Environmental risk associated with accumulation of toxic metalloids in soils of the Odra River floodplain-case study of the assessment based on total concentrations, fractionation and geochemical indices.

The floodplain soils are often heavily enriched in metal(loid)s released from the industrial areas. A related environmental risk depends on their total concentrations and the forms and conditions conducive to mobilization. This study was aimed to examine the concentrations of metal(loid)s in the Odra floodplain soils and to assess the risk associated with their possible contamination. In this study, topsoil and deeper soil layer samples were collected from the inter- and out-of-embankment zones. Total concentrations of Pb, Zn, Cu, As, Mn and Fe, and their extractable fractions were determined in 1 M NH4NO3 (actual solubility) and by BCR sequential extraction. The environmental risk was assessed based on total concentrations, according to legal regulations, geochemical enrichment indices and extractability of elements, with considering soil morphological features. Some topsoil samples from the inter-embankment zone turned out considerably enriched in Pb, Zn, Cu, and As, as confirmed by geochemical indices. Zn and As concentrations in some samples exceeded the permissible values defined by Polish law. Zn and Mn showed a high actual solubility, but a simple experiment proved that it can be efficiently reduced by liming. BCR fractionation showed that all the elements occurred mainly in reducible forms. Therefore, the risk of their release from the layers that do not indicate redoximorphic features was assessed as negligible. The study showed that such a complementary approach is needed to assess the real environmental risk in the case of soils considerably enriched in potentially toxic elements.

Aspergillus niger-mediated release of phosphates from fish bone char reduces Pb phytoavailability in Pb-acid batteries polluted soil, and accumulation in fenugreek.

Soil receiving discharges from Pb-acid batteries dismantling and restoring units (PBS) can have a high concentration of phytoavailable Pb. Reducing Pb phytoavailability in PBS can decline Pb uptake in food crops and minimize the risks to humans and the environment. This pot study aimed to reduce the concentration of phytoavailable Pb in PBS through Aspergillus niger (A. niger)-mediated release of PO43- from fish bone [Apatite II (APII)] products. The PBS (Pb = 639 mg kg-1 soil) was amended with APII powder (APII-P), APII char (APII-C), and A. niger inoculum as separate doses, and combining A. niger with APII-P (APII-P + A. niger) and APII-C (APII-C + A. niger). The effects of these treatments on reducing the phytoavailability of Pb in PBS and its uptake in fenugreek were examined. Additionally, enzymatic activities and microbial biomass carbon (MBC) in the PBS and the indices of plant physiology, nutrition, and antioxidant defense machinery were scoped. Results revealed that the APII-C + A. niger treatment was the most efficient one. Compared to the control, it significantly reduced the Pb phytoavailability (DTPA-extractable Pb fraction) in soil and its uptake in plant shoots, roots, and grain, up to 61%, 83%, 74%, and 92%. The grain produced under APII-C + A. niger were safe for human consumption as Pb concentration in grain was 4.01 mg kg-1 DW, remaining within the permissible limit set by WHO/FAO (2007). The APII-C + A. niger treatment also improved soil pH, EC, CEC, MBC, available P content and enzymatic activities, and the fenugreek quality parameters. A. niger played a significant role in solubilizing PO43- from APII-C, which reacted with Pb and formed insoluble Pb-phosphates, thereby reducing Pb phytoavailability in PBS and its uptake in plants. This study suggests APII-C + A. niger can remediate Pb-polluted soils via reducing Pb phytoavailability in them.

Impacts of oxalic acid-activated phosphate rock and root-induced changes on Pb bioavailability in the rhizosphere and its distribution in mung bean plant.

