Metformin and lamotrigine sorption on a digestate amended soil in presence of trace metal contamination.

The antidiabetic drug metformin and antiepileptic drug lamotrigine are contaminants of emerging concern that have been detected in biowaste-derived amendments and in the environment, and their fate must be carefully studied. This work aimed to evaluate their sorption behaviour on soil upon digestate application. Experiments were conducted on soil and digestate-amended soil as a function of time to study kinetic processes, and at equilibrium also regarding the influence of trace metals (Pb, Ni, Cr, Co, Cu, Zn) at ratio pharmaceutical/metal 1/1, 1/10, and 1/100. Pharmaceutical desorption experiments were also conducted to assess their potential mobility to groundwater. Results revealed that digestate amendment increased metformin and lamotrigine adsorbed amounts by 210% and 240%, respectively, increasing organic matter content. Metformin adsorption kinetics were best described by Langmuir model and those of lamotrigine by Elovich and intraparticle diffusion models. Trace metals did not significantly affect the adsorption of metformin in amended soil while significantly decreased that of lamotrigine by 12-39%, with exception for Cu2+ that increased both pharmaceuticals adsorbed amounts by 5 - 8%. This study highlighted the influence of digestate amendment on pharmaceutical adsorption and fate in soil, which must be considered in the circular economy scenario of waste-to-resource.

Adsorption of Individual and Mixtures of ß-Blockers and Copper in Soils and Sediments.

The (bio)availability of pharmaceuticals at solid/water interfaces is governed by their sorption, which determines their concentrations in groundwaters and surface waters in contact with biota, and can be affected by the presence of other contaminants such as metallic trace elements likely to compete for adsorption sites and form complexes with pharmaceuticals. We studied the adsorption of the pharmaceuticals propranolol and sotalol-two ß-blockers-on one soil and one sediment using batch experiments to assess their (bio)availability. The influence of contact time, pH, and concentration was studied. As in the real environment these contaminants are not alone but in mixtures, and they were studied alone, simultaneously added, and in the presence of Cu2+ , which is known to form coordination complexes with propranolol and sotalol, but their presence in mixtures did not alter their adsorption properties. Sotalol was more mobile in water and thus more bioavailable for organisms than propranolol. The mobility in surface waters of both ß-blockers and thus their bioavailabity for organisms is more important than their risk of transfer to groundwater during rainwater infiltration and to surface water due to runoff. Environ Toxicol Chem 2022;41:2700-2707. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Magnetic properties of biogenic selenium nanomaterials.

Bioreduction of selenium oxyanions to elemental selenium is ubiquitous; elucidating the properties of this biogenic elemental selenium (BioSe) is thus important to understand its environmental fate. In this study, the magnetic properties of biogenic elemental selenium nanospheres (BioSe-Nanospheres) and nanorods (BioSe-Nanorods) obtained via the reduction of selenium(IV) using anaerobic granular sludge taken from an upflow anaerobic sludge blanket (UASB) reactor treating paper and pulp wastewater were investigated. The study indicated that the BioSe nanomaterials have a strong paramagnetic contribution with some ferromagnetic component due to the incorporation of Fe(III) (high-spin and low-spin species) as indicated by electron paramagnetic resonance (EPR). The paramagnetism did not saturate up to 50,000 Oe at 5 K, and the hysteresis curve showed the coercivity of 100 Oe and magnetic moment saturation around 10 emu. X-ray photoelectron spectroscopy (XPS) and EPR evidenced the presence of Fe(III) in the nanomaterial. Signals for Fe(II) were observed neither in EPR nor in XPS ruling out its presence in the BioSe nanoparticles. Fe(III) being abundantly present in the sludge likely got entrapped in the extracellular polymeric substances (EPS) coating the biogenic nanomaterials. The presence of Fe(III) in BioSe nanomaterial increases the mobility of Fe(III) and may have an effect on phytoplankton growth in the environment. Furthermore, as supported by the literature, there is a potential to exploit the magnetic properties of BioSe nanomaterials in drug delivery systems as well as in space refrigeration.

Molecular and Material Engineering of Photocathodes Derivatized with Polyoxometalate-Supported {Mo3S4} HER Catalysts.

