International audience | Accumulation of copper (Cu) in soils due to the application of fungicides may be toxic for organisms and hence affect winegrowing sustainability. Soil parameters such as pH and dissolved organic matter (DOM) are known to affect the availability of Cu. In this study, we investigated the contribution of chromophoric and fluorescent DOM properties to the prediction of Cu availability in 18 organic vineyard soils in the Bordeaux winegrowing area (France). The DOM parameters, assessed through absorbance and fluorescence analyses, and proxies for Cu availability (total soluble Cu and free ionic Cu2+) were measured in 0.01 M KCl extracts. Total soluble Cu (CuKCl) varied 23-fold while free ionic Cu2+ varied by a factor of 4600 among the soils. DOC concentrations were similar among the soils, but the samples differed in the quality of DOM as assessed by optical spectroscopy. Multilinear regression models with and without DOM quality parameters were investigated to predict Cu availability. The best model for CuKCl successfully explained 83% of variance and included pH, CuT, and two DOM fluorescence quality indices, the FI fluorescence index, which distinguishes between microbial and higher plant origins, and the HIX humification index. For the prediction of Cu2+, pH alone explained 88% of variance and adding DOM parameters did not improve modelling. The two Cu availability proxies were related to pH. This study confirms the prominent role of pH in Cu availability and underlines the importance of DOM quality to better predict Cu solubility

Biotechnological strategies have become effective in the remediation of polluted soils as they are cost-effective and do not present a risk of secondary pollution. However, using a single bioremediation technique (microorganism or plant) is not suitable for achieving a high remediation rate of polluted saline-alkali soils with heavy metals. Therefore, the present study aims to assess the effects and mechanisms of combined ryegrass and Fusarium incarnatum on the zinc (Zn)-polluted saline-alkali soil over 45 days. According to the obtained results, the combined Fusarium incarnatum-ryegrass showed the highest remediation rate of 49.35% after 45 days, resulting in a significantly lower soil Zn concentration than that observed in the control group. In addition, the inoculation of Fusarium incarnatum showed a positive effect on the soil EPS secretion. The soil protein contents ranged from 0.035 to 0.055 mg/kg, while the soil polysaccharide contents increased from 0.25 to 0.61 mg/g. The soil microbial flora and ryegrass showed resistance to saline and alkaline stresses through the secretion of extracellular polysaccharides. The three-dimensional fluorescence spectrum (3D-EEM) confirmed that EPS in the soil was mainly a fulvic acid-like substance. The fluorescein diacetate (FDA) hydrolase activity in the saline-alkali soil was first increased due to the effect of Fusarium incarnatum and then decreased to a minimum value of 96 μg/(g·h). In addition, the Fusarium incarnatum inoculation improved the diversity and richness of soil fungi. Although the Fusarium incarnatum inoculation had a slight effect on the germination of ryegrass, it increased the biomass and enrichment coefficient. The results revealed a translocation factor (TF) value of 0.316 at 45 days after ryegrass sowing, showing significant enrichment of the soil Zn heavy metal zinc in the ryegrass roots.

In peri-urban critical zones, soil ecosystems are highly affected by increasing urbanization, causing probably an intense interaction between dissolved organic matter (DOM) and heavy metals in soil. Such interaction is critical for understanding the biogeochemical cycles of both organic matter and heavy metals in these zones. However, limited research has reported the correlative distribution of DOM and heavy metals at high seasonal and spatial resolutions in peri-urban critical zones. In this study, 160 soil samples were collected from the farmland and forestland of Zhangxi watershed, in Ningbo, eastern China during spring, summer, fall and winter four seasons. UV–visible absorption and fluorescent spectroscopy were used to explore the optical characteristics of DOM. The results indicated a mixture of exogenous and autogenous sources of DOM in the Zhangxi watershed, while DOM in farmland exhibited a higher degree of aromaticity and humification than that in forestland. Fluorescent results showed that humic acid-like, fulvic acid-like and microbial-derived humic-like fractions were mostly affected by seasons. The distribution of heavy metals was affected mainly by land-use changes and seasons. Correlation analysis between heavy metals and DOM characteristics and components suggested that aromatic and humic substances were more favorable in binding with EDTA extractable Ni, Cu, Zn and Cd. The bioavailable Cd and Pb decreased due to binding with humic fractions, indicating its great effects on the bioavailability of Cd and Pb. Overall, these findings provide an insight into the correlative distributions of DOM and heavy metals in peri-urban areas, thereby highlighting their biogeochemical cycling in the soil environment.

