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.

Effect of microplastics used in agronomic practices on agricultural soil properties and plant functions: Potential contribution to the circular economy of rural areas.

The extensive use of plastic materials and their improper disposal results in high amounts of plastic waste in the environment. Aging of plastics leads to their breakdown into smaller particles, such as microplastics (MPs) and nanoplastics. This research investigates plastics used in agricultural practices as they contribute to MP pollution in agricultural soils. The distribution and characteristics of MPs in agricultural soils were evaluated. In addition, the effect of MPs on soil properties, the relationship between MPs and metals in soil, the effect of MPs on the fate of pesticides in agricultural soils and the influence of MPs on plant growth were analysed, discussing legume, cereal and vegetable crops. Finally, a brief description of the main methods of chemical analysis and identification of MPs is presented. This study will contribute to a better understanding of MPs in agricultural soils and their effect on the soil-plant system. The changes induced by MPs in soil parameters can lead to potential benefits as it is possible to increase the availability of micronutrients and reduce plant uptake of toxic elements. Furthermore, although plastic pollution remains an emerging threat to soil ecosystems, their presence may result in benefits to agricultural soils, highlighting the principles of the circular economy.

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.

Soil parameters affecting the levels of potentially harmful metals in Thessaly area, Greece: a robust quadratic regression approach of soil pollution prediction.

The behavior and possible contamination risk due to the presence of potentially harmful metals (PHM) were studied based on 2250 soil samples that were collected in a 5-year period (2013-2017) from the plain of Thessaly (prefectures of Karditsa, Trikala, and Larissa). The vertical distribution of metals was also investigated from sample profiles at three depths 0-30, 30-60, and 60-90cm. The soils of the sampling belong to four taxonomy soil orders that are dominant in the studied area (Alfisols, Inceptisols, Endisols, and Vertisols). In a novel approach, robust quadratic regression analysis on multiple variables was used to define prediction models of the concentrations of two metals: Fe which is an essential metal and the toxic Cd. Linear and quadratic regression formulae were estimated based on the iteratively reweighted least squares robust regression approach in an effort to eliminate the impact of the outliers. These formulae define how several soil properties affect the distribution of the considered metals in each soil order. The evaluation of the estimated regression equations based on the R2 metric indicates that they constitute a useful, reliable, and valuable tool for managing, describing, and predicting the pollution in the studied area.

Response of hrpZPsph-transgenic N. benthamiana plants under cadmium stress.

The hrpZPsph gene from Pseudomonas syringae pv. phaseolicola, in its secretable form (SP/hrpZPsph), has previously proven capable of conferring resistance against rhizomania disease as well as abiotic stresses in Nicotiana benthamiana plants, while enhancing plant growth. This study aimed at investigating the response of SP/hrpZPsph-expressing plants under cadmium stress. Transgenic N. benthamiana lines, homozygous for the SP/hrpZPsph gene, and wild-type plants were exposed to Cd at different stress levels (0, 50, 100, 150 µΜ CdCl2). Plants' response to stress was assessed at germination and at the whole plant level on the basis of physiological and growth parameters, including seed germination percentage, shoot and root length, total chlorophyll content, fresh and dry root weight, as well as overall symptomatology, and Cd content in leaves and roots. At germination phase, significant differences were noted in germination rates and post-germination growth among stress levels, with Cd effects being in most cases analogous to the level applied but also among plant categories. Although seedling growth was adversely affected in all plant categories, especially at high stress level, lines #6 and #9 showed the lowest decrease in root and shoot length over control. The superiority of these lines was further manifested at the whole plant level by the absence of stress-attributed symptoms and the low or zero reduction in chlorophyll content. Interestingly, a differential tissue-specific Cd accumulation pattern was observed in wt- and hrpZPsph-plants, with the former showing an increased Cd content in leaves and the latter retaining Cd in the roots. These data are discussed in the context of possible mechanisms underlying the hrpZPsph-based Cd stress resistance.

Spatial and temporal assessment of cadmium and chromium contamination in soils in the Karditsa region (Central Greece).

