An Assessment of the Feasibility of Phytoextraction for the Stripping of Bioavailable Metals from Contaminated Soils.

Phytoextraction has been proposed in many papers as a low-cost method for remediating contaminated soil. However, if national regulation is based on total metal(loid) concentrations in soil, phytoextraction is generally infeasible because of the long time required for remediation. Assessing phytoextraction requires determination of the dynamic rate of metal removal from soil. Phytoextraction may be feasible if the main goal is to reduce the soluble fraction of the metal(loid) with the goal of reducing bioavailability. However, it has been reported that there is a large mass balance mismatch between the reduction of the soluble metal fraction in contaminated soil and metal uptake by plants. Several studies report that the decrease of soluble fraction of metals in soil is higher than can be accounted for by plant uptake. In other words, studies generally overestimate the feasibility of bioavailable contaminant stripping. Therefore, a more rigorous approach is advisable to ensure that papers on bioavailable contaminant stripping include relevant information on mass balances. Furthermore, to implement the concept of bioavailable contaminant stripping, regulations must distinguish between the bioavailable fraction and the total metal concentration in soil. Environ Toxicol Chem 2023;42:558-565. © 2022 SETAC.

The Toxicity of Coated Silver Nanoparticles and Their Stabilizers towards Paracentrotus lividus Sea Urchin Embryos.

Surface modification of nanoparticles with different stabilizers is one of the most widely used methods to improve their stability and applicability. Silver nanoparticle (AgNPs) dispersions with biologically active stabilizers have great potential as plant protection products with synergetic antimicrobial properties and sufficient stability in terms of field application. The obtained AgNPs dispersions have the ability to enhance growth, increase yield and give better protection to various crops. At the same time, it is important to determine the fate, stability, and ecotoxicity of the applied nanosized products. The toxic effects of AgNPs dispersions and their constituents, organic stabilizers and additives, were evaluated using a phenotypic sea urchin embryo assay. Certain AgNPs dispersions with organic stabilizers demonstrated sufficient stability, even in seawater. The toxicity of the AgNPs decreased with the increasing tendency to agglomerate in seawater. Furthermore, the applied stabilizers were hazardous towards sea urchin embryos. They caused pronounced embryo abnormalities at 0.25-2.6 mg/L concentrations. AgNPs exhibited a lethal effect at concentrations that were equal to the MLC or exceeded the MEC of their stabilizers. Silver ions were more toxic towards sea urchin embryos than AgNPs.

Microbial responses are unreliable indicators of copper ecotoxicity in soils contaminated by mining activities.

Metal contamination of soil has become a serious environmental problem worldwide. Many studies have attempted to infer metal ecotoxicity from soil microbial responses. However, much of the data from these studies tends to be inconsistent and difficult to interpret. We hypothesized that microbial response would be a useful indicator of metal toxicity in soils contaminated by copper mining in Chile. Eighty-four topsoils (0-20 cm) were collected from three areas historically contaminated by copper mining (total Cu: 46-1106 mg kg-1, soluble Cu: 0.05-2.3 mg kg-1, pCu2+: 6.3-10, pH: 5.1-7.8, organic matter: 1.1-10%, clay: 0-28%). Based on soil metal concentrations and ecotoxicity thresholds, Cu was expected to be toxic to microorganisms in the studied soils, while the effects of other metals (total Zn: 79-672, As: 1.9-60, Pb: 19-220, Cd: 0.4-5.1 mg kg-1) were expected to be minor. Soil microbial responses (microbial biomass and numbers, nitrogen mineralization and nitrification, and community-level physiological profiles) were also measured. The results showed that the different responses of soil microbes were not correlated with each other. Furthermore, the soil microbial responses were mainly influenced by the physicochemical properties of the soil, not by the metal concentrations in the soil. The effect of copper on the microbial response was either stimulating (positive) or toxic (negative). Of the soil microbial responses measured in this study, only the microbial biomass was useful for calculating dose-response curves. However, the microbial biomass response was not consistent among the different soil copper pools (total copper, soluble copper, and activity of free Cu2+ ions). It is important to emphasize that the thresholds obtained for copper toxicity cannot be adopted in a robust manner because of the different microbial responses in different sampling areas. Thus, in the copper-contaminated soils under study, microbial response was found to be an unreliable indicator of metal toxicity.

Side effects of traditional pesticides on soil microbial respiration in orchards on the Russian Black Sea coast.

