Quantification of quaternary ammonium compounds by liquid chromatography-mass spectrometry: Minimizing losses from the field to the laboratory.

Quaternary Ammonium Compounds (QACs) are widely used in household, medical and industrial settings. As a consequence, they are ubiquitously found in the environment. Although significant efforts have been put into the development of sensitive and reproducible analytical methods, much less effort has been dedicated to the monitoring of QACs upon sample storage and sample preparation. Here we studied the effect of storage, concentration, and extraction procedures on the concentrations of QACs in samples. Thirteen QACs selected amongst benzalkonium compounds (BACs), dialkyldimethylammonium compounds (DADMACs) and alkyltrimethylammonium compounds (ATMACs) were quantified in aqueous and solid samples using LC-MS/MS. Most QACs adsorbed on container walls could be recovered using a short washing step with MeOH containing 2 % v/v formic acid. Concentrations of QACs from aqueous solutions using solid phase extraction (SPE) with Strata-X cartridges and elution with acidified MeOH utilized to wash the emptied containers gave highly satisfactory recoveries (101-111 %). Good recoveries (89-116 %) were also obtained when extracting a spiked organic-rich synthetic soil using accelerated solvent extraction (ASE) with acidified MeOH at low solid/solvent ratio (0.4 g/20 mL). Applying the recommended methodologies to real samples collected from a Canadian wastewater treatment plant (WWTP) gave QAC concentrations in the ranges of 0.01-30 µg/L, < 1.2 µg/L, and 0.05-27 mg/kg for the influent, effluent and biosolids samples, respectively.

Characterization of a partially saturated and glycosylated apocarotenoid from wheat that is depleted upon leaf rust infection.

Recent semi-targeted metabolomics studies have highlighted a number of metabolites in wheat that associate with leaf rust resistance genes and/or rust infection. Here, we report the structural characterization of a novel glycosylated and partially saturated apocarotenoid, reminiscent of a reduced form of mycorradicin, (6E,8E,10E)-4,9-dimethyl-12-oxo-12-((3,4,5-trihydroxy-6-(2-hydroxyethoxy)tetrahydro-2H-pyran-2-yl)methoxy)-3-((3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)dodeca-6,8,10-trienoic acid, isolated from Triticum aestivum L. (Poaceae) variety 'Thatcher' (Tc) flag leaves. While its accumulation was not associated with any of Lr34, Lr67 or Lr22a resistance genes, infection of Tc with leaf rust was found to deplete it, consistent with the idea of this metabolite being a glycosylated-storage form of an apocarotenoid of possible relevance to plant defense. A comparative analysis of wheat transcriptomic changes shows modulation of terpenoid, carotenoid, UDP-glycosyltransferase and glycosylase -related gene expression profiles, consistent with anticipated biosynthesis and degradation mechanisms. However, details of the exact nature of the relevant pathways remain to be validated in the future. Together these findings highlight another example of the breadth of unique metabolites underlying plant host-fungal pathogen interactions.

The potential of Burkholderia thailandensis E264 for co-valorization of C5 and C6 sugars into multiple value-added bio-products.

Despite known metabolic versatility of Burkholderia spp., sugar metabolism and end-product synthesis patterns in Burkholderia thailandensis have been poorly characterized. This work has demonstrated that B. thailandensis is capable of simultaneously uptaking glucose and xylose and accumulating up to 64% of its dry mass as poly(3-hydroxyalkanoate) (PHA) biopolymers, resulting in a PHA titer of up to 3.8 g L-1 in shake flasks. Rhamnolipids - mainly (68-75%) in the form of Rha-Rha-C14-C14 - were produced concomitantly with a titer typically in the range of 0.2-0.4 g L-1. Gluconic and xylonic acids were also detected in titers of up to 5.3 g L-1, and while gluconic acid appeared to be back consumed, xylonic acid formed as a major end product. This first example of co-production of three products from mixed sugars using B. thailandensis paves the way for improving biorefinery economics.

Biosynthesis and properties of polyhydroxyalkanoates synthesized from mixed C5 and C6 sugars obtained from hardwood hydrolysis.