The properties and metal-binding abilities of dissolved organic matter (DOM) rely on its molecular weight (MW) structure. In this study, the spatial differences of DOM in compositions, MW structures, and binding mechanisms with copper (Cu²⁺) in Dongping Lake were investigated by applying excitation-emission matrix combining parallel factor analysis (EEM-PARAFAC), synchronous fluorescence (SF) spectra, two-dimensional correlation spectra (2D-COS), and Fourier transform infrared (FTIR) spectra. The EDOM for the entrance of the Dawen River and PDOM for the macrophyte-dominated region were divided from DOM of Dongping Lake based on hierarchical clustering analysis (HCA) and principal component analysis (PCA) and were size-fractioned into MW < 500 kDa and <100 kDa fractions. According to EEM-PARAFAC, Dongping Lake was dominated by tryptophan-like substances with MW < 500 kDa. The concentration of PDOM was higher than that of EDOM (p < 0.05). 2D-COS showed that protein-like components preceded humic-like components binding to Cu²⁺ regardless of sample type (215 nm > 285 nm > 310–360 nm). The Cu²⁺ binding capacity of DOM exhibited specific differences in space, components, and molecular weights. The humic-like component 1 (C1) and tryptophan-like component 4 (C4) of PDOM showed stronger binding abilities than those of EDOM. Endogenous tryptophan-like component 4 (C4) had a higher binding affinity for Cu²⁺ than humic-like components (logKₐ: C4 > C1 > C2) in PDOM irrespective of MW. Humic-like components with MW < 500 kDa displayed higher binding potentials for Cu²⁺. FTIR spectra showed that the main participants of DOM-Cu complexation included aromatic hydrocarbons, aliphatic groups, amide Ⅰ bands, and carboxyl functional groups. This study provides spatial-scale insights into the molecular weight structure of DOM in influencing the behavior, fate, and bioavailability of heavy metals in lakes.

Marine ecosystems in the Arctic and Antarctica were once thought pristine and away from important human influence. Today, it is known that global processes as atmospheric transport, local activities related with scientific research bases, military and touristic maritime traffic, among others, are a potential source of pollutants. Macroalgae have been recognized as reliable metal-biomonitoring organisms due to their accumulation capacity and physiological responses. Metal accumulation (Al, Cd, Cu, Fe, Pb, Zn, Se, and Hg) and photosynthetic parameters (associated with in vivo chlorophyll a fluorescence) were assessed in 77 samples from 13 different macroalgal species (Phaeophyta; Chlorophyta; Rhodophyta) from areas with high human influence, nearby research and sometimes military bases and a control area, King George Island, Antarctic Peninsula. Most metals in macroalgae followed a pattern influenced by rather algal lineage than site, with green seaweeds displaying trends of higher levels of metals as Al, Cu, Cr and Fe. Photosynthesis was also not affected by site, showing healthy organisms, especially in brown macroalgae, likely due to their great dimensions and morphological complexity. Finally, data did not demonstrate a relationship between metal accumulation and photosynthetic performance, evidencing low anthropogenic-derived impacts associated with metal excess in the area. Green macroalgae, especially Monostroma hariotti, are highlighted as reliable for further metal biomonitoring assessments. In the most ambitious to date seaweed biomonitoring effort conducted towards the Austral pole, this study improved by 91% the overall knowledge on metal accumulation in macroalgae from Antarctica, being the first report in species as Sarcopeltis antarctica and Plocamium cartilagineum. These findings may suggest that human short- and long-range metal influence on Antarctic coastal ecosystems still remains under control.

Per- and polyfluoroalkyl substances (PFASs) have been found to be widely present in soil. Dissolved organic matter (DOM) in soil are supposed to greatly affect the bioavailability of PFASs in soil. Herein, hydroponic experiments were conducted to understand the impacts of two kinds of typical DOM, bovine serum albumin (BSA) and humic acid (HA), on the uptake and translocation of legacy PFASs and their emerging alternatives, perfluorooctane sulfonic acid (PFOS), perfluorooctane acid (PFOA), perfluorohexane sulfonic (PFHxS) and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA) in wheat (Triticum aestivum L.). The results indicated that both HA and BSA significantly inhibited the bioaccumulation and translocation of PFASs in the roots and shoots of wheat, and the impacts of BSA were greater than HA. This difference was explained by the greater binding affinities of the four PFASs with BSA than with HA, as evidenced by the equilibrium dialysis and isothermal titration calorimetry (ITC) analyses. It was noting that inhibition impacts of the BSA-HA mixture (1:1) were lower than BSA alone. The results of Fourier transform infrared (FT-IR) spectroscopy and excitation-emission matrix (EEM) fluorescence spectroscopy suggested that HA could bind with the fluorescent tryptophan residues in BSA greatly, competing the binding sites with PFASs and forming a cover on the surface of BSA. As a result, the binding of PFASs with BSA-HA complex was much lower than that with BSA, but close to HA. The results of this study shed light on the impacts of DOM in soil on the bioaccumulation and translocation of PFASs in plants.

