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Nonessential elements like Sr2+ are incorporated via Ca2+ transport proteins due to their similar chemical properties and are substituted for Ca2+ in hard structures of fishes. Few studies have investigated the uptake kinetics of nonessential elements or the effect the ambient environment has on uptake rates. We tested the hypothesis that temperature and environmental Ca2+ activity would influence uptake and subsequent deposition rates of Sr2+ in the fin rays of lake sturgeon (Acipenser fulvescens). Michaelis–Menten substrate inhibition models were used to measure the kinetics of Sr2+ uptake on lake sturgeon larvae that were exposed to varying temperature and Ca2+ activities. Sr2+ influx increased at higher temperatures (maximum JmaxSr = 56.5 pmol·g−1·h−1) and decreased when larvae were exposed to increasing activities of Ca2+ (minimum JmaxSr = 6.4 pmol·g−1·h−1), indicating Ca2+ has an inhibitory effect on Sr2+ influx. Furthermore, Sr2+ was preferentially accumulated in fin rays and partitioning was significantly affected by temperature and Ca2+ activity, providing, for the first time, an understanding of the underlying physiological mechanisms involved in elemental uptake and deposition of nonessential metals in sturgeons.

Lead (Pb) is a major toxicological concern of the present day that demands immediate attention. The use of aquatic macrophytes with high Pb tolerance and accumulation may be a very convenient and economically viable solution for remediating Pb. We examined the ability of

Field experiments were carried out on sandy loam soil of TypicHaplustepts with various nitrogen levels i.e. 40, 60, 80, 100 and 120 kg ha-1during Ravi seasons of 2015-17. These treatments were compared with control and absolute control to calculate uptake kinetics. Results revealed thatnitrogen uptake rate increased with increase in doses of N,however it was highest with 120 kg N ha-1. During 91-120 days followed the linear trend with increased doses of N and also somewhat 61-90. Uptake rate of N at 121-180 days also followed the similar trend as that of 91-120 days up to 80 kg N ha-1thereafter reduced with higher levels of N. Hence, the uptake rate reduced with higher doses of N and age of crop plant or nearer to maturity.Phosphorus uptake rate was increased sharply at 100 and 120 kg N ha-1during 0-60 and 121-180 days. During 61-90, 91-120 and 121-180 days, P uptake rate was increased linearly with increased doses of N levels. In general, potassium uptake rate increased linearly with increase in time and doses of N, however it was increased exponentially at 120 kg N during 121-180 days. Moreover, K uptake was lower at lower levels of N during 121-180 days in comparison to 91-120 days.Overall uptake rate of N, P and K was more with higher doses of N, and duration and age of crop plants. However, N and K uptake rate was highest at 91-120 days and reduced thereafter. Moreover, the uptake rate of K was higher than N and was least of P. Hence, K accumulation was highest and P was least among the major nutrients. Whereas, N, P and K uptake rate was positively influenced by N input up to the age of120 days of fennel.Therefore, it can be concluded that higher doses of N and age of crop plants has negative relation for the uptake of N, whereas P uptake rate gave a positive relation with higher doses of N and aging of crop plants. In contrast to N and P,K uptake rate shown positive relation to N input and negative at highest levels of N.

The search for alternatives to bioaccumulative perfluoroalkyl acids (PFAAs) is ongoing. New, still highly fluorinated alternatives are produced in hopes of reducing bioaccumulation. To better estimate this bioaccumulative behavior, we performed dialysis experiments and determined membrane/water partition coefficients, Kmem/w, of six perfluoroalkyl carboxylic acids (PFCAs), three perfluoroalkanesulfonic acids, and four alternatives. We also investigated how passive permeation might influence the uptake kinetics into cells, measuring the passive anionic membrane permeability Pion through planar lipid bilayers for six PFAAs and three alternatives. Experimental Kmem/w and Pion were both predicted well by the COSMO-RS theory (log RMSE 0.61 and 0.46, respectively). Kmem/w values were consistent with the literature data, and alternatives showed similar sorption behavior as PFAAs. Experimental Pion values were high enough to explain observed cellular uptake by passive diffusion with no need to postulate the existence of active uptake processes. However, predicted pKa and neutral permeabilities suggest that also the permeation of the neutral species should be significant in case of PFCAs. This can have direct consequences on the steady-state distribution of PFAAs across cell membranes and thus toxicity. Consequently, we propose a model to predict pH-dependent baseline toxicity based on Kmem/w, which considers the permeation of both neutral and anionic species.

International audience; Textile and tannery industries are highly contaminating with discharge of high Cr concentrations. Developing bio-based sorbents with strong affinity for chromate, fast kinetics, and high recyclability is strategic for better reuse of industrial wastewater. Magnetic chitosan micro-particles (MC, for enhancing mass transfer) may constitute a solution for chromate removal from acidic solutions. The functionalization of this support with aminothiazole groups (ATA@MC) or imidazole carboxamide (AIC@MC) significantly improves chromate removal, with sorption capacities close to 6 mmol Cr g-1, at pH 2. The Langmuir and the Sips equations finely fit sorption isotherms, while the pseudo-first order rate equation fits well uptake kinetics (equilibrium within 60 min). Sorption and desorption properties are remarkably stable: sorption efficiency decreases by less than 6% at the fifth cycle (while the desorption efficiency maintains above 99%). The sorbents are highly selective for chromate removal from acidic tannery wastewater (against base metals). FTIR and XPS analyses are used for characterizing the materials and for identifying the binding mechanisms (including chromate reduction into Cr(III)). The sorbents are both showing promising performances for Cr(VI) removal in acidic solutions, including in very complex solutions such as tannery wastewater. AIC@MC is more selective for Cr(VI) removal, while ATA@MC has a broader reactivity for a wider range of metal ions. The antimicrobial properties of the functionalized sorbents are characterized by the determination of the zone of inhibition (ZOI) against Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli and Candida albicans: the inhibition is slightly improved compared with magnetite chitosan microparticles. More generally, the Gram- bacteria are slightly more sensitive to the functionalized sorbents than Gram+ bacteria and Candida fungus.

International audience; A one-pot synthesis procedure is designed for preparing three α-aminophosphonates (R-H, R-COOH, and R-NH2); through the reaction of amine precursors (aniline, anthranilic or o-phenylene diamine, respectively) with salicylaldehyde and triphenylphosphite, under controlled conditions. These materials are first characterized by elemental analysis, FTIR, 1H NMR, 31P NMR, BET, DLS, pHzpc, TGA and titration. In a second step, the sorption properties are compared for U(VI) recovery from mildly acidic solutions. At the optimum pH (i.e., pH 4) the sorbents can be ranked according the series: R-H (1.057 mmol U g−1) > R-NH2 (0.746 mmol U g−1) > R-COOH (0.533 mmol U g−1). The isotherms are fitted by the Langmuir equation. Uranium uptake is relatively fast: under selected experimental conditions, the equilibrium is reached within 90 min of contact. The kinetic profiles are indistinctly fitted by the model of resistance to intraparticle diffusion and the pseudo-first order rate equation. The study of sorption thermodynamics shows substantial changes between the sorbents: uranyl uptake is endothermic with R-H and R-NH2 sorbents, while the reaction is exothermic with R-COOH sorbent. The diversity in functional groups and the speciation of uranyl in sulfuric acid solutions induce metal-binding through a combination of chelation and anion-exchange mechanisms (in function of pH). Sodium bicarbonate solutions achieve complete desorption of uranium from loaded-sorbents; the resins can be recycled for a minimum of 4–5 cycles with limited loss in efficiencies. The successful application of these resins for uranium recovery from acidic ore leachates demonstrates their promising properties for valorization of low-grade ores.