Glucose and xylose are fermentable sugars readily available from lignocellulosic biomass, and are a sustainable carbon substrate supporting industrial biotechnology. Three strains were assessed in this work - Paraburkholderia sacchari, Hydrogenophaga pseudoflava, and Bacillus megaterium - for their ability to uptake both C5 and C6 sugars contained in a hardwood hydrolysate produced via a thermomechanical pulping-based process with concomitant production of poly(3-hydroxyalkanoate) (PHA) biopolymers. In batch conditions, B. megaterium showed poor growth after 12 h, minimal uptake of xylose throughout the cultivation, and accumulated a maximum of only 25 % of the dry biomass as PHA. The other strains simultaneously utilized both sugars, although glucose uptake was faster than xylose. From hardwood hydrolysate, P. sacchari accumulated 57 % of its biomass as PHA within 24 h, whereas H. pseudoflava achieved an intracellular PHA content of 84 % by 72 h. The molecular weight of the PHA synthesized by H. pseudoflava (520.2 kDa) was higher than that of P. sacchari (265.5 kDa). When the medium was supplemented with propionic acid, the latter was rapidly consumed by both strains and incorporated as 3-hydroxyvalerate subunits into the polymer, demonstrating the potential for production of polymers with improved properties and value. H. pseudoflava incorporated 3-hydroxyvalerate subunits with at least a 3-fold higher yield, and produced polymers with higher 3-hydroxyvalerate content than P. sacchari. Overall, this work has shown that H. pseudoflava can be an excellent candidate for bioconversion of lignocellulosic sugars to PHA polymers or copolymers as part of an integrated biorefinery.

A peroxidase-derived ligand that induces Fusarium graminearum Ste2 receptor-dependent chemotropism.

Introduction: The fungal G protein-coupled receptors Ste2 and Ste3 are vital in mediating directional hyphal growth of the agricultural pathogen Fusarium graminearum towards wheat plants. This chemotropism is induced by a catalytic product of peroxidases secreted by the wheat. Currently, the identity of this product, and the substrate it is generated from, are not known. Methods and results: We provide evidence that a peroxidase substrate is derived from F. graminearum conidia and report a simple method to extract and purify the FgSte2-activating ligand for analyses by mass spectrometry. The mass spectra arising from t he ligand extract are characteristic of a 400 Da carbohydrate moiety. Consistent with this type of molecule, glycosidase treatment of F. graminearum conidia prior to peroxidase treatment significantly reduced the amount of ligand extracted. Interestingly, availability of the peroxidase substrate appears to depend on the presence of both FgSte2 and FgSte3, as knockout of one or the other reduces the chemotropism-inducing effect of the extracts. Conclusions: While further characterization is necessary, identification of the F. graminearum-derived peroxidase substrate and the FgSte2-activating ligand will unearth deeper insights into the intricate mechanisms that underlie fungal pathogenesis in cereal crops, unveiling novel avenues for inhibitory interventions.

Enhancement of swine manure anaerobic digestion using membrane-based NH3 extraction.

The influence of suspended solids and pH in anaerobically digested piggery wastewater on membrane-based NH3 extraction was evaluated in batch tests. The increase in pH in the anaerobic broth from 8 to 9 resulted in an increase in NH3 removal efficiencies from 15.8 % ± 0.1 % to 20.9 % ± 0.4 % regardless of the suspended solids. The influence of membrane based NH3 extraction on piggery wastewater treatment was also assessed in a CSTR interconnected with PTFE membrane modules. The decrease in TKN concentrations mediated by membrane operation induced an increase in CH4 yield from 380.4 ± 84.9 up to 566.1 ± 7.8 NmLCH4 g VS fed-1. Likewise, COD and VS removal efficiencies significantly increased from 33.0 % ± 2.0 % and 25.7 % ± 2.3 % up to 61.8 % ± 1.3 % and 37.9 % ± 1.8 %, respectively. Interestingly, the decrease in NH3 concentration entailed a complete assimilation of VFA.

A Systematic Study of Ammonia Recovery from Anaerobic Digestate Using Membrane-Based Separation.