Agricultural use of pesticides has greatly increased worldwide over the last several decades, affecting soil microorganisms. Microbial basal respiration and substrate-induced respiration rates are commonly used to assess the detrimental effects of pesticides on soil quality. The goal of the present study was (1) to compare the impact of different pesticides on soil microbial respiration under field conditions, and (2) to characterize the recovery time of soil microbial respiration after pesticide application. The following pesticides were used in the present study: chlorpyrifos, phosalone, dimethoate (organophosphorus insecticides), λ-cyhalothrin (pyrethroid insecticide), and kresoxim-methyl (fungicide). The application of all the pesticides at commercial doses led to a decrease in soil microbial respiration. The inhibition of basal respiration and substrate-induced respiration rate decreased in the following order: chlorpyrifos > phosalone > dimethoate > λ-cyhalothrin ≈ kresoxim-methyl. Among all the pesticides assessed, chlorpyrifos showed the highest toxicity as well as the highest persistence. Several of the observed results differed greatly from previous studies; thus, local assessments are highly advisable. Given that environmental concerns can be a key decision factor for pesticide selection, assessment of different pesticides-such as undertaken in this study-could help farmers to choose the most appropriate pesticide.

In Vivo Study of Entero- and Hepatotoxicity of Silver Nanoparticles Stabilized with Benzyldimethyl-[3-myristoylamine)-propyl]ammonium Chloride (Miramistin) to CBF1 Mice upon Enteral Administration.

Silver nanoparticles (AgNPs) are the most widely studied antimicrobial nanomaterials. However, their use in biomedicine is currently limited due to the availability of data that prove the nanosilver toxicity associated primarily with oxidative stress development in mammalian cells. The surface modification of AgNPs is a potent technique of improvement of their biocompatibility. The synthetic or natural compounds that combine zero or low toxicity towards human and animal organisms with inherent antimicrobial properties are the most promising stabilizing agents, their use would also minimize the risks of microorganisms developing resistance to silver-based materials. We used a simple technique to obtain 30-60 nm AgNPs stabilized with benzyldimethyl[3-myristoylamine)-propyl]ammonium chloride monohydrate (BAC)-a well-known active ingredient of many antibacterial drugs. The objective of the study was to assess the AgNPs-BAC entero- and hepatotoxicity to CBF1 mice upon enteral administration. The animals were exposed to 0.8-7.5 mg/kg doses of AgNPs-BAC in the acute and to 0.05-2.25 mg/kg doses of AgNPs-BAC in the subacute experiments. No significant entero- and hepatotoxic effects following a single exposure to doses smaller than 4 mg/kg were detected. Repeated exposure to the doses of AgNPs-BAC below 0.45 mg/kg and to the doses of BAC below 0.5 mg/kg upon enteral administration also led to no adverse effects. During the acute experiment, the higher AgNPs-BAC dose resulted in increased quantities of aminotransferases and urea, as well as the albumin-globulin ratio shift, which are indicative of inflammatory processes. Besides, the relative mass of the liver of mice was smaller compared to the control. During the subacute experiment, the groups treated with the 0.25-2.25 mg/kg dose of AgNPs-BAC had a lower weight gain rate compared to the control, while the groups treated with the 2.25 mg/kg dose of AgNPs-BAC showed statistically significant variations in the blood serum transaminases activity, which indicated hepatosis. It should be noted that the spleen and liver of the animals from the groups treated with the 0.45 and 2.25 mg/kg dose of AgNPs-BAC were more than two times smaller compared to the control. In the intestines of some animals from the group treated with the 2.25 mg/kg dose of AgNPs-BAC small areas of hyperemia and enlarged Peyer's patches were observed. Histological examination confirmed the initial stages of the liver and intestinal wall inflammation.

New Relevant Descriptor of Linear QNAR Models for Toxicity Assessment of Silver Nanoparticles.