Understanding the behaviour of particulate matter and chemicals at the sediment-water interface (SWI) is of interest in environmental studies and risk assessments. These processes are still poorly understood, and this work aims to gain relevant insights by using a kinetic reactive transport model. It merges early diagenetic processes and box models for the uptake kinetics. Numerical solutions have been found for synthetic scenarios and for studying real cases from the literature (210Pb and Chernobyl fallout radionuclides in Lake Sniardwy, Poland, and 7Be in sediments from Tema Harbour, Ghana). The study identifies a series of factors that dynamically interact to govern the final fate of tracers in the SWI region, leading to a wide diversity of behaviours. When a term of eddy diffusivity is included in the upper regions of the pore fluid, which seems feasible for some energetic scenarios, it is possible to explain the observed large penetration depths for Cs and Be, while high particle-reactive elements are retained in thinner sediment layers. Desorption from the sediment occurs through the pore fluid as diffusive fluxes. Transient depth profiles of tracer concentrations can last from months up to a year, and they can show subsurface maxima at positions unrelated with the accretion rate. In the application cases, the model explained a wide set of observational data that was beyond the capabilities of other approaches involving physical mixing of solids and equilibrium kd. This modelling study could provide useful guidance for future research works.

Cellular uptake of dissolved methylmercury (MeHg) by phytoplankton is the most important point of entry for MeHg into aquatic food webs. However, the process is not fully understood. In this study we investigated the influence of chemical speciation on rate constants for MeHg accumulation by the freshwater green microalga

International audience; The one-pot synthesis of algal biomass/polyethyleneimine beads, ALPEI (electrostatic interaction followed by calcium ionotropic gelation), produces a stable sorbent whose sorption properties for rare earth elements (REEs) are significantly improved by functionalization. The grafting of sulfonic groups (S-ALPEI), which have high affinity for REEs, increases sorption capacities as high as 2.68 mmol Sc g−1, 0.61 mmol Ce g−1 and 0.53 mmol Ho g−1, at pH close to 4 (equilibrium pH). Sorption isotherms are fitted by the Langmuir equation for scandium and cerium; for holmium, the Freundlich and the Sips equations show better fits. Sorption occurs within 30–40 min; kinetic profiles are fitted by the pseudo-first order rate equation and the Crank equation (resistance to intraparticle diffusion). The sorbent has a marked preference for Sc(III) against Ce(III) and Ho(III) (confirmed by selectivity tests). The sorbent is also selective for REEs against alkali-earth elements. The three metals are readily desorbed (within 20–30 min) using HCl/CaCl2 solution. Desorption remains higher than 99% for 5 cycles while sorption performance is decreased by less than 6% at the fifth cycle. The sorbent is tested for the recovery of valuable metals from red mud solution at different pH values. Despite the large excess of heavy metals in the industrial solution, S-ALPEI shows a good affinity for REEs at pH close to 3.46 with important enrichment factors (in the range 19–118 depending on the metal). The material is fully characterized by BET, TGA, FTIR, XPS, elemental analysis, titration and SEM-EDX analysis. The sorption involves different mechanisms (on amine and sulfonic groups) including electrostatic attraction and chelation depending on pH and metal speciation.

Background The artificial mussel (AM) is a passive sampling device that was originally developed for monitoring metal concentrations in the marine environment, but is also increasingly used in freshwater environments. The AM consists of a non-permeable Perspex tube, which is closed on both sides with a semi-permeable membrane. The space in between contains Chelex-100 beads, which bind metals. The AM allows the determination of the dissolved, bioaccessible metal fraction in water bodies without killing organisms, as well as environments with unfavorable conditions for living bioindicators. In the present study, the use of the AM was adapted for the monitoring of platinum (Pt) in a freshwater ecosystem. Results The elution of Pt from the Chelex-100 beads was optimized. Two modifications to the original method for the use of AMs are recommended, i.e., washing and separation of the beads through centrifugation and elution with a mixture of 4.5 mL HNO3 and 0.5 mL HCl for approximately 2–3 h to ensure the release of all Pt bound to the beads. Additionally, the uptake kinetics of the AM were determined under laboratory conditions over a wide exposure concentration range (0.1–1000 µg/L) showing highly correlated Pt accumulation in the AMs with the aqueous exposure concentration. For the tested Pt exposure concentrations of 0.1, 1, 10, and 100 µg/L, the Pt concentrations in the AMs increased during the exposure period of 6 weeks. At the highest exposure concentration of 1000 µg/L, the increase stagnated after 3 weeks. To validate the AM in the field, the Pt accumulation of the AM was assessed together with that of freshwater clams (Corbicula fluminalis africana), muscle and liver tissue of the three fish species sharptooth catfish (Clarias gariepinus), common carp (Cyprinus carpio) and Mozambique tilapia (Oreochromis mossambicus), as well as water hyacinths (Eichhornia crassipes) at two sampling sites in the Pt mining area of South Africa. Conclusion Results from the present study showed that the AM is a promising tool to monitor Pt concentrations in the freshwater environment at contaminated sites.

Treatment technologies such as ion exchange (IX) process exhibit promising potentials for the removal of toxic per- and poly-fluoroalkyl substances (PFAS) from natural waters. In recent years, industries have started manufacturing PFAS-specific resins which are typically operated in a single use-and-dispose mode until exhaustion. However, this increases the resin demand and the consequent operational cost and environmental burden of the IX process. In this study, the performance of a PFAS-specific resin (A592) was compared with that of a regenerative organic scavenger resin (A860) which is traditionally employed for dissolved organic matter (DOM) and micorpollutant removal. Comparative studies were performed to examine the removal of multiple long- and short-chain carboxylic, sulfonic, precursor and emerging PFAS (including GenX) from synthetic and natural waters. The A592 resin exhibited faster uptake kinetics for PFAS while simultaneously removing 10–15% of DOM. The A860 resin removed ~60–70% of DOM; however, it required approximately 3-fold higher contact times for achieving the same degree of PFAS removal when compared to the PFAS-specific resin. The resin breakthrough (Ctreated (PFAS) > 70 ng/L) was observed around 125,000 ± 5000 bed volumes (BVs) for the PFAS-specific resin (via multiple loading tests), while it ranged between 15,000–27,000 BVs for the organic scavenger. Yet, a mass balance on PFAS and DOM removal indicated ~90–98% site saturation (in milli-equivalents (meqs)) on both IX resins before exhaustion. More importantly, the regenerated organic scavenger resin (A860) exhibited PFAS and DOM removal capabilities for longer operational BVs when compared to A592 operated in a single-use-mode in natural waters.

