic variation in Plasmodium falciparum is mediated by the multicopy var gene family. Each parasite possesses about 60 var genes, and switching between active var loci results in antigenic variation. In the current study, the effect of mosquito and host passage on in vitro var gene transcription was investigated. METHODS: Thirty malaria-naive individuals were inoculated by intradermal or intravenous injection with cryopreserved, isogenic NF54 P. falciparum sporozoites (PfSPZ) generated from 1 premosquito culture. Microscopic parasitemia developed in 22 individuals, and 21 in vitro cultures were established. The var gene transcript levels were determined in early and late postpatient cultures and in the premosquito culture. RESULTS: At the early time point, all cultures preferentially transcribed 8 subtelomeric var genes. Intradermal infections had higher var gene transcript levels than intravenous infections and a significantly longer intrahost replication time (P = .03). At the late time point, 9 subtelomeric and 8 central var genes were transcribed at the same levels in almost all cultures. Premosquito and late postpatient cultures transcribed the same subtelomeric and central var genes, except for var2csa CONCLUSIONS: The duration of intrahost replication influences in vitro var gene transcript patterns. Differences between premosquito and postpatient cultures decrease with prolonged in vitro growth.

Excretion of cytoplasmic proteins (ECP) in Staphylococcus aureus.

Excretion of cytoplasmic proteins (ECP) is a common physiological feature in bacteria and eukaryotes. However, how these proteins without a typical signal peptide are excreted in bacteria is poorly understood. We studied the excretion pattern of cytoplasmic proteins using two glycolytic model enzymes, aldolase and enolase, and show that their excretion takes place mainly during the exponential growth phase in Staphylococcus aureus very similar to that of Sbi, an IgG-binding protein, which is secreted via the Sec-pathway. The amount of excreted enolase is substantial and is comparable with that of Sbi. For localization of the exit site, we fused aldolase and enolase with the peptidoglycan-binding motif, LysM, to trap the enzymes at the cell wall. With both immune fluorescence labeling and immunogold localization on electron microscopic thin sections aldolase and enolase were found apart from the cytoplasmic area particularly in the cross wall and at the septal cleft of dividing cells, whereas the non-excreted Ndh2, a soluble NADH:quinone oxidoreductase, is only seen attached to the inner side of the cytoplasmic membrane. The selectivity, the timing and the localization suggest that ECP is not a result of unspecific cell lysis but is mediated by an as yet unknown mechanism.

Life cycle exposure of the frog Silurana tropicalis to arsenate: Steroid- and thyroid hormone-related genes are differently altered throughout development.

Arsenic contaminates water surface and groundwater worldwide. Several studies have suggested that arsenic acts as an endocrine disruptor in mammalian and non-mammalian species, although its chronic effect during development remains largely unknown. To address this question, life cycle exposures to 0, 0.3 and 0.8ppm of arsenate (pentavalent arsenic; As(V)) were performed in the Western clawed frog (Silurana tropicalis) from the gastrulae stage (developmental stage Nieuwkoop-Faber; NF12) until metamorphosis (NF66). Tissue samples were collected at the beginning of feeding (NF46; whole body), sexual development (NF56; liver), and at metamorphosis completion (NF66; liver and gonadal mesonephros complex). Real-time RT-PCR analysis quantified decreases in mRNA levels of genes related to estrogen- (estrogen receptor alpha and aromatase), androgen- (androgen receptor and steroid 5-alpha-reductase type 2), and cholesterol metabolism- (steroidogenic acute regulatory protein) at stage NF46. Similarly, arsenate decreased steroid 5-alpha-reductase type 2 expression in stage NF56 livers, but transcript increases were observed for both estrogen receptor alpha and steroidogenic acute regulatory protein at this stage. Given the changes observed in the expression of genes essential for proper sexual development, gonadal histological analysis was carried out in stage NF66 animals. Arsenate treatments did not alter sex ratio or produce testicular oocytes. On the other hand, arsenate interfered with thyroid hormone-related transcripts at NF66. Specifically, thyroid hormone receptor beta and deiodinase type 2 mRNA levels were significantly reduced after arsenate treatment in the gonadal mesonephros complex. This reduction in thyroid hormone-related gene expression, however, was not accompanied by any morphological changes measured. In summary, environmentally relevant concentrations of As(V) altered steroidogenesis-, sex steroid signaling- and thyroid hormone-related gene expression, although transcriptional changes varied among tissues and developmental stages.

