Cell wall acts as a major metal sink in plant roots, while a few studies focused on root cell wall binding in plants for the phytostabilization of multi-metal contaminated soils. A pot experiment was performed to characterize root cell wall properties of the mining ecotype (ME) and non-mining ecotype (NME) of Athyrium wardii (Hook.) in response to Cd and Pb. The cell wall was found to be the major sink for Cd (41.3–54.3%) and Pb (71.4–73.8%) accumulation in roots of the ME when exposed to Cd and/or Pb. The ME showed more Cd and Pb accumulation in root cell walls when exposed to Cd and Pb simultaneously, compared with those exposed to single Cd or Pb as well as the NME, suggesting some modifications for cell walls. The uronic acid contents of pectin and hemicellulose 1 (HC1) in root cell walls of the ME increased significantly when exposed to Cd and Pb simultaneously, suggesting enhanced cell wall binding capacity, thus resulting in more Cd and Pb bound to pectin and HC1. In particular, pectin was found to be the predominant binding site for Cd and Pb. Greater pectin methylesterase activity along with a lower degree of methylesterification were observed in the cell walls of the ME when exposed to Cd and Pb simultaneously. Furthermore, the ME present more O–H, N–H, C–OH, C–O–C, C–C and/or Ar–H in root cell walls when exposed to Cd and Pb simultaneously. These changes of root cell wall properties of the ME lead to enhanced cell wall binding ability in response to the co-contamination of Cd and Pb, thus could be considered a key process for enhanced Cd and Pb accumulation in roots of the ME when exposed to Cd and Pb simultaneously.

Aluminum (Al) phytotoxicity is a major limitation in the production of crops in the soils with pH ≤ 5. Boron (B) is indispensable nutrient for the development of higher plants and B role has been reported in the alleviation Al toxicity. Trifoliate orange rootstock was grown in two B and two Al concentrations. The results of the present study showed that Al toxicity adversely inhibited root elongation and exhibited higher oxidative stress in terms of H2O2 and O2− under B-deficiency. Additionally, the X-ray diffraction (XRD) analysis confirmed the increase of the cellulose crystallinity in the cell wall (CW). Al-induced remarkable variations in the CW components were prominent in terms of alkali-soluble pectin, 2-keto-3-deoxyoctonic acid (KDO) and the degree of methyl-esterification (DME) of pectin. Interesting, B supply reduced the pectin (alkali-soluble) under Al toxicity. Moreover, the results of FTIR (Fourier transform infrared spectroscopy) and 13C-NMR (13C nuclear magnetic resonance) spectra revealed the decrease of carboxyl groups and cellulose by B application during Al exposure. Furthermore, B supply tended to decrease the Al uptake, CW thickness and callose formation. The study concluded that B could mitigate Al phytotoxicity by shielding potential Al binding sites and by reducing Al induced alterations in the CW cellulose and pectin components.

Understanding of the interaction of graphene with natural polysaccharides (e.g., alginate) is crucial to elucidate its environmental fate. We investigated the impact of alginate on the agglomeration and stability of ¹⁴C-labeled few-layer graphene (FLG) in varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Enhanced agglomeration occurred at high CaCl₂ concentrations (≥5 mM) due to the alginate gel networks formation in the presence of Ca²⁺. FLG enmeshed within extended alginate gel networks was observed under transmission electron microscope and atomic force microscope. However, background Na⁺ competition for binding sites with Ca²⁺ at the alginate surfaces shielded the gelation of alginate. FLG was readily dispersed by alginate under environmentally relevant ionic strength conditions (i.e., <200 mM Na⁺ and <5 mM Ca²⁺). In comparison with the bare FLG, the slow sedimentation of the alginate-stabilized FLG (158 μg/L) caused continuous exposure of this nanomaterial to freshwater snails, which ingested 1.9 times more FLG through filter-feeding within 72 h. Moreover, surface modification of FLG by alginate significantly increased the whole-body and intestinal levels of FLG, but reduced the internalization of FLG to the intestinal epithelial cells. These findings indicate that alginate will act as a stabilizing agent controlling the transport of FLG in aqueous systems. This study also provides the first evidence that interaction of graphene with natural polysaccharides affected the uptake of FLG in the snails, which may alter the fate of FLG in aquatic environments.

Land application of biosolids or compost constitutes an important route of soil contamination by emerging contaminants such as acetaminophen and sulfamethoxazole. Using 14C labeling, we evaluated the influence of biosolids and compost on individual fate processes of acetaminophen and sulfamethoxazole in soil. The amendment of biosolids or compost consistently inhibited the mineralization of both compounds but simultaneously enhanced the dissipation of their extractable residues or parent form. Immediately after treatment, the majority of 14C-residue became non-extractable, reaching 80.3–92.3% of the applied amount at the end of 84-d incubation. Addition of biosolids or compost appreciably accelerated the formation of bound residue, likely due to the fact that the organic material provided additional sites for binding interactions or introduced exogenous microorganisms facilitating chemical transformations. This effect of biosolids or compost should be considered in risk assessment of these and other emerging contaminants.

This paper tested if culturing the moss Scorpiurum circinatum (Brid.) Fleisch. & Loeske with metal solutions (Cd, Cu, Pb and Zn) for 30 days causes metal bioaccumulation and ultrastructural changes. The results showed that despite the high heavy metal concentrations in treatment solutions, treated samples did not show severe ultrastructural changes and cells were still alive and generally well preserved. Bioaccumulation highlighted that moss cells survived to heavy metal toxicity by immobilizing most toxic ions extracellularly, likely in binding sites of the cell wall, which is the main site of metal detoxification.