Ammonia recovery from synthetic and real anaerobic digestates was accomplished using hydrophobic flat sheet membranes operated with H2SO4 solutions to convert ammonia into ammonium sulphate. The influence of the membrane material, flow rate (0.007, 0.015, 0.030 and 0.045 m3 h-1) and pH (7.6, 8.9, 10 and 11) of the digestate on ammonia recovery was investigated. The process was carried out with a flat sheet configuration at a temperature of 35 °C and with a 1 M, or 0.005 M, H2SO4 solution on the other side of the membrane. Polytetrafluoroethylene membranes with a nominal pore radius of 0.22 µm provided ammonia recoveries from synthetic and real digestates of 84.6% ± 1.0% and 71.6% ± 0.3%, respectively, for a membrane area of 8.6 × 10-4 m2 and a reservoir volume of 0.5 L, in 3.5 h with a 1 M H2SO4 solution and a recirculation flow on the feed side of the membrane of 0.030 m3 h-1. NH3 recovery followed first order kinetics and was faster at higher pHs of the H2SO4 solution and recirculation flow rate on the membrane feed side. Fouling resulted in changes in membrane surface morphology and pore size, which were confirmed by Atomic Force Microscopy and Air Displacement Porometry.

A phenylpropanoid diglyceride associates with the leaf rust resistance Lr34res gene in wheat.

The gene Lr34res is one of the most long-lasting sources of quantitative fungal resistance in wheat. It is shown to be effective against leaf, stem, and stripe rusts, as well as powdery mildew and spot blotch. Recent biochemical characterizations of the encoded ABC transporter have outlined a number of allocrites, including phospholipids and abscisic acid, consistent with the established general promiscuity of ABC transporters, but ultimately leaving its mechanism of rust resistance unclear. Working with flag leaves of Triticum aestivum L. variety 'Thatcher' (Tc) and a near-isogenic line of 'Thatcher' into which the Lr34res allele was introgressed (Tc+Lr34res; RL6058), a comparative semi-targeted metabolomics analysis of flavonoid-rich extracts revealed virtually identical profiles with the exception of one metabolite accumulating in Tc+Lr34res, which was not present at comparable levels in Tc. Structural characterization of the purified metabolite revealed a phenylpropanoid diglyceride structure, 1-O-p-coumaroyl-3-O-feruloylglycerol (CFG). Additional profiling of CFG across a collection of near-isogenic lines and representative Lr34 haplotypes highlighted a broad association between the presence of Lr34res and elevated accumulations of CFG. Depletion of CFG upon infection, juxtaposed to its relatively lower anti-fungal activity, suggests CFG may serve as a storage form of the more potent anti-microbial hydroxycinnamic acids that are accessed during defense responses. Altogether these findings suggest a role for the encoded LR34res ABC transporter in modifying the accumulation of CFG, leading to increased accumulation of anti-fungal metabolites, essentially priming the wheat plant for defense.

Probing allocrite preferences of 2 naturally occurring variants of the wheat LR34 ABC transporter.

For almost a century, the wheat Lr34 gene has conferred durable resistance against fungal rust diseases. While sequence homology predicts a putative ATP binding cassette transporter, the molecules that are transported (allocrites) by the encoded LR34 variants, and any associated mechanism of resistance, remain enigmatic. Here, the in vitro transport characteristics of 2 naturally occurring Lr34 variants (that differ in their ability to mediate disease resistance; Lr34sus and Lr34res) are investigated. Initially, a method to express and purify recombinant LR34Sus and LR34Res pseudo half-molecules from Saccharomyces cerevisiae, is described. Subsequently, a semi-targeted chlorophyll catabolite (CC) extraction from Lr34res-expressing wheat plants was performed based on previous reports highlighting increased accumulation of CCs in Lr34res-expressing flag leaves. Following partial biochemical characterization, this extract was applied to an LR34 in vitro proteoliposome transport assay. Mass spectroscopic analyses of transported metabolites revealed that LR34Sus imported a wheat metabolite of 618 Da and that the LR34Res transporter did not. While the identity of the LR34Sus transported metabolite remains to be confirmed and any allocrites of LR34Res remain to be detected, this work demonstrates that these variants have different allocrite preferences, a finding that may be relevant to the mechanism of disease resistance.

Microwave-assisted extraction of lignin from triticale straw: optimization and microwave effects.