In this study, 76 μm polyoxymethylene (POM) strips were evaluated as a passive air sampler (PAS) for monitoring the volatile emissions from dredged material placed in confined disposal facilities (CDF). Laboratory evaluations were used to assess the uptake kinetics, average equilibrium time, and estimate the POM-air partition coefficients (KPOM-A) of 16 PCB congeners. The uptake kinetics defined the effective averaging time for air sampling and ranged from about a week for dichlorobiphenyls to 2 weeks or more for tetra- and pentachlorobiphenyls at ∼20 °C under internal mass transfer resistance control which was applicable for Log KPOM-A

International audience; Three commercial resins bearing sulfonic, amino phosphonic, or phosphonic/sulfonic reactive groups have been tested for the removal of iron and cadmium from phosphoric acid solutions. The sorption properties are compared for different experimental conditions such as sorbent dosage (0.5–2.5 g L−1), phosphoric acid concentration (from bi-component solutions, 0.25–2 M), and metal concentrations (i.e., in the range 0.27–2.7 mmol Cd L−1 and 0.54 mmol Fe L−1) with a special attention paid to the impact of the type of reactive groups held on the resins. The sulfonic-based resin (MTC1600H) is more selective for Cd (against Fe), especially at high phosphoric acid concentration and low sorbent dosage, while MTS9500 (aminophosphonic resin) is more selective for Fe removal (regardless of acid concentration and sorbent dosage). Equilibrium is reached within 2–4 h. The resins can be ranked in terms of cumulative sorption capacities according the series: MTC1600H > MTS9570 > MTS 9500. Sulfuric acid (0.5–1 M) can be efficiently used for the desorption of both iron and cadmium for MTC1600H, while for MTS9570 (phosphonic/sulfonic resin) sulfuric acid correctly desorbs Cd (above 96% at 1 M concentration), contrary to Fe (less than 30%). The aminophosphonic resin shows much poorer efficiency in terms of desorption. The sulfonic resin (i.e., MTC1600H) shows much higher sorption capacity, better selectivity, comparable uptake kinetics (about 2 h equilibrium time), and better metal desorption ability (higher than 98% with 1 M acid concentration, regardless of the type of acid). This conclusion is confirmed by the comparison of removal properties in the treatment of different types of industrial phosphoric acid solutions (crude, and pre-treated H3PO4 solutions). The three resins are inefficient for the treatment of crude phosphoric acid, and activated charcoal pre-treatment (MTC1600H reduced cadmium content by 77%). However, MTC1600H allows removing over 93% of Fe and Cd for H3PO4 pre-treated by TBP solvent extraction, while the others show much lower efficiencies (

International audience; Silica microspheres are functionalized through the grafting of either polymethacrylic acid or amidoxime groups (mono-functional composite, PMAA/SiO2 and PAO/SiO2, respectively) or in combination (bi-functional composite, PAOxMAA100-x/SiO2). The materials are characterized by textural analysis, TGA, SEM-EDX, elemental analysis, FTIR, XPS, pHPZC in order to confirm the synthesis route, identify the reactive groups and support the interpretation of sorption mechanisms toward Sr(II). The sorption of Sr(II), at optimum pH 8, involves amine groups and hydroxyl/carboxyl groups in the bi-functional composite sorbent. The comparison of sorption properties shows that maximum sorption requires a majority of carboxylic groups from polyacrylic compared with amidoxime functions; optimum formulation: PAO20MAA80/SiO2 sorbent. Sorption isotherms are efficiently fitted by the Langmuir and Sips equations: the maximum sorption capacity reaches around 1.38 mmol Sr g−1. Kinetic profiles for sorption are modeled using the pseudo-first order rate equation; equilibrium is achieved within 40–60 min. Complete desorption of Sr(II) using 1 M HCl solutions is even faster; equilibrium time being 15–20 min. The sorbent can be recycled for 5 cycles with a limited decrease in the sorption performance, and full desorption. In fixed-bed column, the breakthrough curves are fitted by the Thomas equation. In multi-component solutions, the sorbent shows a preferred selectivity according the sequence: K(I) > Ba(II) > Na(I) > Ca(II). Tested on seawater, the sorbent shows high distribution ratio for Sr(II), B(III) and Mo(VI)

Aims: To characterize Ni hyperaccumulation mechanisms in naturally Ni-hyperaccumulating Odontarrhena species, Ni uptake kinetics, and the effect of Fe starvation and Fe or Zn excess thereon, were investigated in the Iranian serpentine endemics O. bracteata (one population) and O. inflata (two populations). Methods: Plants were exposed to a series of Ni concentrations for 4 h, and Ni uptake rates were plotted against the Ni concentration in the solution. Kinetic parameters, Km and Vmax, were calculated from Lineweaver-Burke plots. Results: Ni uptake consistently showed Michaelis–Menten kinetics. Under normal Fe supply the Km was not significantly different between species or populations, however, the Vmax was 3-fold higher in O. bracteata and O. inflata from Baneh than in O. inflata from Marivan. The rate of Ni translocation to the shoot was similar in all of the species/populations. Fe starvation (1 wk) significantly increased the Vmax for Ni uptake in O. bracteata, but not in O. inflata, and a very similar increase in Fe uptake capacity in all the species/populations. Fe excess in the nutrient solution significantly increased the Km for Ni uptake in O. bracteata, but not in O. inflata. Zn excess in the nutrient solution (300 μM) marginally inhibited Ni uptake in O. inflata, but not in O. bracteata. Conclusions: Ni uptake seems to proceed via a Fe deficiency-inducible Fe transporter in O. bracteata, but not in O. inflata. Ni root-to-shoot translocation seems to be mediated by a Fe deficiency-inducible Fe translocation mechanism in all of the species/populations.

International audience; Magnetic chitosan particles were successfully modified by amidoxime-grafting (as evidenced by FTIR analysis, SEM-EDX analysis, elemental analysis, X-ray diffraction (XRD), thermogravimetric analysis and titration). The effect of pH was investigated showing optimum sorption at pH 4 for U(VI) and pH 5 for Eu(III). Uptake kinetics are relatively fast: the equilibrium was reached within 60–90 min; and the kinetic profiles were preferentially fitted by the pseudo-second order rate equation. Sorption isotherms are equally fitted by the Langmuir and the Sips equations; under optimal conditions maximum sorption capacity reaches 1.5 mmol U g−1 and 2.47 mmol Eu g−1. In bi-component solution, at pH close to 4.9, uranyl is enriched on the sorbent (higher selectivity coefficient) while maintaining high sorption capacities. The selectivity for Eu(III) sorption is higher at pH 2.3 but at the expense of a decrease in sorption capacities. Metal ions can be readily and fast desorbed using 0.5 M HCl solutions: 30–90 min are sufficient for achieving the complete desorption of U(VI) and about 95% of Eu(III) desorption. Sorption and desorption performances are maintained almost constant over 5 cycles of sorption/desorption: the sorbent can be efficiently recycled. Uranium was successfully recovered from alkaline leachate of a sedimentary dolostone ore material.