Rhizosphere acidification in leguminous plants can release P from the dissolution of phosphate compounds which can reduce Pb bioavailability to them via the formation of insoluble Pb compounds in their rhizosphere. A soil polluted from Pb-acid batteries effluent (SPBE), having total Pb = 639 mg kg-1, was amended with six different rates (0, 0.5, 1, 2, 4 and 6%) of oxalic acid-activated phosphate rock (OAPR) and their effects on pH, available P and bioavailable Pb concentrations in the rhizosphere and bulk soils of mung bean plant were evaluated. Furthermore, the effects of these variant OAPR rates on Pb concentrations in plant parts, bioaccumulation factor (BAF) and translocation factor (TF) for Pb in grain and traits like productivity, the activities of antioxidant enzymes, and grain biochemistry were investigated. Results revealed that increasing rates of OAPR significantly increased pH values and available P while decreased bioavailable Pb concentrations in the rhizosphere over control. The highest dissolution of P in the rhizosphere was with 4 and 6% OAPR rates. As a result, the formation of insoluble Pb compounds affected on reduced Pb concentrations in shoots, roots, and grain in addition to lower grain BAF and TF values for Pb over control. Likewise, the highest plant productivity, improved grain biochemistry, high Ca and Mg concentrations, least oxidative stress, and enhanced soil alkaline phosphatase activity were found with 4 and 6% OAPR rates. The OAPR 4% rate is suggested for reducing grain Pb concentration, cell oxidative injury, and improving grain biochemistry in mung bean.

Accumulation of Arsenic by Plants Growing in the Sites Strongly Contaminated by Historical Mining in the Sudetes Region of Poland.

The uptake of As by various plants growing in highly enriched sites was examined in order to identify potential As accumulators and to assess the risk associated with As presence in plant shoots. Representative samples of 13 plant species, together with soil samples, were collected from various sites affected by historical As mining: mine and slag dumps, tailings and contaminated soils with As concentrations in a range 72-193,000 mg/kg. Potentially and actually soluble As forms, extracted with 0.43 M HNO3 and, 1M NH4NO3 were examined in relation to As concentrations in plant roots and shoots. The latter differed strongly among the species and within them and were in the ranges 2.3-9400 mg/kg and 0.5-509 mg/kg, respectively. The majority (over 66%) of plant samples had As shoot concentrations above 4 mg/kg, an upper safe limit for animal fodder. The uptake of As by plants correlated well with total and extractable soil As, though As concentrations in plants could not be predicted based on soil parameters. Equisetum spp. and C. epigejos indicated a particularly strong accumulation of As in shoots, while A. capillaris, and H. lanatus showed a limited As root-to-shoot transfer, apparently associated with species-related tolerance to As.

Residues of Persistent Organic Pollutants (POPs) in Agricultural Soils Adjacent to Historical Sources of Their Storage and Distribution-The Case Study of Azerbaijan.

The aim of this study was to identify and examine the levels of organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) in soil collected from the surroundings of historical pesticide storage facilities on former agricultural aerodromes, warehouses, and pesticide distribution sites located in the most important agricultural regions in Azerbaijan. The conducted research included determination of three groups of POPs (occurring together), in the natural soil environment influenced for many years by abiotic and biotic factors that could have caused their transformations or decomposition. In this study, soil samples were collected in 21 georeferenced points located in the administrative area of Bilasuvar, Saatly, Sabirabad, Salyan and Jalilabad districts of Azerbaijan. Soil chemical analysis involved determination of organochlorine compounds (OCP): hexachlorocyclohexanes (HCHs) (three isomers α-HCH, ß-HCH and γ-HCH) and dichlorodiphenyltrichloroethanes (DDTs) (six congeners 2,4'DDT; 4,4'DDT; 2,4'DDE; 4,4'DDE; 2,4'DDE; and 4,4'DDE); polycyclic aromatic hydrocarbons (PAHs): 16 compounds from the United States Environmental Protection Agency US EPA list and, PCBs (seven congeners identified with the following IUPAC numbers: 28, 52, 101, 118, 138, 153, and 180). Our research showed that OCPs reached the highest concentration in the studied areas. The total concentrations of OCPs ranged from 0.01 to 21,888 mg∙kg-1 with significantly higher concentrations of Σ6DDTs (0.01 µg kg-1 to 21880 mg kg-1) compared to ΣHCH (0.14 ng kg-1 to 166.72 µg kg-1). The total concentrations of PCBs in the studied soils was varied from 0.02 to 147.30 µg·kg-1 but only PCB138 and PCB180 were detected in all analyzed samples. The concentrations of Σ16 PAHs were also strongly diversified throughout the sampling areas and ranged from 0.15 to 16,026 mg kg-1. The obtained results confirmed that the agricultural soils of Azerbaijan contained much lower (up to by three orders of magnitude) concentrations of PCBs and PAHs than DDT. It is supported by the fact that PCBs and PAHs were not directly used by agriculture sector and their content results from secondary sources, such as combustion and various industrial processes. Moreover, the high concentrations of PAHs in studied soils were associated with their location in direct neighborhood of the airport, as well as with accumulation of contaminants from dispersed sources and long range transport. The high concentrations of pesticides confirm that deposition of parent OCPs have occurred from obsolete pesticide landfills.