Uptake and transformation of arsenic during the reproductive life stage of Agaricus bisporus and Agaricus campestris.

Fruiting bodies from the Agaricus genus have been found to contain non-toxic arsenobetaine (AB) as a major compound. It is unknown whether AB is formed during the vegetative or reproductive life stages of the fungus, or by the surrounding microbial community, but AB's structural similarity to glycine betaine has led to the hypothesis that AB may be adventitiously accumulated as an osmolyte. To investigate the potential formation of AB during the reproductive life stage of Agaricus species, growth substrate and fungi were collected during the commercial growth of Agaricus bisporus and analyzed for arsenic speciation using HPLC-ICP-MS. AB was found to be the major arsenic compound in the fungus at the earliest growth stage of fruiting (the primordium). The growth substrate mainly contained arsenate (As(V)). The distribution of arsenic in an A. bisporus primordium grown on As(V) treated substrate, and in a mature Agaricus campestris fruiting body collected from arsenic contaminated mine tailings, was mapped using two dimensional XAS imaging. The primordium and stalk of the mature fruiting body were both found to be growing around pockets of substrate material containing higher As concentrations, and AB was found exclusively in the fungal tissues. In the mature A. campestris the highest proportion of AB was found in the cap, supporting the AB as an osmolyte hypothesis. The results have allowed us to pinpoint the fungus life stage at which AB formation takes place, namely reproduction, which provides a direction for further research.

Biochar Soil Amendment Effects on Arsenic Availability to Mountain Brome ().

Biochar is a renewable energy byproduct that shows promise for remediating contaminated mine sites. A common contaminant at mine sites is arsenic (As). In this study, the effects of biochar amendments to a mine-contaminated soil on As concentrations in mountain brome ( Nees ex Steud.) were investigated. In the biochar-amended soil, mountain brome had greater root biomass and decreased root and shoot As concentrations. X-ray absorption near-edge structure spectroscopy results showed that arsenate [As(V)] is the predominant species in both the nonamended and biochar-amended soils. Soil extraction tests that measure phosphate and arsenate availability to plants failed to accurately predict plant tissue As concentrations, suggesting the arsenate bioavailability behavior in the soils is distinct from phosphate. Results from this study indicate that biochar will be a beneficial amendment to As-contaminated mine sites for remediation.

Manipulation of Superparamagnetic Beads on Patterned Exchange-Bias Layer Systems for Biosensing Applications.

A technology platform based on a remotely controlled and stepwise transport of an array arrangement of superparamagnetic beads (SPB) for efficient molecular uptake, delivery and accumulation in the context of highly specific and sensitive analyte molecule detection for the application in lab-on-a-chip devices is presented. The near-surface transport of SPBs is realized via the dynamic transformation of the SPBs' magnetic potential energy landscape above a magnetically stripe patterned Exchange-Bias (EB) thin film layer systems due to the application of sub-mT external magnetic field pulses. In this concept, the SPB velocity is dramatically influenced by the magnitude and gradient of the magnetic field landscape (MFL) above the magnetically stripe patterned EB substrate, the SPB to substrate distance, the magnetic properties of both the SPBs and the EB layer system, respectively, as well as by the properties of the external magnetic field pulses and the surrounding fluid. The focus of this review is laid on the specific MFL design in EB layer systems via light-ion bombardment induced magnetic patterning (IBMP). A numerical approach is introduced for the theoretical description of the MFL in comparison to experimental characterization via scanning Hall probe microscopy. The SPB transport mechanism will be outlined in terms of the dynamic interplay between the EB substrate's MFL and the pulse scheme of the external magnetic field.

Arsenic speciation in edible mushrooms.

The fruiting bodies, or mushrooms, of terrestrial fungi have been found to contain a high proportion of the nontoxic arsenic compound arsenobetaine (AB), but data gaps include a limited phylogenetic diversity of the fungi for which arsenic speciation is available, a focus on mushrooms with higher total arsenic concentrations, and the unknown formation and role of AB in mushrooms. To address these, the mushrooms of 46 different fungus species (73 samples) over a diverse range of phylogenetic groups were collected from Canadian grocery stores and background and arsenic-contaminated areas. Total arsenic was determined using ICP-MS, and arsenic speciation was determined using HPLC-ICP-MS and complementary X-ray absorption spectroscopy (XAS). The major arsenic compounds in mushrooms were found to be similar among phylogenetic groups, and AB was found to be the major compound in the Lycoperdaceae and Agaricaceae families but generally absent in log-growing mushrooms, suggesting the microbial community may influence arsenic speciation in mushrooms. The high proportion of AB in mushrooms with puffball or gilled morphologies may suggest that AB acts as an osmolyte in certain mushrooms to help maintain fruiting body structure. The presence of an As(III)-sulfur compound, for the first time in mushrooms, was identified in the XAS analysis. Except for Agaricus sp. (with predominantly AB), inorganic arsenic predominated in most of the store-bought mushrooms (albeit with low total arsenic concentrations). Should inorganic arsenic predominate in these mushrooms from contaminated areas, the risk to consumers under these circumstances should be considered.

