Bismuth Film along with dsDNA-Modified Electrode Surfaces as Promising (bio)Sensors in the Analysis of Heavy Metals in Soils.

Heavy metals constitute pollutants that are particularly common in air, water, and soil. They are present in both urban and rural environments, on land, and in marine ecosystems, where they cause serious environmental problems since they do not degrade easily, remain almost unchanged for long periods, and bioaccumulate. The detection and especially the quantification of metals require a systematic process. Regular monitoring is necessary because of seasonal variations in metal levels. Consequently, there is a significant need for rapid and low-cost metal determination methods. In this study, we compare and analytically validate absorption spectrometry with a sensitive voltammetric method, which uses a bismuth film-plated electrode surface and applies stripping voltammetry. Atomic absorption spectroscopy (AAS) represents a well-established analytical technique, while the applicability of anodic stripping voltammetry (ASV) in complicated sample matrices such as soil samples is currently unknown. This sample-handling challenge is investigated in the present study. The results show that the AAS and ASV methods were satisfactorily correlated and showed that the metal concentration in soils was lower than the limit values but with an increasing trend. Therefore, continuous monitoring of metal levels in the urban complex of a city is necessary and a matter of great importance. The limits of detection of cadmium (Cd) were lower when using the stripping voltammetry (SWASV) graphite furnace technique compared with those obtained with AAS when using the graphite furnace. However, when using flame atomic absorption spectroscopy (flame-AAS), the measurements tended to overestimate the concentration of Cd compared with the values found using SWASV. This highlights the differences in sensitivity and accuracy between these analytical methods for detecting Cd. The SWASV method has the advantage of being cheaper and faster, enabling the simultaneous determination of heavy elements across the range of concentrations that these elements can occur in Mediterranean soils. Additionally, a dsDNA biosensor is suggested for the discrimination of Cu(I) along with Cu(II) based on the oxidation peak of guanine, and adenine residues can be applied in the redox speciation analysis of copper in soil, which represents an issue of great importance.

Green and sustainable practices for an energy plant cultivation on naturally contaminated versus spiked soils. The impact of ageing soil pollution in the circular economy framework.

Silybum marianum L. Gaertn. or milk thistle is an energy-produced weed that has been shown to be tolerant of heavy metal-contaminated soils. In the present study, its cultivation was studied in soils laboratory-spiked (artificial) with Cu and Zn solutions. Meanwhile, plant growing on naturally contaminated soils of Mediterranean regions, both urban and rural, was investigated. The metal concentrations spiked in artificial polluted soils were estimated to be roughly equivalent to those in naturally contaminated soils. Plants grown in artificially contaminated soils incorporated the metal added to the soils more rapidly and in higher proportions. The contamination of soil samples was carried out using different chemical reagents, salts containing the metals with oxidation number II, highlighting the fact that the reagent containing the metal is crucial regarding artificial soil pollution. Statistically significant differences were observed between the individual pollution patterns, as far as plant metals uptake concern. It was also found that the aged, contaminated soils transfer lower levels of metals to the plants. Therefore, aging or weathering of contamination alters toxicity levels in the soil environment by determining transport and uptake into the soil-to-plant system. Eventually, from the present research, it emerged the fact that in urban soils that have aged perennial pollution, the uptake of metals by plants is probably lower than in rural ones. Furthermore, with proper management, it is possible to grow plants, with low nutrient requirements, in urban soils by adopting smart, green and eco-friendly techniques, enhancing sustainable cultivation in the framework of circular economy.

Influence of soil inorganic amendments on heavy metal accumulation by leafy vegetables.

The present study aims to assess the effect of four inorganic soil amendments, such as lime (CaCO3), red mud consisting of 75% hematite (Fe2O3), gypsum (CaSO4·2H2O), and Al oxide (Al2O3), of an alkaline heavy metal-contaminated soil. For this purpose, a pot experiment was conducted by physically mixing individual six subsamples of a soil sample collected from Thessaly area with four inorganic soil amendments along with two leafy plants, spinach and lettuce. Al oxide causes the maximum reduction of the water-soluble Cu concentration, as its concentrations is no longer detectable. The Cu availability index decreases when aluminum oxide was used. The use of gypsum and red mud caused almost equal reduction while the smallest decrease was caused by the use of lime. The Zn availability index decreased equally when aluminum oxide and gypsum were mixed with the soil sample. The highest reduction of Cu and Zn transfer coefficient (TC) was observed when the Al2O3 was used. In spinach, Zn TC reduction was 39.8% and Cu TC reduction was 41.0%. In lettuce, the addition of Al2O3 led to Cu TC reduction of over 37.3% and Zn TC reduction of up to 38.7%. Generally, Al2O3 nanoparticles may function as suitable sorbents for the removal of Zn and Cu from soil samples, with an increasing effectiveness in spinach rather than lettuce. Liming materials seem to increase the soil alkalinity and promote the complexation of soluble heavy metals with hydroxide ions leading to immobilization of heavy metals in soil and reduce their amount in leafy vegetables. Remediation of contaminated soils is considered necessary to reduce environmental risks and to achieve the means available to increase agricultural production of safe and quality food.