In this work, we aimed at monitoring Cd and Cr levels in surface soils in the Karditsa region (Central Greece). Soil samples were obtained throughout 3 years (2010 to 2012) and analyzed for extractable (DTPA) and for "pseudo"-total concentrations (aqua regia) of Cd and Cr. The temporal variability, recorded twice per year, was also assessed. Significant spatial variability was recorded and illustrated by the respective thematic maps created using geostatistics, with the use of ordinary kriging. We found a possible geochemical connection and interactions between the two studied metals that indicated common lithogenic origin, while Cd was found further enriched due to likely applied phosphate fertilizers over long periods of time. We conclude that although the mapping of soil properties and metal contents is a useful tool when initially visiting an area, further in-depth studies should be conducted; such studies should address issues related to bioavailability of soil pools that may be linked to plant concentrations and possible risks of metals being transferred to plants or even humans.

Soil and maize contamination by trace elements and associated health risk assessment in the industrial area of Volos, Greece.

Agricultural lands adjacent to industrial activities are vulnerable due to the risk of trace elements (TEs) being accumulated into crops and subsequently humans. One such case concerns the industrial area of Volos, Greece, a suspected contaminated area which has never been studied. We measured Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn in soil and maize (leaves and grains) and assessed health risk of human exposure via soil ingestion and grain consumption. We found that the most highly enriched elements in soils were Tl (enrichment factor = 19), Se (17.68), Sb (14.81), As (7.89), Ni (6.91), Mo (5.22) and Cr (4.33); they all likely derived from anthropogenic activities and in particular from a nearby major steel factory, except for Ni which is known to be lithogenically elevated in that area. Synchrotron XANES spectra analysis revealed that As species were associated with ferrihydrite, and predominant species were As(V) (at ca. 85%) and As(III) (at ca. 15%). Although the total content of the studied elements was high, the ammonium bicarbonate-DTPA extractions recovered very low element concentrations, probably due to the fact that soil conditions decelerated solubility (i.e., soils were alkaline, clayey, and with high Fe oxides content). This was confirmed by the soil-to-grain transfer index, which was particularly low for all studied elements. In 5% of sampled grains concerning Cd, and in 40% concerning Pb, the European food-related regulation limits were surpassed. Health risk assessment showed a dramatically elevated risk for Tl via soil ingestion (hazard quotient, HQ = 2.399), a value that contributed 74% of the total risk. Similarly, concerning the grain consumption-related health risk, Tl was the predominant contributor (HQ = 0.128, contributing 40% of the total risk). Such elevated Tl risk which has rarely been reported previously, led to a considerably high hazard index (HI) well above the threshold of HI = 1. Cancer risk was below the 1 × 10-4 risk threshold for As and Pb. Our findings indicate that this study should be pivotal concerning similar industrially-affected agricultural soils of suspected contamination, since less-expected toxic elements such as Tl here may be primary contributors to health risk.

Bioavailability and health risk assessment of potentially toxic elements in Thriasio Plain, near Athens, Greece.

Elevated concentrations of potentially toxic elements (PTEs) are usually found in areas of intense industrial activity. Thriasio Plain is a plain near Athens, Greece, where most of the heavy industry of the country has been situated for decades, but it also is a residential and horticultural area. We aimed at measuring the levels of PTEs in soils and indigenous plant species and assessing the health risk associated with direct soil ingestion. Samples of soils at roadsides and growing plants were collected from 31 sites of that area. Concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V and Zn were measured in both soils (as pseudo-total) and aerial plant tissues. We found that As, Cd, Cr, Cu, Ni, Pb and Zn were higher than maximum regulatory limits. Element concentrations in plants were rather lower than expected, probably because indigenous plants have developed excluder behaviour over time. Copper and Zn soil-to-plant coefficients were highest among the other elements; for Cu this was unexpected, and probably associated with recent Cu-releasing industrial activity. Risk assessment analysis indicated that As was the element contributing more than 50 % of the health risk related to direct soil ingestion, followed by Cr, Pb, and, surprisingly, Mn. We concluded that in a multi-element contamination situation, elevated risk of PTEs (such as As, Cr and Pb) may reduce the tolerance limits of exposure to less-toxic elements (here, Mn).