Advancing PFAS characterization: Development and optimization of a UV-H2O2-TOP assay for improved PFCA chain length preservation and organic matter tolerance.

As per- and polyfluoroalkyl substances (PFAS) infiltrate the environment via industrial, commercial, and domestic sources, the demand for robust, cost-effective, and straightforward analytical assays intensifies to enhance PFAS characterization and quantification. To address this demand, this study introduces a novel UV-H2O2-TOP assay, identifying optimal parameters such as pH (5-9), oxidant concentration (500 mM H2O2), activation rate (63 mM H2O2 h-1), and an acceptable total organic carbon (TOC) limit (~1000 mg/L TOC) to achieve maximum PFAA precursor conversion. Additional work was performed further optimizing the UV-TOP assay, by confirming its superiority to heat activation, identifying the effectiveness of different persulfate salts, and investigating different concentrations of sodium persulfate and sodium hydroxide at a 1:2.5 ratio on PFCA yield. Our investigation concluded by applying the UV-H2O2-TOP assay, using sodium persulfate as the TOP assay oxidant, to 6:2 FTS and five different AFFF samples. High-resolution mass spectrometry and an expanded analytical suite support sample analysis, facilitating direct quantification of ultra-short chain perfluoroalkyl carboxylates (PFCAs) and common fluorotelomer compounds including 5:3/5:1:2 fluorotelomer betaine and 6:2 fluorotelomer sulfonamido betaine. Results highlight several advantages of this tandem UV-activated method, including enhanced preservation of perfluoroalkyl chains (post-oxidation of 6:2 fluorotelomer sulfonate resulted in 28 % PFHpA, 47 % PFHxA, 25 % C3-C5 PFCA), capacity to handle high TOC limits (1000 mg/L TOC), and ability to incorporate higher persulfate concentrations in a single oxidation cycle.

Mechanochemical degradation of per- and polyfluoroalkyl substances in soil using an industrial-scale horizontal ball mill with comparisons of key operational metrics.

Horizontal ball mills (HBMs) have been proven capable of remediating per- and polyfluoroalkyl substances (PFAS) in soil. Industrial-sized HBMs, which could easily be transported to impacted locations for on-site, ex-situ remediation, are readily available. This study examined PFAS degradation using an industrial-scale, 267 L cylinder HBM. This is the typical scale used in the industry before field application. Near-complete destruction of 6:2 fluorotelomer sulfonate (6:2 FTS), as well as the non-target PFAS in a modern fluorotelomer-based aqueous film forming foam (AFFF), was achieved when spiked onto nepheline syenite sand (NSS) and using potassium hydroxide (KOH) as a co-milling reagent. Perfluorooctanesulfonate (PFOS) showed much better and more consistent results with scale-up regardless of KOH. Perfluorooctanoate (PFOA) was examined for the first time using a HBM and behaved similarly to PFOS. Highly challenging field soils from a former firefighting training area (FFTA) were purposefully used to test the limits of the HBM. To quantify the effectiveness, free fluoride analysis was used; changes between unmilled and milled soil were measured up to 7.8 mg/kg, which is the equivalent of 12 mg/kg PFOS. Notably, this does not factor in insoluble fluoride complexes that may form in milled soils, so the actual amount of PFAS destroyed may be higher. Soil health, evaluated through the assessment of key microbial and associated plant health parameters, was not significantly affected as a result of milling, although it was characterized as poor to begin with. Leachability reached 100 % in milled soil with KOH, but already ranged from 81 to 96 % in unmilled soil. A limited assessment of the hazards associated with the inhalation of PFAS-impacted dust from ball-milling, as well as the cross-contamination potential to the environment, showed that the risk was low in both cases; however, precautions should always be taken.

Occurrence and mobility of thiolated arsenic in legacy mine tailings.