The use of silver nanoparticles (NPs) in medical, industrial and agricultural fields is becoming more widespread every year. This leads to an increasing number of experimental toxicological and microbiological studies of silver NPs aimed at establishing the risk-benefit ratio for their application. The following key parameters affecting the biological activity of silver dispersions are traditionally taken into consideration: mean diameter of NPs, surface potential of NPs and equilibrium concentration of Ag+. These characteristics are mainly predetermined by the chemical nature of the capping agent used for stabilization. However, the extent to which they influence the biological activity and the toxicity of silver NPs varies greatly. In this work, dispersions of silver NPs stabilized with a wide array of substances of different chemical nature were used for quantitative evaluation of whether the various measurable properties of silver NPs fit as descriptors of linear QNAR (quantitative nanostructure-activity relationship) models for silver NP toxicity evaluation with respect to a model eukaryotic microorganism-Saccharomyces cerevisiae yeast cells. It was shown that among the factors that determine silver NP toxicity, the charge of particles, their colloidal stability and the ability to generate Ag+ ions carry more importance than the descriptors related to the particle size. A significant synergistic effect between the ζ-potential and the colloidal stability of silver NPs on their toxicity was also discovered. Following this, a new descriptor has been proposed for the integral characterization of the silver dispersion colloidal stability. According to the obtained data, it can be considered applicable for building QNAR models of higher efficacy. The validity testing of the proposed model for theoretical prediction of silver NP toxicity using a wide range of living organisms has shown that this new descriptor correlates with toxicity much better compared to most traditionally used descriptors. Consequently, it seems promising in terms of being used not only in situations involving the rather narrow array of the objects tested, but also for the construction of silver NP toxicity models with respect to other living organisms.

Chilean regulations on metal-polluted soils: The need to advance from adapting foreign laws towards developing sovereign legislation.

Chile as a major international Cu producer faces serious soil contamination issues in mining areas. Currently Chile does not have any specific law governing the maximum permissible concentrations of metals in soils to protect ecosystems and human health. Chile heavily relies on the use of environmental laws of 14 foreign countries; the choice of the country depends on the similarity of its environmental conditions with those in Chile. In this study, we used an online database to compare the similarity of Chilean rocks to those in foreign countries. Likewise, we performed soil sampling and determined the background concentrations of Cu, As, Pb, and Zn in soils of the Aconcagua basin, the largest river basin in the Valparaiso Region of central Chile. The results showed that geochemical patterns in Chile have the greatest resemblance to New Zealand, Mexico, and Italy. The background Cu concentration in the Aconcagua basin (134 mg kg-1) exceeded the legislated limits of New Zealand (100 mg kg-1) and Italy (120 mg kg-1), whereas the background Zn concentration (200 mg kg-1) exceeded the legislated limit of Italy (150 mg kg-1). Due to the elevated natural abundance of Cu and Zn in Chile, international laws should not be applied in Chile for the assessment of soil contamination. In addition, we assessed ecological risk using the results of our previous studies obtained by analyzing native field-contaminated soils of the Valparaiso region. In the Aconcagua basin, Cu posed high risk for plants in 11% of the samples, whereas As posed high risk for earthworms in 48% of the samples. We suggest that future studies are required to search for other organisms that can serve as biomarkers of metal toxicity because our previous studies were limited to plants and earthworms. Importantly, As posed high risk to human health in 25% of the samples in our study. There is a need for future studies to demonstrate empirically an association between soil As and children's blood As in order to establish the national threshold values of soil As to protect human health. We conclude that there is an urgent need in Chile to advance from the current approach of adapting foreign laws to developing Chilean sovereign environmental legislation.

Versatile synthesis of PHMB-stabilized silver nanoparticles and their significant stimulating effect on fodder beet (Beta vulgaris L.).

Silver nanoparticles (AgNPs) are well-known bactericidal agents. However, information about the influence of AgNPs on the morphometric parameters and biochemical status of most important agricultural crops is limited. The present study reports the influence of AgNPs stabilized with cationic polymer polyhexamethylene biguanide hydrochloride (PHMB) on growth, development, and biochemical status of fodder beet Beta vulgaris L. under laboratory and greenhouse conditions. PHMB-stabilized AgNPs were obtained via sodium borohydride reduction of silver nitrate in an aqueous solution. The average diameter of thus prepared AgNPs was 10 nm. It appears that the results of experiments with laboratory-grown beets in the nanosilver-containing medium, where germination of seeds and growth of roots were suppressed, do not correlate with the results of greenhouse experiments. The observed growth-stimulating action of PHMB-stabilized AgNPs can be explained by the change of activity of oxidases and, consequently, by the change of auxins amount in plant tissues. In beets grown in the presence of PHMB-stabilized AgNPs no negative deviations of biological parameters from normal values were registered. Furthermore, the SEM/EDS examination revealed no presence of silver in the tissues of the studied plants.