Presently lignin is used as fuel but recent interests in biomaterials encourage the use of this polymer as a renewable feedstock in manufacturing. The present study was undertaken to explore the potential applicability of microwaves to isolate lignin from agricultural residues. A central composite design (CCD) was used to optimize the processing conditions for the microwave (MW)-assisted extraction of lignin from triticale straw. Maximal lignin yield (91%) was found when using 92% EtOH, 0.64 N H(2)SO(4), and 148 °C. The yield and chemical structure of MW-extracted lignin were compared to those of lignin extracted with conventional heating. Under similar conditions, MW irradiation led to higher lignin yields, lignins of lower sugar content, and lignins of smaller molecular weights. Except for these differences the lignins resulting from both types of heating exhibited comparable chemical structures. The present findings should provide a clean source of lignin for potential testing in manufacturing of biomaterials.

Analysis of the key intermediates of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) in groundwater: occurrence, stability and preservation.

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a widely used explosive that is present in soils at a number of military sites, including training and testing ranges. Because of its relatively weak adsorption to soil, RDX frequently migrates through the unsaturated zone and causes groundwater contamination. In the environment, RDX can transform to produce mono-, di-, and tri-nitroso derivatives (MNX, DNX, and TNX) and the ring cleavage products methylenedinitramine (MEDINA) and 4-nitro-2,4-diazabutanal (NDAB). The present study was undertaken to analyze RDX and its products in groundwater samples taken from various US military sites. The stability of some of the common transformation intermediates of RDX, including the nitroso derivatives, NDAB and MEDINA, under typical conditions in a groundwater aquifer is not well understood, and appropriate preservation methods for these compounds have not been established. Therefore, we studied the inherent stability of these compounds in deionized water and in groundwater, and evaluated various preservation techniques, including adjustment of pH, temperature, and salinity. NDAB and nitroso derivatives were stable under typical ambient environmental conditions, but MEDINA was highly unstable. The addition of sea salts (10% w/v) was found to stabilize MEDINA when the samples were stored at 4 °C. Using appropriate preservation techniques, we detected nitroso derivatives and NDAB, but no MEDINA, at some of the sites investigated. Stabilizing RDX intermediate products in field samples to allow detection is important because the presence of any of these chemicals can indicate past contamination by RDX and provide insight into the occurrence of in situ natural attenuation.

Role of soil interstitial water in the accumulation of hexahydro-1,3,5-trinitro-1,3,5-triazine in the earthworm Eisenia andrei.

The uptake of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from soil by the earthworm Eisenia andrei was examined by using the equilibrium partitioning (EqP) theory and a three-compartment model including soil (S), interstitial water (IW), and earthworms (E). The RDX concentrations were measured using U.S. Environmental Protection Agency (U.S. EPA) Method 8330A and high-performance liquid chromatography (HPLC). The S-IW studies were conducted using four natural soils with contrasting physicochemical properties that were hypothesized to affect the bioavailability of RDX. Each soil was amended with nominal RDX concentrations ranging from 1 to 10,000 mg/kg. The HPLC analysis showed that the IW extracted from soil was saturated with RDX at 80 mg/kg or greater soil concentrations. The calculated S-IW coefficient (K(p)) values for RDX ranged from 0.4 to 1.8 ml/g soil, depending on the soil type, and were influenced by the organic matter content. In the IW-E studies, earthworms were exposed to nonlethal RDX concentrations in aqueous media. The uptake of RDX by the earthworms correlated well (r(2) = 0.99) with the dissolved RDX concentrations. For the E-S studies, earthworms were exposed to RDX-amended soils used in the S-IW studies. The bioconcentration factors (BCF; ratios of E-to-IW RDX concentrations) were relatively constant ( approximately 5) up to 80 mg/kg soil RDX concentrations, which encompass the RDX saturation limit in the interstitial water of the tested soils. At this concentration range, the RDX uptake from interstitial water was likely dominated by passive diffusion and could be used as an indicator of bioavailability. Other mechanisms may be involved at greater RDX soil concentrations.

Dissolution of a new explosive formulation containing TNT and HMX: comparison with octol.

GIM (Greener Insensitive Material) is a new explosive formulation made of HMX (51.5%), TNT (40.7%), and a binder, ETPE (7.8%), which is currently investigated by the Canadian Department of National Defense for a wider use by the Army. In the present study, dissolution of GIM in water was measured and compared to the dissolution of octol (HMX/TNT: 70/30). Although the presence of ETPE did not prevent completely TNT and HMX from dissolving, GIM appeared to dissolve more slowly than octol. The ETPE was shown to prevent the formulation particles from collapsing and to retard the dissolution of both TNT and HMX by limiting their exposure to water. In both octol and GIM, the dissolution rate of the particles was governed by the compound(s) that are slower to dissolve, i.e. HMX in octol, and HMX and ETPE in GIM. A model based on Fick's diffusion law allowed fitting well the dissolution data of octol but was less appropriate to fit the data of GIM likely due to a physical rearrangement of the solid upon dissolution. The present findings demonstrate that ETPE in GIM decreases the risks of explosives leakage from particles of the new formulation and should facilitate the collecting of non-exploded GIM particles in training sites.