International audience; Cellulose and chitosan have intrinsic sorption properties for Nd(III); however, their efficiency for metal recovery can be easily improved by a relatively simple chemical modification. The grating of aspartic acid via an intermediary chlorination step of the polysaccharides allows increasing sorption capacities due to the specific reactivity of carboxylate groups. The grafting process is confirmed by elemental analysis, FTIR spectrometry, while the physical properties of the derivatives are characterized by XRD (crystallinity) and TGA (thermogravimetric analysis). The sorption properties are carried out by investigating the effect of the pH, studying the uptake kinetics and evaluating the thermodynamics (sorption isotherms). The sorption properties of modified sorbents are systematically compared to the performance of raw materials. Sorption capacity is doubled after grafting aspartic acid onto biopolymer backbone. Sorption isotherms are described by the Freundlich and the Langmuir equation and maximum sorption capacities reach up to 77-80 mg Nd g(-1) at pH 5. The uptake kinetics are described by the pseudo-first order reaction rate and under selected experimental conditions the equilibrium is reached within 3 h of contact. The sorption is spontaneous, endothermic. Metal desorption can be successfully performed with 0.5 M nitric acid and the sorbents can be recycled for at least 4 sorption/desorption cycles without significant loss in sorption/desorption performances.

Human activities have increased the availability and distribution of dissolved inorganic N (DIN) in the biosphere. Streams can remove some of this excess DIN, but in-stream uptake pathways of NO3− and NH4+ can be sensitive to the concentration of DIN. DIN uptake kinetics (i.e., changes in uptake in response to changes in concentration) are used to predict how streams will respond to increased DIN. This concentration–uptake relationship is unclear for NH4+ because of complex interactions governing uptake, including the influence of dissimilatory processes (i.e., nitrification) on total uptake. We used sequential pulse additions of NO3− and NH4+ to investigate DIN uptake in 3 subalpine streams in Rocky Mountain National Park, Colorado, USA. Mass removal rates (U; µg m–2 min–1) of NO3− were higher than NH4+, but NH4+ had greater uptake rate relative to concentration (vf; mm/min). We used a new method of estimating nitrification that accounts for concomitant NH4+ uptake and found that 7 to 19% of the ...

In situ extraction of steroid hormones from waste water using adsorption-based integrative passive samplers represents a promising approach for their monitoring in water at ultra-trace concentrations. Three passive samplers, namely a POCIS, a Chemcatcher fitted with an Empore SDB-RPS disk, and an Empore SDB-RPS disk-based sampler with enhanced water flow, were calibrated in situ in treated municipal wastewater for the purpose of monitoring five estrogens (17-β-estradiol, 17-α-estradiol, 17-α-ethinylestradiol, estrone and estriol) at sub ng per litre concentrations. Uptake of steroids to samplers during 14-day exposure in wastewater was compared with steroid concentrations in daily collected composite water samples. Sampling rates were obtained from a numerical solution of first order uptake kinetics equations describing the uptake of compounds into a passive sampler over time. Mass transfer of steroids in the Chemcatcher fitted with naked Empore disks was more than two times faster than in the POCIS sampler. The uptake capacity of the applied Empore disk was not sufficient for integrative uptake of all tested steroids during the entire 14-day exposure. Time-weighted average concentrations of steroids estimated at concentrations in units of ng L−1 using the in situ-calibrated samplers were within a factor of two from values obtained using composite water samples.

International audience; The copolymerization of styrene with divinylbenzene (DVB) in the presence of silica particles produces a commercial silica-supported polymer (SiO2-P) that was chemically reacted with acrylonitrile to synthesize silica-supported polyacrylonitrile (PAN/SiO2). PAN/SiO2 was functionalized by grafting amidoxime moieties to produce PAO/SiO2 sorbent (silica-supported polyacrylamidoxime). The sorbent (PAO/SiO2) was characterized by XPS, TGA, FTIR, pHpzc, elemental and SEM-EDX analyses and tested for Ga(III) recovery from aqueous solutions. The sorption performance was investigated through the study of pH effect, sorption isotherms at different temperatures, and uptake kinetics under slightly acidic conditions (around pH 4) and at pH close to 13.7 (similar to Bayer liquor). The equilibrium was reached within 60 min; the kinetic profiles can be fitted by the pseudo-second order rate equation (PSORE) and the resistance to intraparticle diffusion equation (RIDE). The maximum sorption capacity reaches 1.34 mmol Ga g−1 at 25 °C (1.76 mmol Ga g−1 at 55 °C): the sorption process is endothermic for solutions prepared by alkaline dissolving of Ga2O3. The sorption capacities are higher for solutions prepared with Ga(NO3)3 salt: the maximum sorption capacity increased up to 2.1–2.6 mmol Ga g−1 (from 25 to 55 °C). Langmuir and Sips equations were used for fitting sorption isotherms. Metal desorption and sorbent recycling were performed using 1.5 M HCl solution. Forty-five minutes were sufficient for achieving complete desorption of Ga(III). Sorption and desorption performances remain stable for a minimum of 5 cycles. Sorbent selectivity for gallium recovery was demonstrated in the presence of an excess of competitor cations. The sorbent was successfully applied for Ga(III) recovery from Bayer liquor at high pH values (around 13): combining relatively high efficiency and selectivity compared with LSC-600 amidoxime resin.

The sorption properties of a functionalized magnetic chitosan sorbent have been investigated for the recovery of Ni(II) and Pb(II) from aqueous solutions. This material was prepared by one-pot co-precipitation of chitosan with formation of magnetic core, followed by a series of grafting steps to immobilize hydrazinyl amine derivative at the surface of chitosan layer. The physico-chemical characteristics of this composite material were investigated using FTIR, XRD, XPS, thermogravimetric, titration, elemental analyses. In a second step, the sorbent was tested for heavy metal sorption on synthetic solutions through the study of pH effect, sorption isotherms and uptake kinetics, selective sorption (in function of pH), metal desorption and sorbent recycling. Sorption isotherms were modeled using the Sips equation while the uptake kinetics was fitted by the pseudo-second order rate equation. The sorption capacity reached 4.3 mmol Ni g−1 and 2.5 mmol Pb g−1 but the sorbent was more selective to Pb(II) over Ni(II), especially in acidic conditions. The decrease in sorption capacity at the fifth cycle does not exceed 8%. In the final step of the study, the sorbents were successfully applied for metal recovery from multi-metal synthetic solution and from a contaminated stormwater collected in a local mining area.