Effects of biochar and zeolite soil amendments with foliar proline spray on nickel immobilization, nutritional quality and nickel concentrations in wheat.

Since Ni-rich soils are a threat to the environment, growing edible crops on Ni-rich soils can pose a serious risk to human, animal, plant and ecosystem health and, hence, is considered as a challenging task for the researchers. Contrarily, limiting the bioavailability of Ni in such soils upon the addition of suitable amendments cum foliar spray of proteinogenic amino acids having an objective to alleviate stress to crop plants can considerably reduce the environmental risk. In this pot trail, we substantiate the effects of biochar (BR) and zeolite (ZL) addition in the soil along with proline (PN) spray on the resistance, and stress responses of wheat against Ni as well as on Ni translocation and accumulation in wheat plants grown on a Ni-rich soil contaminated by electroplating effluent. The treatments, applied with and without PN spray, involved: no amendment; BR; ZL; and a concoction of both amendments (BR50%+ZL50%). We found that BR50%+ZL50% treatment significantly immobilized Ni in the soil, reduced its accumulation in the shoot, root, and grain, blocked membrane lipid peroxidation and showed an improvement in photosynthetic parameters, the status of antioxidant activities, grain biochemistry and grain yield, compared to the control. Interestingly, exogenous PN spray caused a significant additive effect on the aforementioned parameters in the wheat plants grown on BR50%+ZL50% treated soil. Our results involved a reduced Ni bioavailability in wheat rhizosphere due to BR50%+ZL50% in soil and, furthermore, the additive effect of PN spray to scavenging ROS, obstructing peroxidation of lipid membrane and, thus providing resilience to wheat plant against Ni stress. The suggested technique can make Ni-rich soils suitable for cultivation and production of high-quality food by minimizing Ni bioavailability and toxicity to plants.

Antimony in soils of SW Poland-an overview of potentially enriched sites.

Great concern has been recently focused on antimony in the environment due to the potential risks posed by this metalloid to humans. In Poland, the concentrations of Sb in soils have not been well recognized. The aim of this study was to identify the sites in south-western Poland where soils are considerably enriched in Sb and to make a rough assessment of a related environmental risk. One hundred forty-four samples were collected from 20 Lower Silesian locations chosen as potentially enriched in Sb that included historical mining sites, tailings impoundments, close vicinities of operating copper smelters, and landfills as well as currently operating and historical shooting ranges. Total concentrations of Sb in soils were determined, and related pollution indices were calculated. Several locations were found where soils contain high concentrations of Sb, with a maximum that exceeded 5600 mg kg-1 Sb in the alluvial soil affected by historical mining. Sequential extraction showed a considerably high percentage of Sb extracted in potentially soluble fractions 1 (non-specifically sorbed) and 2 (specifically sorbed), particularly in the samples collected from shooting ranges and in some samples from historical mine areas. This result provides a strong premise for further risk- and remediation-oriented examination of soils in those sites. More detailed research is needed to determine a spatial extent of soil contamination in the sites identified as highly enriched in Sb. Contrary to these findings, soil material collected from copper tailings impoundments, surroundings of smelters, and landfills did not show any particular enrichment in Sb.

The Release of Antimony from Mine Dump Soils in the Presence and Absence of Forest Litter.