Fate of CL-20 in sandy soils: degradation products as potential markers of natural attenuation.

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH(2)=N-C(=N-NO(2))-CH=N-CHO or its isomer N(NO(2))=CH-CH=N-CO-CH=NH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil.

Contribution of hydrolysis in the abiotic attenuation of RDX and HMX in coastal waters.

Sinking of military ships, dumping of munitions during the two World Wars, and military training have resulted in the undersea deposition of numerous unexploded ordnances (UXOs). Leaching of energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from these UXOs may cause adverse ecological effects so that the long-term fate of these chemicals in the sea should be known. The present study assesses the contribution of alkaline hydrolysis into the natural attenuation of RDX and HMX in coastal waters. Alkaline hydrolysis rates were shown to be unaffected by the presence of sodium chloride, the most common component in marine waters. Kinetic parameters (E(a), ln A, k(2)) quantified for the alkaline hydrolysis of RDX and HMX in deionized water (30-50 degrees C, pH 10-12) agreed relatively well with abiotic degradation rates determined in sterilized natural coastal waters (50 and 60 degrees C, variable salinity) even if the latter were generally slightly faster than the former. Furthermore, similar products (HCHO, NO(2)(-), O(2)NNHCH(2)NHCHO) were obtained on alkaline hydrolysis in deionized water and abiotic degradation in coastal waters. These two findings suggested that degradation of nitramines in sterilized natural coastal waters, away from light, was mainly governed by alkaline hydrolysis. Kinetic calculations using the present parameters showed that alkaline hydrolysis of RDX and HMX in marine waters at 10 degrees C would respectively take 112 +/- 10 and 2408 +/- 217 yr to be completed (99.0%). We concluded that under natural conditions hydrolysis should not contribute significantly to the natural attenuation of HMX in coastal waters whereas it could play an active role in the natural attenuation of RDX.

Experimental evidence for in situ natural attenuation of 2,4- and 2,6-dinitrotoluene in marine sediment.

Dinitrotoluenes (DNTs) are widely used in the manufacturing of explosives and propellants hence causing contamination of several terrestrial and aquatic environments. The present study describes biotransformation of 2,4-DNT and 2,6-DNT in marine sediment sampled from a shipwreck site near Halifax Harbour. Incubation of either 2,4-DNT or 2,6-DNT in anaerobic sediment slurries (10% w/v) at 10 degrees C led to the reduction of both DNTs to their corresponding diaminotoluene (2,4-DAT and 2,6-DAT) via the intermediary formation of their monoamine derivatives (ANTs). The production of diaminotoluene was enhanced in the presence of lactate for both DNT isomers. Using [(14)C]-2,4-DNT less than 1% mineralization was observed as determined by liberated (14)CO(2). Sorption of DNTs, ANTs, and DATs was thus investigated to learn of their fate in marine sediments. Under anaerobic conditions, sorption followed the order: DNTs (K(d)=8.3-11.7lkg(-1))>ANTs (K(d)=4.5-7.0lkg(-1))>DATs (K(d)=3.8-4.5lkg(-1)). Incubation of 2,4-DAT in aerobic sediment led to rapid disappearance from the aqueous phase. LC/MS analysis of the aqueous phase and the acetone sediment extract showed the formation of azo- and hydrazo-dimers and trimers, as well as unidentified polymers. Experiments with radiolabelled 2,4-DAT showed a mass balance distributed as follows: 22% in the aqueous phase, 24% in acetone extracts, and 50% irreversibly bound to sediment. We concluded that DNT in anoxic marine sediment can undergo in situ natural attenuation by reduction to DAT followed by oxidative coupling to hydrazo-oligomers or irreversible binding to sediment.

Interactions of aqueous selenium (-II) and (IV) with metallic sulfide surfaces.

