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The leaching of potentially toxic elements from different industrial solid wastes (ISWs) must be understood to manage the environmental concerns they pose. The objective of this research was to investigate the effect of clay mineral (bentonite) and nanoparticle (MgO) on potentially toxic elements (Cr, Cu, Ni, Zn) leaching in some ISWs, when they leached with different leaching solutions. The highest amount of Zn and Ni was leached from ceramic factory waste (CFW) and stone cutting wastes (SCW), respectively, while the highest amount of Cr was leached from leather factory waste (LFW). In ISWs, the leaching percentage of Cu, Ni, and Zn were up to 11.2%, whereas the greatest leaching percentage of Cr was 26.7% of the total content. The addition of bentonite and MgO decreased potentially toxic element leaching. The results of effluents speciation of SFW indicated that at the beginning of leaching with CaCl 2 , nitric acid, and citric acid, 75.1%, 84.1%, and 39.6% of Cr were in different forms of Cr (III), respectively, while at the end of leaching the percentage of Cr (III) species were decreased and Cr (VI) species were increased to 83.6%, 88.4%, and 93.4%, respectively. The addition of bentonite and especially MgO to the ISWs reduced the leaching of potentially toxic elements as well as reduced the percentage of Cr (VI) in the effluents of SFW. The findings suggested that bentonite has the potential to be a low-cost and environmentally acceptable adsorbent for minimizing the leaching of Cr and other potentially toxic elements from ISWs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Heavy metals are among the most important environmental pollutants which accumulate in various organs and are associated with several toxic effects. This study was performed to determine the status of heavy metals in river buffaloes in Khuzestan province, Iran, and its relationship with hematologic and serum biochemical parameters. A total of 103 apparently healthy buffaloes were sampled from the region. The concentration of heavy metals, including lead (Pb), mercury (Hg), and cadmium (Cd), was determined in serum samples by atomic spectroscopy. In addition, complete blood counts and serum biochemical profiles were assessed. The serum concentration of Cd, Pb, and Hg in the sampled buffaloes, as mean±standard error, were 0.55±0.01, 6.51±0.10, and 6.28±0.09 µg/l, respectively, which are within the permissible serum levels in the livestock. Serum Cd and Hg levels showed no significant relationship with hematologic or biochemical analytes. However, there were significant negative correlations between Pb levels and phosphorus, magnesium, sodium, as well as potassium concentrations, while serum iron was positively correlated with lead ( P <0.05). In addition, there was a significant positive correlation between Hg level and serum aspartate aminotransferase activity ( P <0.05). Despite the fact that river buffaloes in Khuzestan spend a long time daily in the Karun River with high industrial pollution, no serum evidence of heavy metal toxicity was found in these animals. It can be suggested that river buffaloes in Khuzestan seem to be resistant to the environmental pollution caused by heavy metals. However, further studies are required to confirm this issue and identify its possible explanations., Competing Interests: The authors declare that they have no conflict of interest.