Molecular engineering of efficient HER catalysts is an attractive approach for controlling the spatial environment of specific building units selected for their intrinsic functionality required within the multistep HER process. As the {Mo3S4} core derived as various coordination complexes has been identified as one as the most promising MoSx-based HER electrocatalysts, we demonstrate that the covalent association between the {Mo3S4} core and the redox-active macrocyclic {P8W48} polyoxometalate (POM) produces a striking synergistic effect featured by high HER performance. Various experiments carried out in homogeneous conditions showed that this synergistic effect arises from the direct connection between the {Mo3S4} cluster and the toroidal {P8W48} units featured by a stoichiometry that can be tuned from two to four {Mo3S4} cores per {P8W48} unit. In addition, we report that this effect is preserved within heterogeneous photoelectrochemical devices where the {Mo3S4}-{P8W48} (thio-POM) assembly was used as cocatalyst (cocat) onto a microstructured p-type silicon. Using a drop-casting procedure to immobilize cocat onto the silicon interface led to high initial HER performance under simulated sunlight, achieving a photocurrent density of 10 mA cm-2 at +0.13 V vs RHE. Furthermore, electrostatic incorporation of the thio-POM anion cocat into a poly(3,4-ethylenedioxythiophene) (PEDOT) film is demonstrated to be efficient and straightforward to durably retain the cocat at the interface of a micropyramidal silicon (SimPy) photocathode. The thio-POM/PEDOT-modified photocathode is able to produce H2 under 1 Sun illumination at a rate of ca. 100 µmol cm-2 h-1 at 0 V vs RHE, highlighting the excellent performance of this photoelectrochemical system.

Enrofloxacin and copper plant uptake by Phragmites australis from a liquid digestate: Single versus combined application.

Application of anaerobically digested sludges and manure (digestates) to agricultural fields reduces the need for fertilizer application, but might also pose environmental risks due to the introduction of various pollutants -including metal trace elements and pharmaceuticals- to amended soils. The simultaneous presence of different contaminants can affect plant uptake, altering the performance of phytoremediation. This work aims to investigate and compare the single and combined effects of Enrofloxacin (Enro) and Cu on their plant uptake from digestate solutions. Plant uptake experiments were carried out by exposing, for 5 days, Phragmites australis to three different concentrations of a liquid digestate doped with Cu and/or Enro. Contaminant concentrations were afterward determined in both plant tissues and digestate solutions. Contaminant speciation in solution and Cu speciation in plant roots were also assessed. Cu plant uptake (mostly in plant roots, Cu concentration varied between 55 and 254 µg·g-1) was observed, especially at low concentration of digestate. At high digestate concentration, Cu uptake decreased due to the formation of Cu-DOC complexes rendering Cu less bioavailable. The presence of the antibiotic slightly further reduced Cu plant uptake due to the formation of Cu-Enro complexes. Plant roots also accumulated Enro, an accumulation also higher for the lowest concentration of digestate (an increase of 40%), and that slightly increased in the presence of Cu (up to 226 µg·g-1). However, proportion of free Enro in solution decreased (up to 70%) in the presence of Cu due to complexation. Cu speciation in plant roots confirmed the implication of the complexation in the uptake of Cu and Enro when they are simultaneously present in solution. Thus, the presence of amendments (such as digestates) increasing the DOC content, in addition to the interactions between contaminants, should be taken into account for field crop soils as well as for phytoremediation technologies.

Mutations of Histidine†13 to Arginine and Arginine 5 to Glycine Are Responsible for Different Coordination Sites of Zinc(II) to Human and Murine Peptides.

Because mice and rats do not naturally develop Alzheimer's disease, genetically modified animals are required to study this pathology. This striking difference in terms of disease onset could be due to three alterations in the murine sequence (R5G, Y10F and H13R) of the amyloid-ß peptide with respect to the human counterpart. Whether the metal-ion binding properties of the murine peptide are at the origin of such different amyloidogenicity of the two peptides is still an open question. Herein, the main zinc binding site to the murine amyloid-ß at physiological pH has been determined through the combination of several spectroscopic and analytical methods applied to a series of six peptides with one or two of the key mutations. These results have been compared with the zinc binding site encountered in the human peptide. A coordination mechanism that demonstrates the importance of the H13R and R5G mutations in the different zinc environments present in the murine and human peptides is proposed. The nature of the minor zinc species present at physiological pH is also suggested for both peptides. Finally, the biological relevance and fallouts of the differences determined in zinc binding to human versus murine amyloid-ß are also discussed.

Combining sorption experiments and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to study the adsorption of propranolol onto environmental solid matrices - Influence of copper(II).