The present study was initiated to determine the capacity of sulfide minerals (pyrite FeS2 and chalcopyrite CuFeS2) to delay the migration of inorganic selenium species in geological formations. Interactions between Se(IV) and Se(-II) and synthetic and natural sulfide minerals were investigated under anoxic conditions using the batch method. Significant sorption of selenium occurred under acidic conditions. Analysis of the solids after Se sorption using X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) demonstrated the presence of reduced selenium species on the metallic sulfide surfaces, thus suggesting an oxido-reduction process coupled with sorption. Selenium reduction occurred concomitantly with the oxidation of pyritic sulfur, whereas metallic species (Fe, Cu) were not involved in the redox process. Formation of ferroselite (FeSe2) was postulated to take place on the synthetic solid while surface complexation or ionic exchange processes were more likely on the natural solids.

Use of headspace solid-phase microextraction for the quantification of poly(3-hydroxybutyrate) in microbial cells.

Biopolymers such as poly(hydroxyalkanoates) (PHAs) have received much attention due to their physico-chemical properties, biodegradability, and biocompatibility that make them good candidates for industrial and medical applications. Produced by some microorganisms PHAs accumulate within the cells of these organisms. The optimization of microbial processes to produce PHAs at a lower cost requires rapid and accurate techniques for quantification of the biopolymer in biomass. The present study describes a method based on solid-phase microextraction (SPME) coupled to gas chromatography (GC) for the determination of poly(3-hydroxybutyrate) (PHB) in Alcaligenes latus cells. First PHB was depolymerized by either methanolic or hydrolytic digestion into methyl 3-hydroxybutyrate (Me-3-HB) or crotonic acid (CA), respectively. The resulting analytes were then subjected to analysis by headspace SPME/GC with flame ionization detection (FID). The two depolymerization/SPME/GC-FID methods were optimized and applied to the analysis of PHB in bacterial biomass harvested from a fermentation process that uses A. latus. Results were compared with those obtained using GC-FID analysis of MeOH/CHCl(3) digested samples. Excellent agreement was found between the three methods but the two SPME-based methods were environmentally friendly and easier to perform.

XPS and XAS studies of copper(II) sorbed onto a synthetic pyrite surface.

Compounds containing copper are likely candidates to delay iodide migration in environmental media through the formation of sparingly soluble phases. Preliminary experiments showed that iodide was neither sorbed onto chalcopyrite nor by a binary system pyrite/copper(II), although significant amounts of copper were present at the pyrite surface. In the present study, spectroscopic studies (XPS, XANES and EXAFS) were thus performed to determine the nature of sorbed copper species. Although introduced as Cu(II), copper was mainly present at the oxidation state (I) on the pyrite surface suggesting a heterogeneous reduction process. Moreover, copper appeared tetrahedrally coordinated to two sulfur and two oxygen atoms onto the pyrite surface, a chemical environment, which seemingly stabilized the metal and made it unreactive towards iodide.

Sorption of Sr(II) and Eu(III) onto pyrite under different redox potential conditions.

Understanding sorption processes is fundamental for the prediction of radionuclide migration in the surroundings of a deep geological disposal of high-level nuclear wastes. Pyrite (FeS2) is a mineral phase often present as inclusions in temperate soils. Moreover, it constitutes an indirect corrosion product of steel, a containment material that is candidate to confine radionuclides in deep geological disposals. The present study was thus initiated to determine the capacity of pyrite to immobilize Sr(II) and Eu(III). An air oxidized pyrite and a freshly acid-washed (non-oxidized) pyrite were used in background electrolytes of varying reducing-oxidizing ability (NaCl, NH3OHCl, and NaClO4) to study the sorption of both cationic species. The sorptive capacity of pyrite appeared directly correlated to the oxidation of the surface. Non-oxidized pyrite had nearly no affinity for the studied cations whereas Sr(II) and Eu(III) species were significantly retained by oxidized pyrite surface. Using the surface complexation theory, sorption mechanisms were modeled with the Fiteql v3.2 and the Jchess 2.0 codes. Sorption of both Sr and Eu was well fitted, assuming hydroxylated species as the major surface species. This study demonstrates that not only the components of a barrier but also the redox conditions and specifications should be well characterized to predict transport of contaminants in the surrounding of a nuclear wastes disposal.