International audience; Magnetic chitosan nanoparticles, activated by glycidyl methacrylate, can be functionalized by grafting diethylenetriamine (DETA) and dithizone for improving U(VI) sorption at pH around 5. The physicochemical properties of the materials have been characterized by a wide variety of analytical techniques. Uranyl sorption increases with the pH (progressive deprotonation of amine and sulfur groups). Uptake kinetics are controlled by the agitation mode: the equilibrium time is reduced while using ultrasonic treatment (especially at highest frequency: 80 kHz): the cavitation effect improves the accessibility to internal reactive groups (sorption capacity is increased). The diffusivity coefficient is increased by 4–5 times. In the case of microwave, the sorption capacity is significantly reduced (especially for R-Dithizone, down to 0.8 mmol U g−1) because of temperature increase, which limits the sorption (exothermic mechanism). Mass transfer is tremendously enhanced: equilibrium time is less than 60 s (30 min for ultrasonic treatment and 120 min with mechanical agitation). Sorption capacity at monolayer saturation (Langmuir) decreases with increasing the temperature from 2.20 to 1.74 mmol U g−1 for R-Amine (from 1.77 to 1.22 mmol U g−1 for R-Dithizone). The sorption enthalpy is close to −19.7 kJ mol−1 for R-Amine (with positive entropy change, ΔS°) and −34.2 kJ mol−1 for R-Dithizone (negative ΔS°). Metal desorption is highly efficient using 0.3 M Na2CO3 /0.1 M H2O2 solution. Metal desorption is instantaneous (less than 1 min) and complete when using microwave treatment. The ultrasonic treatment allows improving desorption efficiency and decreasing the concentration of the eluent compared with mechanical agitation. The process is successfully applied for uranyl separation from the leachates of marine sediments, especially in the presence of Complexon III (masking agent).

This work aims to provide insight on the effects of chromium (Cr) uptake in seagrasses at environmentally relevant exposure concentrations; information on this issue can further increase the utility of marine angiosperms as indicators of trace metal contamination. Cr uptake kinetics, effects on physiological and structural cell traits, and the uptake-effects relationship in Halophila stipulacea leaves incubated in 0.01–10 mg L−1 (0.2–200 μM) of Cr (VI) were examined. An initial uptake was followed by a decrease at 0.01–0.5 mg L−1 (0.2–10 μM); at higher exposures, the fit of uptake data to a Michaelis-Menten-type equation was significant (p

The capacity of leaves to take up chemicals from the atmosphere and water influences how contaminants are transferred into food webs and soil. We provide a proof of concept of a passive dosing method to measure leaf/polydimethylsiloxane partition ratios (Kleaf/PDMS) for intact leaves, using polychlorinated biphenyls (PCBs) as model chemicals. Rhododendron leaves held in contact with PCB-loaded PDMS reached between 76 and 99% of equilibrium within 4 days for PCBs 3, 4, 28, 52, 101, 118, 138 and 180. Equilibrium Kleaf/PDMS extrapolated from the uptake kinetics measured over 4 days ranged from 0.075 (PCB 180) to 0.371 (PCB 3). The Kleaf/PDMS data can readily be converted to fugacity capacities of leaves (Zleaf) and subsequently leaf/water or leaf/air partition ratios (Kleaf/water and Kleaf/air) using partitioning data from the literature. Results of our measurements are within the variability observed for plant/air partition ratios (Kplant/air) found in the literature. Log Kleaf/air from this study ranged from 5.00 (PCB 3) to 8.30 (PCB 180) compared to log Kplant/air of 3.31 (PCB 3) to 8.88 (PCB 180) found in the literature. The method we describe could provide data to characterize the variability in sorptive capacities of leaves that would improve descriptions of uptake of chemicals by leaves in multimedia fate models.

International audience; Thiourea-formaldehyde (TF) resin is prepared by polycondensation of its two precursors; the incorporation of pre-formed magnetite particles allows synthesizing a magnetic derivative of TF (MTF). These materials are applied to the sorption of two dyes (titan yellow, TY, and rose bengal, RB). Ultrasonic treatment (UT) is tested as an alternative to mechanical agitation (MA). The two sorbents are characterized by scanning electron microscopy, vibrating-sample magnetometry, BET surface area analysis, thermogravimetric analysis, Fourier-transform infrared and NMR spectroscopy, zetametry. Sorption properties are compared for TF and MTF under both MA and UT; considering pH effect, uptake kinetics (modeled using the pseudo-second order rate equation, and resistance to intraparticle diffusion), sorption isotherms (fitted by the Langmuir and Sips equations), the effect of competitor ions, and the desorption efficiency. Optimum sorption occurs at pH 3 (balance between (a) the electrostatic interactions between protonated groups (sorbent) and anionic forms of the dyes, and (b) the competitor effects of counter anions). UT strongly decreases the contact time required for reaching equilibrium (from 240 min to 30 min). UT increases the sorption capacities: in the range 0.3–0.6 mmol dye g−1 (MA) up to 0.9–1 mmol dye g−1. The magnetic core does not change kinetics, while it increases TF sorption capacities for both TY and RB. Under UT, the maximum sorption capacities are comparable for TF and MTF; however, the affinity of MTF remains higher than TF for the two dyes. Alkaline NaCl solutions completely desorb the dyes; UT decreases both the contact time and the NaCl concentration required for achieving the complete desorption of loaded dyes. The sorbents are recycled with high stability in sorption performance for at least five cycles.

International audience; A one-pot synthesis procedure was used for preparing two derivatives of chitosan bearing α-aminophosphonate moieties. Chitosan functionalization was performed by reacting chitosan with glutaraldehyde and triphenylphosphite or trimethylphosphite under selected experimental conditions. The materials (CS-Ph and CS-Me, respectively) were characterized using different analytical procedures for confirming their suggested structures: scanning electron microscopy (coupled to energy dispersive X-ray analysis), Fourier-transform infra-red spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy analyses, thermogravimetric analysis and elemental analysis. The sorption properties of these materials were compared for U(VI) recovery through the study of pH effect, sorption isotherms, thermodynamics, uptake kinetics and sorbent recycling (metal desorption and sorbent re-use). The sorption isotherms were modeled using the Langmuir and the Sips equations while the kinetic profiles were preferentially fitted by the pseudo-second order rate equation. The comparison of sorption properties shows that the methyl α-aminophosphonate derivative is much more effective in uranium recovery than the phenyl derivative: maximum sorption capacities reached at pH 5 around 245 mg U g−1 and 114 mg U g−1, respectively. Tentative explanations are suggested associated to the acid-base properties, the steric hindrance and the donor/acceptor behavior of reactive groups. Experimental data show that uranyl sorption process proceeds via an exothermic and spontaneous reaction for the two sorbents. Metal desorption was successfully tested using sodium bicarbonate solutions and the sorbent was recycled four times: the sorption and desorption efficiencies progressively decreased but remained relatively high at the fourth cycle (sorption: 88–90% of initial sorption and desorption decreasing by 5% between the first and the fourth cycles). Finally, the sorbents were efficiently tested on acidic ore leachate.