The bioavailability of pharmaceuticals is governed by their sorption in soils/sediments, as the retention processes determine their concentration in surface- and ground-water. The adsorption of these contaminants can involve various solid components such as organic matter, clays and metallic oxides, and their distribution among these solid components depends on contaminant and solid properties. In this paper we studied the adsorption of the pharmaceutical propranolol - a beta-blocker - on eight different solids (six soils, one sediment and one kaolinite-based sample) by batch experiments. The influence of contact time, propranolol concentration and pH was considered, as well as the presence of copper(II). The investigated solids displayed a wide variability in terms of CEC (cationic exchange capacity) and organic carbon and carbonates contents. The influence of pH was negligible in the pH range from 5.5 to 8.6. The adsorbed amounts were greatly dependent on the solid and two groups of solids were evidenced: three soils of high CEC and organic carbon contents which retained high amounts of propranolol, and three soils, the sediment and the kaolinite-based sample (low CEC and organic carbon content) displaying a low adsorption capacity for the beta-blocker. A linear model enabling the determination of the sorption parameters Kd and Koc was pertinent to describe the adsorption isotherms but the Koc values showed a great variability. It was shown that organic carbon content alone could not explain propranolol adsorption. The CEC value was identified as influent parameter and a simple empirical model was proposed to describe propranolol adsorption. At microscopic and molecular scales, ToF-SIMS experiments indicated (i) a decrease of potassium on the surface upon propranolol adsorption with a distribution of the beta-blocker similarly to alumino-silicates, iron and organic carbon on the surface confirming a cation exchange mechanism and (ii) the absence of degradation products and copper-propranolol complexes.

A Trishistidine Pseudopeptide with Ability to Remove Both CuΙ and CuΙΙ from the Amyloid-ß Peptide and to Stop the Associated ROS Formation.

The pseudopeptide L, derived from a nitrilotriacetic acid scaffold and functionalized with three histidine moieties, is reminiscent of the amino acid side chains encountered in the Alzheimer's peptide (Aß). Its synthesis and coordination properties for CuΙ and CuΙΙ are described. L efficiently complex CuΙΙ in a square-planar geometry involving three imidazole nitrogen atoms and an amidate-Cu bond. By contrast, CuΙ is coordinated in a tetrahedral environment. The redox behavior is irreversible and follows an ECEC mechanism in accordance with the very different environments of the two redox states of the Cu center. This is in line with the observed resistance of the CuΙ complex to oxidation by oxygen and the CuΙΙ complex reduction by ascorbate. The affinities of L for CuΙΙ and CuΙ at physiological pH are larger than that reported for the Aß peptide. Therefore, due to its peculiar Cu coordination properties, the ligand L is able to target both redox states of Cu, redox silence them and prevent reactive oxygen species production by the CuAß complex. Because reactive oxygen species contribute to the oxidative stress, a key issue in Alzheimer's disease, this ligand thus represents a new strategy in the long route of finding molecular concepts for fighting Alzheimer's disease.

Link between Affinity and Cu(II) Binding Sites to Amyloid-ß Peptides Evaluated by a New Water-Soluble UV-Visible Ratiometric Dye with a Moderate Cu(II) Affinity.

Being able to easily determine the Cu(II) affinity for biomolecules of moderate affinity is important. Such biomolecules include amyloidogenic peptides, such as the well-known amyloid-ß peptide involved in Alzheimer's disease. Here, we report the synthesis of a new water-soluble ratiometric Cu(II) dye with a moderate affinity (109 M-1 at pH 7.1) and the characterizations of the Cu(II) corresponding complex by X-ray crystallography, EPR, and XAS spectroscopic methods. UV-vis competition was performed on the Aß peptide as well as on a wide series of modified peptides, leading to an affinity value of 1.6 × 109 M-1 at pH 7.1 for the Aß peptide and to a coordination model for the Cu(II) site within the Aß peptide that agrees with the one mostly accepted currently.

Zinc(II) Binding Site to the Amyloid-ß Peptide: Insights from Spectroscopic Studies with a Wide Series of Modified Peptides.

The Zn(II) ion has been linked to Alzheimer's disease (AD) due to its ability to modulate the aggregating properties of the amyloid-ß (Aß) peptide, where Aß aggregation is a central event in the etiology of the disease. Delineating Zn(II) binding properties to Aß is thus a prerequisite to better grasp its potential role in AD. Because of (i) the flexibility of the Aß peptide, (ii) the multiplicity of anchoring sites, and (iii) the silent nature of the Zn(II) ion in most classical spectroscopies, this is a difficult task. To overcome these difficulties, we have investigated the impact of peptide alterations (mutations, N-terminal acetylation) on the Zn(Aß) X-ray absorption spectroscopy fingerprint and on the Zn(II)-induced modifications of the Aß peptides' NMR signatures. We propose a tetrahedrally bound Zn(II) ion, in which the coordination sphere is made by two His residues and two carboxylate side chains. Equilibria between equivalent ligands for one Zn(II) binding position have also been observed, the predominant site being made by the side chains of His6, His13 or His14, Glu11, and Asp1 or Glu3 or Asp7, with a slight preference for Asp1.