This study examined the changes in antimony (Sb) solubility in soils, using organic matter introduced with forest litter, in various moisture conditions. Soils containing 12.8⁻163 mg/kg Sb were taken from the top layers of dumps in former mining sites in the Sudetes, South-West Poland. Soils were incubated for 90 days either in oxic or waterlogged conditions, with and without the addition of 50 g/kg of beech forest litter (FL). Water concentrations of Sb in some experimental treatments greatly exceeded the threshold values for good quality underground water and drinking water, and reached a maximum of 2.8 mg/L. The changes of Sb solubility caused by application of FL and prolonged waterlogging were, in various soils, highly divergent and in fact unpredictable based on the main soil properties. In some soils, the application of forest litter prompted the release of Sb from soil solid phase, while in the others it acted contradictorily. Soil waterlogging resulted, in most cases, in the increased release of Sb compared to oxic conditions, and this effect was enhanced by the addition of forest litter. However, in two soils the presence of forest litter counteracted the effects of waterlogging and diminished the quantities of released Sb.

Improvement in productivity, nutritional quality, and antioxidative defense mechanisms of sunflower (Helianthus annuus L.) and maize (Zea mays L.) in nickel contaminated soil amended with different biochar and zeolite ratios.

Nickel (Ni) contaminated soils pose a potential ecological risk to the environment, soil health, and quality of food produced on them. We hypothesized that application of miscanthus biochar (BC) and cationic zeolite (ZE) at various proportions into a Ni contaminated soil can efficiently immobilize Ni and reduce its bioavailability to sunflower (Helianthus annuus L.) and maize (Zea mays L.). An electroplating effluent contaminated soil was amended with BC and ZE, as sole treatments (2% w/w) and their combinations of various ratios (BC, ZE, BC25%ZE75%, BC50%ZE50% and BC75%ZE25%) for immobilization of Ni in the soil. Furthermore, the associated effects of these treatments on residual and DTPA-extractable Ni from the soil; concentrations of Ni in shoots, roots, and grain; growth, physiology, biochemistry and the antioxidant defence mechanisms of sunflower and maize were investigated. Results revealed that BC50%ZE50% treatment efficiently reduced DTPA-extractable Ni in the soil, Ni concentrations in shoots, roots, and grain, while improved selective parameters of both plants. Interestingly, the BC75%ZE25% treatment significantly improved the biomass, grain yield, physiology, biochemistry and antioxidant defense machinery, while decreased Ni oxidative stress in both sunflower and maize, compared to rest of the treatments. The results demonstrate that the BC50%ZE50% treatment can efficiently reduce Ni concentrations in the roots, shoots and grain of both sunflower and maize whereas, an improvement in biomass, grain yield, physiological, biochemical, and antioxidant defense machinery of both crops can only be achieved with the application of BC75%ZE25% treatment in a Ni contaminated soil.

Arsenic extractability and uptake by velvetgrass Holcus lanatus and ryegrass Lolium perenne in variously treated soils polluted by tailing spills.

Phytostabilization should be considered as an appropriate phytoremediation technique to restore the area affected by tailing spills in Zloty Stok, where arsenic ores were mined and processed for several centuries. The study aimed to compare the suitability of velvetgrass (Holcus lanatus L.) and ryegrass (Lolium perenne L.) for development of plant cover in that area. Various treatments commonly applied to support phytostabilization were examined. A pot experiment was carried out to assess the effects of soil amendment with phosphate (P), sewage sludge (SS) and iron salts (Fe) on arsenic extractability and its uptake by grass. Four kinds of soil material, containing 356-5350 mg kg(-1) As, were examined. Velvetgrass proved to be more resistant than ryegrass to the toxicity of soil arsenic. Ammonium sulphate extractability of As in soils correlated well with As concentrations in the biomass of both grass species. In three of four tested soils, application of Fe failed to decrease As extractability and to reduce its concentrations in the aboveground parts of grasses. Application of P and SS resulted in increased As solubility in soils, but their effects on plant biomass and As uptake were ambiguous. SS had a strong beneficial influence on the growth of velvetgrass, while such an effect was not observed for ryegrass.