The oxidation of magnetite into maghemite and its coating by natural organic constituents are common changes that affect the reactivity of iron oxide nanoparticles (IONP) in aqueous environments. Certain ubiquitous compounds such as humic acids (HA) and phosphatidylcholine (PC), displaying a high affinity for both copper (Cu) and IONP, could play a critical role in the interactions involved between both compounds. The adsorption of Cu onto four different IONP was studied: magnetite nanoparticles (magnNP), maghemite NP (maghNP), HA- and PC-coated magnetite NP (HA-magnNP and PC-magnNP, respectively). According to the results, the percentage of adsorbed Cu increases with increasing pH, irrespective of the IONP. Thus, protonation/deprotonation reactions are likely involved within Cu adsorption mechanism. Contrary to the other studied IONP, HA-magnNP favor Cu adsorption at most of the pH tested including acidic pH (pH = 3), suggesting that part of the active surface sites for Cu²⁺ were not grabbed by protons. The Freundlich adsorption isotherm of HA-magnNP provides the highest sorption constant KF (bonding energy) and n value which supports a heterogeneous sorption process. The heterogeneous adsorption between HA-magnNP and Cu²⁺ can be explained by both the diversity of the binding sites HA procured and the formation of multidendate complexes between Cu²⁺ and some of the HA functional groups. Such favorable adsorption process was neither observed on PC-coated-magnNP nor on maghNP, whose behaviors were comparable to that of magnNP. On another hand, HA and PC coatings considerably reduced iron (Fe) dissolution from magnNP as compared with magnNP. It was suggested that HA and PC coatings either provided efficient shield against Fe leaching or fostered dissolved Fe re-adsorption onto the functional groups at the coated magnNP surfaces. Thus, this study can help to better understand the complex interfacial reactions between cations-organic matter-colloidal surfaces which are relevant in environmental and agricultural contexts.This work showed that magnetite NP properties can be affected by surface modifications, which drive NP chemical stability and Cu adsorption, thereby affecting the global water chemistry.

The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log Kadsfreundlich=8.36 against 11.76 for NPG and ferrihydrite, respectively). The adsorption is dependent upon pH, in response to the Pb(II) adsorption by the oxygenated binding sites developed on account of the surface UV oxidation under environmental conditions. They could be able to compete with Fe or humic colloids for Pb binding regards to their amount and specific areas. Nanoplastics could therefore be efficient vectors of Pb and probably of many other metals as well in the environment.

Heavy metal pollution of water sources has raised global environmental sustainability concerns, calling for the development of high-performance materials for effective pollution treatment. Herein, we report a facile approach to synthesize carbonaceous nanofiber/NiAl layered double hydroxide (CNF/LDH) nanocomposites for high-efficiency elimination of heavy metals from aqueous solutions. The CNF/LDH nanocomposites were characterized by three-dimensional architectures formed by the gradual self-assembly of flower-like LDH on CNF. The nanocomposites exhibited excellent hydrophilicity and high structural stability in aqueous solutions, guaranteeing the high availability of active sites in these environments. High-efficiency elimination of heavy metal ions by the CNF/LDH nanocomposites was demonstrated by the high uptake capacities of Cu(II) (219.6 mg/g) and Cr(VI) (341.2 mg/g). The sorption isotherms coincided with the Freundlich model, most likely because of the presence of heterogeneous binding sites. The dominant interaction mechanisms consisted of surface complexation and electrostatic interaction, as verified by a combination of X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy analyses and density functional theory calculations. The results presented herein confirm the importance of CNF/LDH nanocomposites as emerging and promising materials for the efficient removal of heavy metal ions and other environmental pollutants.

The Atlantic killifish (Fundulus heteroclitus) is a resilient estuarine species that may be subjected to anthropogenic contamination of its natural habitat, by toxicants such as nickel (Ni). We investigated Ni accumulation and potential modes of Ni toxicity, in killifish, as a function of environmental salinity. Killifish were acclimated to 4 different salinities [0 freshwater (FW), 10, 30 and 100% seawater (SW)] and exposed to 5 mg/L of Ni for 96 h. Tissue Ni accumulation, whole body ions, critical swim speed and oxidative stress parameters were examined. SW was protective against Ni accumulation in the gills and kidney. Addition of Mg and Ca to FW protected against gill Ni accumulation, suggesting competition with Ni for uptake. Concentration-dependent Ni accumulation in the gill exhibited saturable relationships in both FW- and SW-acclimated fish. However SW fish displayed a lower Bmax (i.e. lower number of Ni binding sites) and a lower Km (i.e. higher affinity for Ni binding). No effect of Ni exposure was observed on critical swim speed (Ucrit) or maximum rate of oxygen consumption (MO2max). Markers of oxidative stress showed either no effect (e.g. protein carbonyl formation), or variable effects that appeared to depend more on salinity than on Ni exposure. These data indicate that the killifish is very tolerant to Ni toxicity, a characteristic that may facilitate the use of this species as a site-specific biomonitor of contaminated estuaries.

The implications of biochar aging regarding their material properties as well as their interactions with other contaminants are not vivid. We report the role of biochar aging on sorption behavior of di-alkyl phthalates (PAEs). Biochars used in this study were produced from peanut-shell and their aging was simulated by chemical oxidation. The structural composition and morphology of the obtained biochars, before and after oxidation with HNO3/H2SO4, were analyzed by element composition, XPS, DRIFT, and SEM/EDX. Several experimental results unequivocally showed oxygen enrichment in the mixed acid treated samples compared to their precursors. Despite surface area reduction and pore destruction, increased PAEs sorption on oxidized biochar surfaces portrayed existence of strong PAEs binding sites. The adsorption of PAEs on oxidized biochar surface is a cumulative influence of hydrophobic interactions and pi–pi electron donor–acceptor interactions. Our results suggest that imminent aging of biochar upon environmental exposure may change their sorbent properties.