International audience; A composite material (PAN-Na-Y-zeolite) was prepared by polymerization of acrylonitrile in the presence of Na-Y zeolite. The A composite was functionalized by amidoximation through the reaction of hydroxylamine on nitrile groups of the composite. The sorbent (APNa-Y-zeolite) was fully characterized by FTIR spectrometry, XRD diffraction, thermogravimetric analysis, scanning electron microscopy, zetametry and BET analysis. The sorption properties of APNa-Y-zeolite were investigated for the recovery of Cu(II), Cd(II) and Pb(II) from synthetic solutions before being tested for the purification of local tap water. Sorption properties were characterized through the study of pH effect, uptake kinetics, sorption isotherms. The pseudo-second order rate equation fitted well kinetic profiles. Sorption isotherms were modeled using the Langmuir, the Freundlich and the Sips equations. Thermodynamic parameters were evaluated through variation of temperature. While the sorption of Cu(II) and Cd(II) was endothermic, Pb(II) recovery was exothermic. Metal ions were successfully desorbed using 5 M HCl solutions. High concentrations of NaCl hardly alter sorption performance, contrary to humic acid that slightly reduces metal binding.

There is limited study to simultaneously determine the relative bioavailability of heavy metals such as Cd, Pb, Cu, Cr(VI), and Ni in soil samples. In the present study, the bioaccessibility of heavy metals using in vitro assay was compared with the relative bioavailability of heavy metals using in vivo mouse model. The bioaccessibility of heavy metals ranged from 9.05 ± 0.97 % (Cr) to 42.8 ± 3.52 % (Cd). The uptake profile of heavy metals in soil and solution samples in mouse revealed that the uptake kinetics could be fitted to a two-compartment model. The relative bioavailability of heavy meals ranged from 34.8 ± 7.0 % (Ni) to 131 ± 20.3 % (Cu). Poor correlation between bioaccessibility and relative bioavailability of heavy metals was observed (r (2) = 0.11, p > 0.05). The relative bioavailability of heavy metals was significantly higher than the bioaccessibility of heavy metals (p

Given the importance of the watershed protection plans, direct determination of phosphorus (P) mineralization rates in advanced wastewater treatment facility effluents is crucial for developing the most protective strategies minimiz eutrophication in receiving surface waters. In this study, algal bioassays were used to determine the uptake rate of dissolved P in effluents from a broad range of advanced nutrient removal technologies (e.g., membrane biological reactor, traditional biological, tertiary membrane, Blue PRO™, etc.). Dissolved P uptake kinetics were fit to a gamma model and three first-order decay models. A traditional one-pool model correlated poorly with the experimental data (i.e., r2 = 0.73 ± 0.09), whereas two-pool model and three-pool models performed much better (i.e., r2 > 0.9). These models also provided strong evidence for the existence of recalcitrant P in the effluents from these tertiary facilities. The Gamma model showed the mineralization of organic P followed a reactive continuum and further suggested the partitioning of P loads with different bioavailability levels should be accounted for the future modeling practices. From a modeling perspective, the Gamma model should be considered to be the theoretically best model as it gave the most parsimonious fit to the data using the fewest terms. Our study suggested that the current Total Maximum Daily Load (TMDL) model could be easily modified with the updated mineralization kinetics, which should lead to both ecological and economic benefits.

Arbuscular mycorrhizal fungi (AMF) appear to be highly associated with arsenic (As) uptake in host plants because arsenate (As(V)) and phosphorus (P) share the same transporter, whereby AMF can enhance P uptake. A short-term experiment was conducted for low- (0 to 0.05 mM As) and high-affinity (0 to 2.5 mM As) uptake systems, to investigate the AMF role on As uptake mechanism in plants, which may explain As uptake kinetics in upland rice cultivar: Zhonghan 221. When concentration of As ranged from 0 to 0.05 mM, Funneliformis geosporum (Fg) significantly decreased arsenite (As(III)) and monomethylarsonicacid (MMA) uptake when (p0.05) compared to non-mycorrhizal (NM) treatment, since the major route for (As(III)) in rice roots-rice silicon transporter Lsi1 would be influenced by Fg inoculation at high As concentrations. Fg can also reduce As(V) uptake significantly (p0.05) under both uptake systems relative to NM treatment, whereas, Funneliformis mosseae (Fm) increased As(V) and MMA uptake in rice roots, with MMA uptake rate generally lower than As(III) and As(V). Using suitable AMF species inoculation with rice, As uptake and accumulation in rice grains can be reduced and the risk to human health, once consumed, can be minimized.

Arsenic (As) and cadmium (Cd) are noxious and carcinogenic pollutants that can be removed from water by using emerging, ecofriendly, phytofiltration technology that employs Micranthemum umbrosum. After culturing M. umbrosum for 7 days in a hydroponic experiment, accumulation of 1219±44.11 µg As g−1 and 799.40±30.95 µg Cd g−1 were observed in the leaves, from 1000 µg As L−1 and 1000 µg Cd L−1 of water, respectively. Plant and water samples were analyzed for assessing the As and Cd accumulations, translocations, phytotoxic effects, uptake mechanisms and kinetics, and for evaluating the potential of M. umbrosum in As and Cd phytofiltration. The uptake pattern was leaf>stem>root for both pollutants. The plant showed higher resistance to As than to that to Cd. Uptake of inorganic As species was much greater than that of organic As and was found at above the substrate concentration. However, Cd showed similar uptake pattern to that of inorganic As species, and the data was better fit to a non-linear than a linear model. Low molecular weight substances that have thiol group(s) may be responsible for the binding of As in plants whereas Cd showed a different mechanism to that of As. M. umbrosum showed good As phytofiltration capabilities without any phytotoxic effects, but it was found to be a moderate accumulator of Cd with some phytotoxic effect compare to some other previously studied plant.

The main objective of this study was to evaluate the performance of a model for simulating the uptake of various pesticides on passive air samplers (PAS). From 2006-2007 a series of PAS using XAD-resin were deployed at Egbert, a rural agricultural site in southern Ontario, Canada, to measure the uptake of pesticides for time periods ranging from two months to one year. A continuous increase in sequestered amounts was observed for most pesticides, except for trifluralin and pendimethalin, which could conceivably be subject to substantial degradation inside the sampler. Continuous low-volume active air samples taken during the same period, along with data on weather conditions, allowed for the simulation of the uptake of the pesticides using the model (PAS-SIM). The modelled accumulation of pesticides on the PAS over the deployment period was in good agreement with the experimental data in most cases (i.e., within a factor of two) providing insight into the uptake kinetics of this type of sampler in the field. Passive sampling rates (PSR, m(3) d(-1)) were determined from the empirical data generated for this study using three different methods and compared with the PSRs generated by the model. Overall, the PAS-SIM model, which is capable of accounting for the influence of temperature and wind variations on PSRs, provided reasonable results that range between the three empirical approaches employed and well-established literature values. Further evaluation and application of the PAS-SIM model to explore the potential spatial and temporal variability in PAS uptake kinetics is warranted, particularly for established monitoring sites where detailed meteorological data are more likely to be available.