We studied the occurrence of dissolved thiolated Arsenic (As) in legacy tailings systems in Ontario and Nova Scotia, Canada, and used aqueous and mineralogical speciation analyses to assess its governing geochemical controls. Surface-accessible and inundated tailings in Cobalt, Ontario, contained ∼1 wt-% As mainly hosted in secondary arsenate minerals (erythrite, yukonite, and others) and traces of primary sulfide minerals (cobaltite, gersdorffite and others). Significant fractions of thiolated As (up to 5.9 % of total dissolved As) were detected in aqueous porewater and surface water samples from these sites, comprising mostly monothioarsenate, and smaller amounts of di- and tri-thioarsenates as well as methylated thioarsenates. Tailings at the Goldenville and Montague sites in Nova Scotia contained less (<0.5 wt-%) As, hosted mostly in arsenopyrite and As-bearing pyrite, than the Cobalt sites, but exhibited higher proportions of dissolved thiolated As (up to 17.3 % of total dissolved As, mostly mono- and di-thioarsenate and traces of tri-thioarsenate). Dissolved thiolated As was most abundant in sub-oxic porewaters and inundated tailings samples across the studied sites, and its concentrations were strongly related to the prevailing redox conditions and porewater hydrochemistry, and to a lesser extent, the As-bearing mineralogy. Our novel results demonstrate that thiolated As species play an important role in the cycling of As in mine waste systems and surrounding environments, and should be considered in mine waste management strategies for high-As sites.

Bazooka is required for polarisation of the Drosophila anterior-posterior axis.

The Drosophila anterior-posterior (AP) axis is determined by the polarisation of the stage 9 oocyte and the subsequent localisation of bicoid and oskar mRNAs to opposite poles of the cell. Oocyte polarity has been proposed to depend on the same PAR proteins that generate AP polarity in C. elegans, with a complex of Bazooka (Baz; Par-3), Par-6 and aPKC marking the anterior and lateral cortex, and Par-1 defining the posterior. The function of the Baz complex in oocyte polarity has remained unclear, however, because although baz-null mutants block oocyte determination, egg chambers that escape this early arrest usually develop normal polarity at stage 9. Here, we characterise a baz allele that produces a penetrant polarity phenotype at stage 9 without affecting oocyte determination, demonstrating that Baz is essential for axis formation. The dynamics of Baz, Par-6 and Par-1 localisation in the oocyte indicate that the axis is not polarised by a cortical contraction as in C. elegans, and instead suggest that repolarisation of the oocyte is triggered by posterior inactivation of aPKC or activation of Par-1. This initial asymmetry is then reinforced by mutual inhibition between the anterior Baz complex and posterior Par-1 and Lgl. Finally, we show that mutation of the aPKC phosphorylation site in Par-1 results in the uniform cortical localisation of Par-1 and the loss of cortical microtubules. Since non-phosphorylatable Par-1 is epistatic to uninhibitable Baz, Par-1 seems to function downstream of the other PAR proteins to polarize the oocyte microtubule cytoskeleton.

Variability of bioaccessibility results using seventeen different methods on a standard reference material, NIST 2710.

Bioaccessibility is a measurement of a substance's solubility in the human gastro-intestinal system, and is often used in the risk assessment of soils. The present study was designed to determine the variability among laboratories using different methods to measure the bioaccessibility of 24 inorganic contaminants in one standardized soil sample, the standard reference material NIST 2710. Fourteen laboratories used a total of 17 bioaccessibility extraction methods. The variability between methods was assessed by calculating the reproducibility relative standard deviations (RSDs), where reproducibility is the sum of within-laboratory and between-laboratory variability. Whereas within-laboratory repeatability was usually better than (<) 15% for most elements, reproducibility RSDs were much higher, indicating more variability, although for many elements they were comparable to typical uncertainties (e.g., 30% in commercial laboratories). For five trace elements of interest, reproducibility RSDs were: arsenic (As), 22-44%; cadmium (Cd), 11-41%; Cu, 15-30%; lead (Pb), 45-83%; and Zn, 18-56%. Only one method variable, pH, was found to correlate significantly with bioaccessibility for aluminum (Al), Cd, copper (Cu), manganese (Mn), Pb and zinc (Zn) but other method variables could not be examined systematically because of the study design. When bioaccessibility results were directly compared with bioavailability results for As (swine and mouse) and Pb (swine), four methods returned results within uncertainty ranges for both elements: two that were defined as simpler (gastric phase only, limited chemicals) and two were more complex (gastric + intestinal phases, with a mixture of chemicals).