Adsorption and co-adsorption of diclofenac and Cu(II) on calcareous soils.

Pharmaceuticals are emerging contaminants and their presence in different compartments of the environment has been detected in many countries. In this study, laboratory batch experiments were conducted to characterize the adsorption of diclofenac, a widely used non-steroidal anti-inflammatory drug, on six calcareous soils. The adsorption of diclofenac was relatively low, which may lead to a risk of groundwater contamination and plant uptake. A correlation between the soil-water distribution coefficient Kd and soil characteristics has been highlighted. Indeed, diclofenac adsorption as a function of soil organic matter content (% OM) and Rt=% CaCO3/% OM was successfully described through a simple empirical model, indicating the importance of considering the inhibiting effect of CaCO3 on OM retention properties for a better assessment of diclofenac fate in the specific case of calcareous soils. The simultaneous co-adsorption of diclofenac and copper - a ubiquitous pollutant in the environment - at the water/soil interface, was also investigated. It appeared quite unexpectedly that copper did not have a significant influence on diclofenac retention.

Adsorption of enrofloxacin in presence of Zn(II) on a calcareous soil.

As a result of their consumption, excretion, disposal and persistence, antibiotics enter the soil environment and may be transported to surface and ground waters. During their transfer through soils, retention processes play a key role in their mobility. Antibiotics often coexist with heavy metals in soils due to agricultural practices and other sources of inputs. In this context, this study deals with the co-adsorption of Zn(II) and enrofloxacin (ENR), a widely-used veterinary antibiotic, on a calcareous soil using batch retention experiments and X-ray Absorption Near Edge Structure (XANES) spectroscopy. To improve our understanding of the interaction of this emerging organic contaminant with metal cations at the water-soil interface, the ternary system containing ENR, Zn(II) and a selected calcareous soil was investigated over a pH range between 7 and 10, at different solid-solution contact times and ENR concentrations. The presence of Zn(II) slightly influenced the retention of the antibiotic, leading to an increase of the adsorbed ENR amounts. The distribution coefficient Kd value increased from 0.66 Lg(-1) for single ENR adsorption to 1.04 Lg(-1) in presence of Zn(II) at a 1/2 ENR/Zn(II) ratio. The combination of adsorption isotherm data, solution speciation diagrams and XANES spectra evidenced a small proportion of Zn(II)-ENR complexes at soil pH leading to the slight increase of ENR adsorption in presence of zinc. These results suggest that it is necessary to consider the interaction between ENR and metal cations when assessing the mobility of ENR in soils.

Transcriptional response of stress-regulated genes to industrial effluent exposure in the cockle Cerastoderma glaucum.

This study assessed the responses of molecular biomarkers and heavy metal levels in Cerastoderma glaucum exposed for 1 week to two industrial effluents (1%) discharged into the Tunisian coastal area, F1 and F2, produced by different units of production of a phosphate treatment plant. A significant uptake of metals (Cd, Cu, Zn, and Ni) was observed in exposed cockles compared to controls, with an uptake higher for F1 than for F2. A decrease in LT50 (stress on stress test) was also observed after an exposure to the effluent F1. Treatments resulted in different patterns of messenger RNA (mRNA) expression of the different genes tested in this report. Gene transcription monitoring performed on seven genes potentially involved in the tolerance to metal exposure showed that for both exposures, mechanisms are rapidly and synchronically settled down to prevent damage to cellular components, by (1) handling and exporting out metal ions through the up-regulation of ATP-binding cassette xenobiotic transporter (ABCB1) and metallothionein (MT), (2) increasing the mRNA expression of antioxidant enzymes (catalase (CAT), superoxide dismutases, CuZnSOD and MnSOD), (3) protecting and/or repairing proteins through the expression of heat shock protein 70 (HSP70) mRNAs, and (4) increasing ATP production (through the up-regulation of cytochrome c oxidase 1 (CO1)) to provide energy for cells to tolerate stress exposure. The tools developed may be useful both for future control strategies and for the use of the cockle C. glaucum as a sentinel species.