Dissolved organic matter (DOM) plays a central role in regulating productivity and nutrient cycling in freshwaters. It is therefore vital that we can representatively sample and preserve DOM in freshwaters for subsequent analysis. Here we investigated the effect of filtration, temperature (5 and 25 °C) and acidification (HCl) on the persistence of low molecular weight (MW) dissolved organic carbon (DOC), nitrogen (DON) and orthophosphate in oligotrophic and eutrophic freshwater environments. Our results showed the rapid loss of isotopically-labelled glucose and amino acids from both filtered (0.22 and 0.45 μm) and unfiltered waters. We ascribe this substrate depletion in filtered samples to the activity of ultra-small (< 0.45 μm) microorganisms (bacteria and archaea) present in the water. As expected, the rate of C, N and P loss was much greater at higher temperatures and was repressed by the addition of HCl. Based on our results and an evaluation of the protocols used in recently published studies, we conclude that current techniques used to sample water for low MW DOM characterisation are frequently inadequate and lack proper validation. In contrast to the high degree of analytical precision and rigorous statistical analysis of most studies, we argue that insufficient consideration is still given to the presence of ultra-small microorganisms and potential changes that can occur in the low MW fraction of DOM prior to analysis.

Este artículo contiene 10 páginas, 3 figuras, 3 tablas., The capacity of stream biofilms to transform and assimilate N in highly N-loaded streams is essential to guarantee the water quality of freshwater resources in urbanized areas. However, the degree of N saturation experienced by urban streams and their response to acute increases in N concentration are largely unknown. We measured changes in the rates of NH4 1 uptake (UNH4) and oxidation (UAO) resulting from experimental increases in NH4 1-N concentration in mature biofilms growing downstream of a wastewater treatment plant (WWTP) and, thus, naturally exposed to high N concentration. We investigated the responses of UNH4 and UAO to NH4 1-N increases and the abundance of NH4 1 oxidizing bacteria and archaea (AOB and AOA) in epilithic and epipsammic biofilms. UNH4 and UAO increased with increasing NH4 1-N concentration for the 2 biofilm types, suggesting no N saturation under ambient levels of NH4 1-N. Thus, these biofilms can contribute to mitigating N excesses and the variability of NH4 1-N concentrations from WWTP effluent inputs. The 2 biofilm types exhibited different Michaelis–Menten kinetics, indicating different capacity to respond to acute increases in NH4 1-N concentration. Mean UNH4 and UAO were 5 higher in epilithic than epipsammic biofilms, coinciding with a higher abundance of AOA1AOB in the former than in the later (76 104 vs 14 104 copies/cm2). AOB derived from active sludge dominated in epilithic biofilms, so our results suggest that WWTP effluents can strongly influence in-stream NH4 1 processing rates by increasing N inputs and by supplying AOA1AOB that are able to colonize some stream habitats., This research was funded by the projects MEDSOUL (CGL2014-59977-C3-2-R), NITRISED (201530E062), and NICUS (CGL-2014-55234-JIN) from the I1D program of the SpanishMinistry of Economy, and funds provided by the European Union Commission. SNM was supported by a JAE predoctoral fellowship from the Spanish National Research Council (CSIC) and fund provided by the Velux Stiftung Swiss Foundation.

Eulimnogammarus cyaneus and Eulimnogammarus verrucosus, closely related amphipod species endemic to Lake Baikal, differ with respect to body size (10- to 50-fold lower fresh weights of E. cyaneus) and cellular stress response (CSR) capacity, potentially causing species-related differences in uptake, internal sequestration, and toxic sensitivity to waterborne cadmium (Cd). We found that, compared to E. verrucosus, Cd uptake rates, related to a given exposure concentration, were higher, and lethal concentrations (50%; LC50) were 2.3-fold lower in E. cyaneus (4 weeks exposure; 6 °C). Upon exposures to species-specific subacutely toxic Cd concentrations (nominal LC1; E. cyaneus: 18 nM (2.0 μg L–1); E. verrucosus: 115 nM (12.9 μg L–1); 4 weeks exposure; 6 °C), Cd amounts in metal sensitive tissue fractions (MSF), in relation to fresh weight, were similar in both species (E. cyaneus: 0.25 ± 0.06 μg g–1; E. verrucosus: 0.26 ± 0.07 μg g–1), whereas relative Cd amounts in the biologically detoxified heat stable pr...

International audience; The incorporation of glutaraldehyde-crosslinked polyethyleneimine (GLA-PEI) in algal biomass beads (AB/PEI) substantially increases the sorption capacity for Pd(II) and Pt(IV) compared to pure algal beads (Laminaria digitata) prepared by an original one-pot synthesis procedure (using a homogeneous ionotropic Ca-gelation, without addition of supplementary alginate). The sorption properties are compared to a reference material (alginate beads). Sorption efficiency increases with pH in relation with deprotonation of carboxylate and amine groups, limitation of the competition effect of counter anions and effect of metal speciation. Sorption isotherms (fitted by the Langmuir equation) show maximum sorption capacities close to 1.28 mmol Pd g−1 and 0.59 mmol Pt g−1 for the composite sorbent at pH 2.5, with a marked preference for Pd(II) against Pt(IV) (sorption isotherms in bi-component solutions), especially for alginate and algal beads that are more selective than AB/PEI (an excess of chloride ions limits this selectivity). The uptake kinetics are controlled by the resistance to intraparticle diffusion though the kinetic profiles are well fitted by the pseudo-second order rate equation. The drying conditions have critical impact on the diffusion properties: freeze-drying limits the irreversible collapse of the porous structure (which happens with air-drying): the presence of cellulose-like fibers (and/or agglomerates of GLA-PEI) in AB and AB/PEI limits this impact.

International audience; The grafting of urea and biuret on alginate backbone (confirmed by MR spectrometry analysis) increases by 53-84% the sorption efficiency of the biopolymer for Cd(II), Cu(II) and Pb(II) recovery from mild acidic solutions (i.e., pH in the range 4.5-5.5). Sorption isotherms are successfully described by the Langmuir and the Sips equations: maximum sorption capacities reach up to 3.7 mmol Cd g(-1), 4.7 mmol Cu g(-1) and 4.8 mmol Pb g(-1) for alginate-urea beads. The affinity of the sorbent for metal ions is correlated to the electronic properties (softness) and configuration of hydrated ions and to the HSAB properties (Hard and Soft Acid-Bases rules) of the ligands present on the sorbent. The diffusion properties are playing a significant role in the control of the uptake kinetic profiles; however, the pseudo-second order rate equation also allows a good fit of experimental sorption kinetics. In multi-component solutions the sorbents maintain a higher affinity for Pb(II) over the other two divalent cations.

The uptake kinetics of elemental gaseous Hg (Hg(0)) in three species of epiphytic lichens (Pseudevernia furfuracea, Evernia prunastri, and Xanthoria parietina) were investigated under four different Hg concentrations (10, 15, 30, and 45 μg/m(3)) and three different temperatures (10, 20, and 30 °C) with the aim of evaluating the lichen efficiency for Hg(0) accumulation and their potential use in the estimate of atmospheric concentrations of this metal in the field. The results showed that under our experimental conditions the lichens accumulated Hg according to exposure time and that the metal is not released back to the atmosphere after Hg(0) was removed from the air (clearance). Pseudevernia furfuracea showed the highest Hg accumulation capacity and Evernia prunastri showed the lowest, but in these species the metal uptake kinetics was affected by temperature. Xanthoria parietina showed an intermediate metal accumulation capacity and a Hg accumulation rate independent of temperature (in the range 10-30 °C). The use of first-order kinetics equations for Hg uptake in X. parietina and available field data on Hg bioaccumulation in this species allowed reliable estimates of atmospheric Hg concentrations in the environment.