The coexistence of per- and polyfluoroalkyl substances (PFASs) and heavy metals have been found in soils. However, the interaction between the combined pollutants in soils remains unclear. In this study, the adsorption processes of single and combined Cr(VI) and chlorinated polyfluoroalkyl ether potassium sulfonate (F–53 B) in red, yellow and black soils were simulated. When compared with the single F–53 B and Cr(VI), the adsorption amount of the combined F–53 B and Cr(VI) on soils changed with the types of soils. The interactions between F–53 B and Cr(VI) in soils affected their adsorption behavior. The adsorption of the combined F–53 B and Cr(VI) best fit second-order kinetics and the Freundlich equation. Moreover, aluminum and iron oxides are highly correlated with adsorption of F–53 B and Cr(VI). Both F–53 B and Cr(VI) can form complexes with aluminum and iron oxides through electrostatic interactions, but PFOS could be bridged with iron oxides to form an inner sphere complex and with aluminum oxides to form an outer sphere complex. The coexistence of F–53 B and Cr(VI) could change the fluorescent group of dissolved organic matter (DOM) in soils due to the complexation between F–53 B and DOM. In addition, F–53 B increased the acid-soluble portion of Cr and decreased its residual form, which promoted the environmental risk of Cr in soils.

Plant leaf cuticles play a critical role in the accumulation and transport of atmospheric polycyclic aromatic hydrocarbons (PAHs). The relationship between the distribution and retained amount of PAHs on the leaf cuticles and the leaves micro-zone structures is still unclear. In this study, a confocal microscopic fluorescence spectral analysis (CMFSA) system with a spatial resolution of 200 nm was established as a direct and noninvasive means to determine the microscopic distribution and quantify the retained amount of benzo[a]pyrene (B[a]P) at Aegiceras corniculatum (Ac), Kandelia obovata (Ko) and Avicennia marina (Am) leaf cuticle micro-zones (0.096 mm²). The linear ranges for the established method were 10–1900 ng spot⁻¹ for Ac, 15–1700 ng spot⁻¹ for Ko and 30–1800 ng spot⁻¹ for Am, and the detection limits were 0.06 ng spot⁻¹ for Ac, 0.06 ng spot⁻¹ for Ko and 0.07 ng spot⁻¹ for Am. Notably, B[a]P formed clusters and unevenly distributed at the leaf cuticles. On the adaxial cuticles, B[a]P was mainly accumulated unevenly along the epidermis cell wall, and it was also distinctively distributed in the secretory cells around salt glands for Ac and Am. On the abaxial leaf cuticles, B[a]P was concentrated in the salt glands and stomata apart from being unevenly distributed in the epidermis cell wall. Moreover, the amount of B[a]P retained presented a negative correlation with the polarity of leaf cuticles, which resulted in the amount of B[a]P retained on the adaxial leaf cuticles being significantly higher than that on abaxial leaf cuticles. Our results provide a potential in situ method for investigating the distribution and retained amount of PAHs at plant leaf surface micro-zones, which would contribute to further studying and understanding the mechanism of migration and transformation of PAHs by plant leaves from a microscopic perspective.

Polyaromatic hydrocarbons (PAHs), such as pyrene, benzo[a]pyrene, phenanthrene, and anthracene induce toxic, carcinogenic, and mutagenic effects on living organisms and are considered as primary pollutants. Traditional methods for their identification are often laborious and time-consuming and do not account for the heterogeneous nature of their distribution. Here we present confocal microscopy as a rapid and accurate technique for direct analysis of PAHs in soil samples without the complexity of sample pre-processing which might delay results for several days. The method uses the intrinsic fluorescence of PAHs for detection and their emission spectra for the identification of different PAHs. A clear difference was observed in the fluorescence spectral properties of phenanthrene, pyrene and naphthalene in real-time environmental samples. The post-processing of confocal scans obtained in the detection stage of PAHs was completed through the application of ImageJ software. Intrinsic fluorescence-based detections of PAHs may open new avenues in terms of rapid detection and identification of PAHs in heterogeneous complex soil samples.

The objective of this study was to evaluate the biological and nutritional characteristics of Spodoptera frugiperda (Lepidoptera: Noctuidae), an arthropod pest widely distributed in agricultural regions, after exposure to nano-CeO₂ via an artificial diet and to investigate the presence of cerium in the body of this insect through X-ray fluorescence mapping. Nano-CeO₂, micro-CeO₂, and Ce(NO₃)₃ were incorporated into the diet (0.1, 1, 10, and 100 mg of Ce L⁻¹). Cerium was detected in caterpillars fed with diets containing nano-CeO₂ (1, 10 and 100 mg of Ce L⁻¹), micro-CeO₂ and Ce(NO₃)₃, and in feces of caterpillars from the first generation fed diets with nano-CeO₂ at 100 mg of Ce L⁻¹ as well. The results indicate that nano-CeO₂ caused negative effects on S. frugiperda. After it was consumed by the caterpillars, the nano-CeO₂ reduced up to 4.8% of the pupal weight and 60% of egg viability. Unlike what occurred with micro-CeO₂ and Ce(NO₃)₃, nano-CeO₂ negatively affected nutritional parameters of this insect, as consumption rate two times higher, increase of up to 80.8% of relative metabolic rate, reduction of up to 42.3% efficiency of conversion of ingested and 47.2% of digested food, and increase of up to 1.7% of metabolic cost and 8.7% of apparent digestibility. Cerium caused 6.8–16.9% pupal weight reduction in second generation specimens, even without the caterpillars having contact with the cerium via artificial diet. The results show the importance of new ecotoxicological studies with nano-CeO₂ for S. frugiperda in semi-field and field conditions to confirm the toxicity.