Biochemical processes in the rhizosphere affect the availability and distribution of heavy metals (HMs) in various forms. Rhizosphere soil (RS) and non-rhizosphere soil (NRS) samples were collected from 10 fields under tarragon (Artemisia dracunculus L.) cultivation to investigate the release kinetics and distribution of HMs including cadmium (Cd), cobalt (Co), copper (Cu), iron (Fe), and zinc (Zn) in five fractions. The cumulative amounts of Cu and Fe released after 88 h were in the following ranges, respectively: 1.31-2.76 and 3.24-6.35 mg kg -1 in RS and 1.41-2.72 and 3.15-5.27 mg kg -1 in NRS. The parabolic diffusion and pseudo-second-order equations provided the best fit to the release kinetics data of Cu and Fe, respectively. The cation exchange model (CEM) based on Gaines-Thomas selectivity coefficients implemented in the PHREEQC program could well simulate the release of Cu and Fe suggesting that cation exchange was the dominant mechanism in the release of Fe and Cu from soils by 0.01 M CaCl 2 . Cadmium was predominantly found in fraction F2, while other HMs were mainly present in fraction F5. According to the risk assessment code, there was a very high risk for Cd, a medium risk for Co and Cu, a very low risk for Fe, and a low risk for Zn. Correlation analysis showed that soil physicochemical properties were effective in the distribution and transformation of HMs. Significant positive correlations between five fractions indicated that different forms of HMs can potentially transform into each other., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

With growing urbanization and agriculture, the quantity of sewage sludge production increases every year. For the purpose of risk management, it is crucial to figure out how much heavy metals are transported to different parts of plants when sewage sludge is used. A greenhouse experiment was carried out to investigate the accumulation of heavy metals in wheat (Triticum aestivum L.) grown in 30 calcareous soils. The soils in this study were subjected to three different treatments: soils treated with sewage sludge at a rate of 2.5%, soils treated with sewage sludge at a rate of 2.5% and enriched with heavy metals, and control soils that received neither sewage sludge nor heavy metals. Wheat grown in sewage sludge-treated soils had the highest mean dry matter, and was 2.11 and 1.25 times greater than wheat grown in control and spiked-sewage sludge-treated soils, respectively. In all treatments, wheat roots had greater heavy metal levels than wheat shoots. Among all the heavy metals examined, Pb and Cu had the highest bioconcentration factors for roots and shoots (BCF Roots and BCF Shoots ) in control and sewage sludge-treated soils, followed by Cd in spiked-sewage sludge-treated soils, and Co and Ni had the lowest BCF Roots and BCF Shoots across all treatments. In spiked-sewage sludge-treated soils, the root restriction for heavy metals translocation was more important for Co, Cu, and Ni than for Pb and Zn, indicating that wheat can be grown safely in a variety of calcareous soils amended with sewage sludge with high content of Cd, Co, Cu, and Ni. Reducing the transfer of Pb and Zn from soils to wheat in soils treated with sewage sludge yet having high concentrations of these heavy metals should be considered as a top priority strategy for preserving wheat products. Since a wide range of calcareous soils was used in this study and because calcareous soils make up the majority of soils in the Middle East, the findings are relevant for all of the countries in this region., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The pollution of Iranian agricultural soils with trace elements (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) was assessed and compared with other agricultural soils around the world. Experimental data on trace element content in Iranian agricultural areas in the west and north were collected from the literature: 39 studies covered a total of 46 agricultural sites of 17 provinces in Iran, in order to characterize their patterns of accumulation of trace elements. Two pollution indices, namely, the pollution index (PI) and the integrated pollution index (IPI), were used to evaluate trace element accumulation. The data revealed a remarkable variation in trace element content among soils in different areas. Exploratory data analyses (EDAs) showed that a number of trace elements (Pb, Cu, and Zn) are asymmetrically distributed and scattered. Surveys indicated that 45.5% of the studied samples had elevated PI values for Cd, 13.0% for Cu, and 16.7% for Pb, clearly indicating an anthropogenic contribution of these three elements. The IPI of the agricultural soils also indicated that most areas are classified as having moderate and high pollution. Higher contents of trace elements (except for Mn) were found in some cities of the Isfahan, Hamadan, and Tehran provinces. Excessive application of conventional and organic fertilizers, pesticides, animal manure, and sewage sludge for enhancing crop production is responsible for high trace element content in Iran's agricultural soils. This in turn, through the food chain, is a threat to human health. Analysis of the correlation between trace elements exhibited that Cu, Pb, and Zn (Cd, Pb and Zn) were very closely associated with each other, showing that their prevalent sources are common and the efforts to regulate them linked in common actions. We consider this evaluation as a viable approach to other similar areas in the Middle East and beyond, which could be used by environmental scientists for risk assessment and decision making., (© 2021. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Compared to noncalcareous soils, data on the soil-to-plant transfer of heavy metals and their response to sewage sludge (SS) in calcareous soils with diverse properties are limited. Cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) transfer from soil to cabbage ( Brassica oleracea L. var. capitata) under greenhouse conditions in 30 diverse soils amended with two types of sewage sludge (non-spiked and spiked with heavy metals) were investigated. Three transfer factors were calculated for heavy metals in three treated soils including control soils (CS), soils treated with non-spiked SS (NSS), and soils treated with spiked SS (PSS). The bio-concentration factor of heavy metals from soil to root (BCF Roots ) in cabbage in three treatments was as follows: CS: Pb > Cu > Co > Zn > Ni; NSS: Pb > Co > Cu ≥ Zn > Ni; and PSS: Pb > Cd > Zn > Co > Cu > Ni. The same order was found for the bio-concentration factor of heavy metals from soil to shoots (BCF Shoots ) in PSS, and in CS and NSS treatments except that the position of Co, Cu, and Zn was changed. Based on the heavy metals translocation from plant roots to shoots, Cd, Cu, and Zn were the heavy metals that posed the highest risk due to the higher shoot content in all treatments, whereas Ni and Pb posed relatively lesser risk. Generally, the percentage of sand and silt in BCF Roots and BCF Shoots was quite effective for Co, Ni, and Zn and it seems that soil texture is an important variable in heavy metals bioavailability. In conclusion, our findings highlight the significance of using SS to increase cabbage growth in soils contaminated with heavy metals. Furthermore, cabbage may be a good choice for phytoremediation of heavy metal-contaminated calcareous soils in terms of soil remediation. Novelty statement In recent years, sewage sludge production has increased as well as related waste disposal strategies because of the increasing population and growing demand for agricultural products. Sewage sludge utilization as a low-cost fertilizer has spread in some parts of Iran and the world. On the other hand, unnecessary and unproductive use of sewage sludge results in the accumulation of heavy metals in soils, adding them to food and the potential risk to human health. Currently, work on the transfer of heavy metals from soil to plant after soil treated with sewage sludge has focused on the bioavailability of heavy metals using specific extractants. The assessment of the transfer of heavy metals from soil to different parts of plants using sewage sludge has been less studied. In this study, the transfer of heavy metals (Cd, Co, Cu, Ni, Pb, and Zn) from several soils (30 soils samples) having diverse physical and chemical properties to the tissues of the cabbage plant in control soils, and two types of sewage sludge (nonspiked and spiked with heavy metals) were investigated. The novelty of this study is that the measured bio-concentration factor of heavy metals from soil to root and from soil to shoot and translocation of heavy metals from plant roots to shoots and correlations between these parameters and soil properties are reported for the first time in diverse calcareous soils.

In this study, pot experiments were conducted to determine the effects of industrial solid wastes (ISWs) (ceramic, stone, and sugar factory wastes) and organic wastes (rice husk and wheat straw) on growth and heavy metals uptake by tomato (Lycopersicum esculentum) plants. The soil was treated with 10% of ISWs and 5% of organic wastes. The fractionation of heavy metals also has been studied in all treated soils. It was observed that the addition of ISWs in soil increased heavy metal contents in all fractions. The addition of organic wastes to control and treated soils decreased exchangeable fraction and increased organic matter and residual fractions. Following the ceramic factory and stone cutting waste addition, tomato yield significantly decreased as compared to control soil. The application of ISWs caused an increase in heavy metal contents of tomato plants. In control and ISWs-treated soils, dry matter yield of tomato grown in the presence of wheat straw was significantly restricted, while the application of rice husk increased tomato shoot and root dry weight. Results of experiments indicated that the application of both organic wastes significantly decreased heavy metal uptake by tomato plants. The investigation of health risk index (HRI) values indicated that in these industrial areas, potential health risk by intake of heavy metals from tomato for both adults and children generally assumed to be safe. The values of HRI were lesser when rice husk was applied to the soil. In general, these results highlighted that the application of rice husk in soils contaminated with ISWs increased the growth and yield of tomato and reduced the heavy metal toxicity for tomato consumption in contaminated soils.