Under laboratory conditions, the absorption law of three kinds of nutrients by three species of algae was investigated, the results showed that: the concentration of nitrate nitrogen, ammonium nitrogen and activated phosphate in the culture medium reduced with the extension of time. Enteromorpha intestinalis,Sargassum fusiforme and Sargassum thunbergii showed the highest uptake for nitrate nitrogen, ammonium nitrogen and activated phosphate, respectively;S. fusiforme, E. intestinalis and S. fusiforme showed the lowest uptake for nitrate nitrogen,ammonium nitrogen and activated phosphate, respectively. It illustrated that macroalgae could effectively reduce nutrients from the surrounding water.

Degradation and enantioselective bioaccumulation of diniconazole in earthworms (Eiseniafetida) in artificial soil was investigated using liquid chromatography-tandem mass spectrometry (LC-MS/MS) method under laboratory condition. Three exposure concentrations (1 mg/kg, 10 mg/kg and 25 mg/kg) of diniconazole in soil (dry weight) to earthworms were used. The uptake kinetics fitted the first-order kinetics well. The bioaccumulation factors (BAF) of R, S isomers were 6.6046 and 8.5115 in 25 mg/kg dose exposure, 2.6409 and 2.9835 in 10mg/kg dose exposure, 1.7784 and 2.0437 in 1 mg/kg dose exposure, respectively. Bioaccumulation of diniconazole in earthworm tissues was enantioselective with a preferential accumulation of S-diniconazole and the enantiomer fractions were about 0.45-0.50 in all three level dose exposures. In addition, it was obvious that both R-diniconazole and S-diniconazole had bioaccumulation effect in earthworm. Diniconazole was metabolized to 1,2,4-triazole, (E)-3-(1H-1,2,4-triazol-1-yl) acrylaldehyde, (E, S)-4-(2, 4-dichlorophenyl)-2, 2-dimethyl-5-(1H-1,2,4-triazol-1-yl)pent-4-ene-1,3-diol, and (E)-4-(2, 4-dichlorophenyl)-3-hydroxy-2,2-dimethyl-5-(1H-1,2,4-triazol-1-yl) pent-4-enoic acid in earthworms; the metabolites of 1,2,4-triazole and (E)-3-(1H-1,2,4-triazol-1-yl)acrylaldehyde could be detected in soil as well.

International audience; Nickel-potassium ferrocyanide (along with other ferrocyanide sub-products, as shown by mineralization, SEM-EDX and XRD analyses) has been immobilized in highly porous discs of chitin for the sorption of Cs(I) from near neutral solutions. The immobilization process allows synthesizing stable materials that can bind up to 80 mg Cs g(-1), (i.e., 240 mg Cs g(-1), ion-exchanger). Cesium sorption is hardly affected by the pH between pH 2 and 8. The sorbent is selective to Cs(I) even in the presence of high concentrations of Na(I), K(I), Rb(I) or NH4+. The pseudo-second order rate equation fits well kinetic profiles: the rate coefficient increases with the flow rate of recirculation (to force the access to potentially non-interconnected pores), as an evidence of the control of uptake kinetics by diffusion properties. In fixed-bed columns, the breakthrough curve is accurately described by the Clark model and the sorption capacity (at sorbent saturation) is consistent with the values obtained in sorption isotherms. Preliminary tests performed on Cs-137 spiked solutions confirm the efficiency of the material for the treatment of effluents bearing radionuclides.

After synthesis of parent PGMA micro-particles by dispersion polymerization method, diethylenetriamine (DETA) is grafted on the polymer (DETA-PGMA). In the last step, methylene phosphonic groups are grafted on DETA-PGMA by reaction of phosphonic acid groups onto amine functions in the presence of formaldehyde to produce polyaminophosphonic acid sorbent (PPA-PGMA). The sorbent is characterized by elemental analysis, FTIR spectrometry, XPS, XRD, TG-TDA and SEM-EDX analyses. The sorption properties of the material are tested for the sorption of La(III) and Y(III): the effect of pH on sorption performance is investigated before studying uptake kinetics, sorption isotherms (and thermodynamics), metal desorption and sorbent recycling. Maximum sorption capacities reach up to 0.79 mmol La g−1 and 0.73 mmol Y g−1 at pH 5 (optimum initial pH value). Sorption isotherms are characterized by a saturation plateau: the Langmuir equation fits well data. The sorption on micron-sized particles is fast and equilibrium is reached within 3–4 h: the kinetic profiles are modelled by the Crank equation (resistance to intraparticle diffusion) though the pseudo-first order rate equation fits well experimental data. Nitric acid (0.5 M) solutions can be used for metal recovery and the sorbent is re-used for at least 6 cycles of sorption and desorption with limited decrease in performance (less than 7%). The sorbent has a preference at pH 5 for La(III) vs. Y(III) but the selectivity coefficient is not high enough for potentiating the selective separation of the two metals.

General Research Fund from the Hong Kong Research Grants Council [662610]; Key Project from the Natural Science Foundation of China [21237004]

Green tides outbreak frequently around Lianyungang surrounding waters in recent years. In order to understand the nutrient response relationship with the typical Enteromorpha species, the experiment investigated uptake kinetics of NO3-N, NH4-N and PO4-P with Michaelis-Menten equation. It was found that the Ks values of Enteromorpha linza are lower than that of Enteromorpha prolifera, which indicated E. linza have a better ability to adapt low nutrient environment. Vmax for various nitrogen species followed the order of NO3-N > NH4-N, indicating ammonia absorption can inhibit the uptake of nitrate. The study provided a theoretical basis for exploring the Enteromorpha outbreak mechanism and marine ecological effects assessment.

Heterogeneous reactions of nitrogen dioxide (NO2) on soils collected from Dalian (S1) and Changsha (S2) were investigated over the relative humidity (RH) range of 5%-80% and temperature range of 278-328 K using a horizontal coated-wall flow tube. The initial uptake coefficients of NO2 on S2 exhibited a decreasing trend from (10 +/- 1.3) x 10(-8) to (3.1 +/- 0.5) x 10(-8) with the relative humidity increasing from 5% to 80%. In the temperature effect studies, the initial uptake coefficients of S1 and S2 decreased from (10 +/- 1.2) x 10(-8) to (3.8 +/- 0.5) x 10(-8) and from (16 +/- 2.2) x 10(-8) to (3.8 +/- 0.4) x 10(-8) when temperature increased from 278 to 288 K for S1 and from 278 to 308 K for S2, respectively. As the temperature continued to increase, the initial uptake coefficients of S1 and S2 returned to (7.9 +/- 1.1) x 10(-8) and (20 +/- 3.1) x 10(-8) at 313 and 328 K, respectively. This study shows that relative humidity could influence the uptake kinetics of NO2 on soil and temperature would impact the heterogeneous chemistry of NO2.