Copper, nickel and zinc speciation in a biosolid-amended soil: pH adsorption edge, µ-XRF and µ-XANES investigations.

Metal solid phase speciation plays an important role in the control of the long-term stability of metals in biosolid-amended soils. The present work used pH-adsorption edge experiments and synchrotron-based spectroscopy techniques to understand the solid phase speciation of copper, nickel and zinc in a biosolid-amended soil. Comparison of metal adsorption edges on the biosolid-amended soil and the soil sample showed that Cu, Ni, and Zn can be retained by both soil and biosolid components such as amorphous iron phases, organic matter and clay minerals. These data are combined with microscopic results to obtain structural information about the surface complexes formed. Linear combination fitting of K-edge XANES spectra of metal hot-spots indicated consistent differences in metal speciation between metals. While organic matter plays a dominant role in Ni binding in the biosolid-amended soil, it was of lesser importance for Cu and Zn. This study suggests that even if the metals can be associated with soil components (clay minerals and organic matter), biosolid application will increase metals retention in the biosolid-amended soil by providing reactive organic matter and iron oxide fractions. Among the studied metals, the long-term mobility of Ni could be affected by organic matter degradation while Cu and Zn are strongly associated with iron oxides.

Molecular properties affecting the adsorption coefficient of pesticides from various chemical families.

Forty pesticides were selected in function of their chemical families and their physico-chemical properties to represent a wide range of pesticide properties. Adsorption of these pesticides was studied on two soils by batch experiments. The two soils differed largely in organic matter and calcite contents. Distribution coefficient Kd was determined for each pesticide on the two soils. Adsorption was higher for the soil having the highest organic matter content and the lowest calcite content. In order to identify pesticide properties governing retention, eight molecular descriptors were determined from three-dimensional (3D) structure of molecules. Class-specific quantitative structure properties relationship (QSPR) soil adsorption models using one and two parameters were developed from experimental Kd. Three properties seemed to influence most retention of pesticides: hydrophobicity, solubility, and polarisability. Models combining these properties were suggested and discussed.

Aging effect on Zn retention on a calcareous soil: column experiments and synchrotron X-ray micro-spectroscopic investigation.

In this study, a combination of column experiments and micro-analytical techniques exploiting synchrotron generated X-rays was used to assess the effect of aging time on Zn retention and mobility in the specific case of calcareous soils (high pH value, ≈ 8). The samples were subjected to aging for 2, 6, 17, and 63 days. Freshly added Zn mainly existed as an exchangeable form, and this metal fraction decreased over time due to Zn redistribution to stronger binding sites. Thus, after aging for 63 days, 45% of Zn is remobilized from exchangeable sites to stronger binding sites. µ-XRF maps were used to find correlations among elements in the sample, and µ-XANES spectra were recorded to precise Zn speciation. These analyses evidenced an increasing partitioning of Zn from organic matter to iron oxy(hydr)oxides over time. The occurrence of hydrozincite is evidenced in all samples.

Use of a new water-soluble Zn sensor to determine Zn affinity for the amyloid-ß peptide and relevant mutants.

Evaluation of Zn affinity for the amyloid-ß peptide involved in Alzheimer's disease and its modified counterparts is reported. This was made possible by the use of a new water-soluble chelator, the properties of which have also been described. Changes in the peptide sequence that impact Zn affinity are briefly discussed.

Impact of lime-stabilized biosolid application on Cu, Ni, Pb and Zn mobility in an acidic soil.

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl2, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl2 and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2 × 15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.

Leaching potential of phenylurea herbicides in a calcareous soil: comparison of column elution and batch studies.

The transfer of eleven phenylurea herbicides through soil columns was investigated in laboratory conditions in order to determine leaching properties in a calcareous soil. Elution curves with distilled water were plotted after herbicide application on the soil column. Phenylurea retention by the soil indicating interactions with soil can be classified as follows: fenuron < fluometron ≤ isoproturon = monuron < metoxuron < monolinuron < metobromuron < chlorotoluron < linuron = diuron < chlorbromuron. The number and nature of halogen atoms on the phenyl ring had an important influence on leaching. Retention was higher for molecules with higher number of halogen, and it was also higher for bromine than chlorine. Column elution experiments were compared to batch experiments from which the distribution coefficients K d were determined. According to Kendall correlation coefficients, parameter m/m 0 max from column experiments was relatively well linked to K d. In case of phenylurea, a linear relationship between K d and m/m 0 max was established.

Fate of nickel in a lime-stabilized biosolid, a calcareous soil and soil-biosolid mixtures.

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil-biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid-soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.