Biochar and nanoparticle (NP) have the ability to sorb potentially toxic elements (PTEs) from soil and reduce toxicity and leaching into water bodies. However, there is need to tailor biochar formulations to soil types. In this study, we investigate the mobility and chemical forms of Cd, Cr, Cu, Ni, and Zn in a spiked, alkaline soil after amendment with combination of NPs (nano-Fe (NF), nano-clay (NC)) and biochars (almond shell 500 °C, walnut shell 400 °C) in different doses (0, 2.5, 5, and 10%). Many previous studies concluded biochar immobilized PTEs due to an increase in soil pH, which can be disregarded here (soil pH 7.9). In a twenty-week column leaching experiment biochar addition significantly decreased PTE leaching and NP addition further immobilized PTEs in most cases. On average almond biochar more effectively reduced Zn leaching and walnut biochar was more effective in decreasing the leaching of Cd, Cr, and Ni (e.g. 5% biochar reduced Cr leaching by 68%). Copper was immobilized effectively by both biochars. Nano-clay combined with walnut biochar performed best in all treatments, in particular for Cd, Ni, and Zn (e.g. 10% walnut biochar only and in combination with NC reduced Zn leaching by 14.2% and 58.5%, respectively). After amendment, PTEs were present in the Fe-Mn oxides, organic and residual fractions and less in the exchangeable fraction, reducing PTE availability and leachability. The results demonstrate that even for cationic PTEs that behave similarly in the environment optimal biochar-mineral formulations can differ., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Overuse of chemical and organic fertilizers in greenhouse (GH) crop production may cause the accumulation of heavy metals in soils and risks to human health. The aims of this study were to compare physical and chemical properties of GH with open-field (OF) soils, to clarify the buildup of heavy metals and phosphorus (P) in soils, and to assess the risks of selected heavy metals in soils and cucumber ( Cucumis sativus L.) and tomato ( Lycopersicon esculentum Mill.) from GH vegetables in Hamedan, western Iran. The average total and Olsen P of GH soils were significantly higher than the OF soils for both vegetables. The order of total and available heavy metal content in tomato GH soils has been set as zinc (Zn) > nickel (Ni) > chromium (Cr) > lead (Pb) > copper (Cu) > cadmium (Cd) and Zn > Cr > Cu > Pb > Ni > Cd, respectively. The same order was found for cucumber GH soils, except that the position of Pb and Cu was changed. The results indicated that in both GH cucumber and tomato soils, the mean content of total and available Zn, available Cu, Ni, and Pb, was extra than in OF soils. There were no significant differences between average total Cr, Cu, Ni, and Pb in GH and OF soils. Tomato vegetables had higher heavy metal content and transfer factors, particularly for Cr than cucumber vegetables. According to the health risk indices, Cr and Pb represented a high potential risk for health through cucumber and tomato consumption. There were limited Cd, Cu, Pb, and Zn inputs from the irrigation waters, while the input of Cr and Ni may be important. However, the amount of manure application and heavy metal content of the manures was significant.

We evaluated the effect of geomaterials (modified zeolite and bentonite using CaCl 2 ) and nanoparticles (ZnO and MgO) on the mono-metal and competitive sorption of cadmium (Cd), copper (Cu), nickel (Ni), and zinc (Zn) in an alkaline soil treated with three sewage sludges (SSs) collected from Isfahan, Rasht and Shiraz, Iran. The three SSs increased Cu sorption compared to the control. Sorption of Cd and Zn increased by the addition of Isfahan SS, but decreased by that of Rasht SS. Isfahan SS increased significantly the distribution coefficient of Cd, Cu, and Zn by 1.9, 1.2 and 1.5 times, respectively, compared to the control. The geomaterials and nanoparticles increased metal sorption in the SS-amended soil. Zeolite and MgO were the best sorbents for Cu in Rasht and Shiraz SS-treated soil, while ZnO and MgO were better in Isfahan SS-treated soil. Bentonite showed the highest Cd sorption capacity in Isfahan SS-treated soil, and MgO in the Shiraz SS-treated soil. ZnO showed the highest sorption capacity for Ni among the three SSs treatments. The nanoparticles showed higher sorption capacity for Zn than the geomaterials. We conclude that zeolite, bentonite, ZnO and MgO could be suitable immobilizing agents for Cd, Cu, Ni, and Zn in SS-amended alkaline soils., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This study was conducted to investigate the effect of industrial solid wastes (ISWs) and salinity on growth and heavy metals uptake by cucumber (Cucumis sativus L.). The soil was treated with 5% and 10% of the ceramic factory (CFW), stone cutting (SCW) and sugar factory (SFW) wastes. Plant of cucumber was grown under greenhouse conditions in control and ISWs treated soils and stressed with electrical conductivities of 0, 4 and 8 dS m -1 . Plants were harvested after 2 months and separated into root, shoot, and fruit. Then, dry weights and heavy metals contents in each fraction of plants were determined. The addition of all ISWs in soil increased total heavy metals content in the soil. In all treatments, growth parameters of cucumber decreased when irrigated with saline waters. As compared to control soil, the addition of CFW and SCW to soil decreased plant dry weight, while, it was improved with the addition of the SFW. The result of plant analysis showed that there was an increase in the contents of heavy metals (except Cr) in all parts of cucumber with the addition of ISWs. Salinity decreased the content of Zn uptake and increased another heavy metal uptake by all parts of the plants. The application of ISWs and salinity did not show a significant effect on bioconcentration (BCF) and transfer factor (TF) of heavy metals in plants. The health risk index (HRI) values of all heavy metals for both adults and children were found to be less than 1, so, the health risk of heavy metal for people who consume cucumber grown in these industrial areas was generally assumed to be safe., (Copyright © 2019 Elsevier Inc. All rights reserved.)

This experiment was conducted to investigate the potential risk of toxic elements in paddy soils and rice straws, bran, and husked grains in Kuchesfahan, Gilan, Iran. The average content of total and DTPA-extractable of Cd, Cu, Fe, Mn, Ni, Pb, and Zn were 7.0, 26.3, 20728.8, 1516.7, 43.8, 16.6, and 211.8 mg kg -1 , and 0.32, 14.1, 97.3, 63.4, 1.7, 4.8, and 56.2 mg kg -1 , respectively. In addition, the average content of Cd, Cu, Fe, Mn, Ni, Pb, and Zn in rice grain was 0.16, 2.4, 135.5, 34.1, 2.0, 0.6, and 15.0 mg kg -1 , respectively. The average transfer factor for Cd, Cu, Fe, Mn, Ni, Pb, and Zn from soil to straw was 0.38, 0.16, 0.004, 0.13, 0.3, 0.04, and 0.09, respectively. The average values of estimated daily intake for Cd, Cu, Fe, Mn, Ni, Pb, and Zn through rice consumption for adult are respectively, estimated to be 0.0004, 0.005, 0.32, 0.08, 0.005, 0.0015, and 0.035 mg kg -1 body weight per day. There was no health risk index (HRI) values for adult greater than 1 (except three samples for Fe, and one sample for Mn and Cd); indicated that intake of single metal through the consumption of rice was safe. The average of heath index (HI) value for rice consumption was 0.33 and 0.35 for adult and children, respectively. Therefore, combination of several potentially toxic elements may not cause risk to local residents. Spatial distributions of HRI were obtained for potentially toxic metals in husked grains.

The objectives of this study were to investigate competitive sorption behaviour of heavy metals (Cd, Cu, Mn, Ni, Pb and Zn) under different management practices and identify soil characteristics that can be correlated with the retention and mobility of heavy metals using 65 calcareous soil samples. The lowest sorption was found for Mn and Ni in competition with the other metals, indicating the high mobility of these two cations. The Freundlich equation adequately described heavy metals adsorption. On the basis of Freundlich distribution coefficient, the selectivity sequence of the metal adsorption was Cu > Pb > Cd > Zn > Ni > Mn. The mean value of the joint distribution coefficient (K dΣsp) was 182.1, 364.1, 414.7, 250.1, 277.7, 459.9 and 344.8 l kg(-1) for garden, garlic, pasture, potato, vegetables, wheat and polluted soils, respectively. The lowest observed K dΣsp in garden soil samples was due to the lower cation exchange capacity and lower carbonate content. The results of the geochemical modelling under low and high metal addition indicated that Cd, Ni, Mn and Zn were mainly retained via adsorption, while Pb and Cu were retained via adsorption and precipitation. Stepwise forward regression analysis showed that clay, organic matter and CaCO3 were the most important soil properties influencing competitive adsorption of Cd, Mn, Ni and Zn. The results in this study point to a relatively easy way to estimate distribution coefficient values.

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.