Mechanistic Evidence for Hg Removal from Wastewater by Biologically Produced Sulfur.

A significant quantity of biologically produced sulfur (BPS) is generated as a by-product of chemical and biological desulfurization processes applied to landfill gas treatment. The beneficial upcycling of BPS has seen limited use in the environmental context. The effectiveness and underlying mechanism of BPS as an adsorbent for removing Hg2+ from both solution and wastewater were elucidated based on experiments encompassing surface characterization, adsorption isotherms, kinetics, and thermodynamics. The BPS exhibited remarkable efficacy in removing Hg2+ from solution, with the Langmuir model accurately describing the adsorption process and showing a maximum adsorption capacity of 244 mg g-1. Surface analysis through X-ray photoelectron spectroscopy and scanning electron microscopy revealed that Hg2+ complexed with sulfide on BPS surfaces, forming stable HgS. The adsorbed Hg was strongly retained in BPS, with less than 0.2% of the adsorbed Hg desorbed by strong acids. Adsorption kinetics followed the double-exponential first-order model, showing an initial rapid adsorption phase wherein 75% of the initial Hg2+ was removed within 5 min, followed by a slower adsorption rate. The thermodynamic parameters suggested that adsorption of Hg2+ by BPS was a spontaneous and endothermic process. Additionally, BPS effectively removed Hg2+ from wastewater, showing preference for Hg over other co-existing metals. These findings underscore the potential of BPS as an effective adsorbent for Hg2+ removal from wastewater.

Comparison and analysis of soil microbial communities in organic and conventional paddy fields by farming season.

Interest in soil health and biodiversity conservation has become increasingly important. Consequently, studies comparing the chemical and biological characteristics of organic and traditional paddy soils have been increasing. Soil microorganisms are essential in nutrient cycling; however, their diversity is challenging to ascertain because of their environmental sensitivity and complex interactions. Particularly, in domestic rice cultivation, the soil undergoes multiple irrigation and drainage processes during crop growth, providing a diverse ecological environment for soil microorganisms. The objective of this study is to compare the microbial community and diversity between paddy soils in two agricultural systems. We selected organic and conventional paddy fields in Yangpyeong, Gyeonggi Province, and collected monthly samples from August to November 2022 for analysis. Bacteria and fungi were amplified from the 16S rRNA V3V4 region, ITS 3-4 region respectively, For the comparison of microbial diversity, Alpha diversity indices (Chao1, Shannon, Gini-Simpson indices) were analyzed. The results indicated genus-level differences in microbial communities, with the genera Mucor and Sirastachys exclusively present in organic paddy soils, while the genus Ustilaginoidea was exclusively found in conventional paddy soils. Among them, Ustilaginoidea is reported to be a fungus causing false smut disease, causing damage to crop growth and quality. Additionally, the comparison of microbial diversity between the two farming showed no significant differences (p>0.05). In conclusion, When the microbial communities present in both farming systems were examined, organic farming appeared to be more advantageous than conventional farming regarding crop disease and health. This study provides essential soil chemical and microbiological data for understanding the fundamental characteristics of paddy soils in South Korea.

Alginate-encapsulated biochar as an effective soil ameliorant for reducing Pb phytoavailability to lettuce (Lactuca sativa L.).

The alginate-biochar formulation for metal removal from aquatic environments has been widely tried but its use for lowering phytoavailability of metals in the soil-crop continuum is limited. Biochar has been increasingly used as a soil amendment due to its potential for soil carbon sequestration and sorption capacity. Handling of powdery biochar as a soil top-dressing material is, however, cumbersome and vulnerable to loss by water and wind. In this experiment, biochar powder, which was pyrolyzed from oak trees, was encapsulated into beads with alginate, which is a naturally occurring polysaccharide found in brown algae. Both batch and pot experiments were conducted to examine the effects of the alginate-encapsulated biochar beads (BB), as compared to its original biochar powdery form (BP), on the Pb adsorption capacity and phytoavailability of soil Pb to lettuce (Lactuca sativa L.). The BB treatment improved reactivity about six times due to a higher surface area (287 m2 g-1) and five times due to a higher cation exchange capacity (50 cmolc kg-1) as compared to the BP treatment. The maximum sorption capacity of Pb was increased to 152 from 81 mg g-1 because of surface chemosorption. Adsorption of Pb onto BB followed multiple first-order kinetics and comprised fast and slow steps. More than 60% of the Pb was adsorbed in the fast step, i.e., within 3 h. Also, the BB treatment, up to the 5% level (w/w), increased soil pH from 5.4 to 6.5 and lowered the phytoavailable fraction of Pb in soil from 5.7 to 0.3 mg kg-1. The Pb concentrations in lettuce cultivated at 5% for the BP and BB treatments were similar but 63 and 66% lower, respectively, than those of the control soil. The results showed that the encapsulation of biochar with alginate enhanced adsorption by the biochar.

A Simplified Method for Anionic Surfactant Analysis in Water Using a New Solvent.

Anionic surfactants (AS) are becoming a major emerging contaminant of waters due to their widespread use in household and industrial products. The standard chloroform method for analysis of AS in water relies on chloroform extraction of a methylene blue active substance (MBAS), which contains ion pairs between methylene blue (MB) molecules (positively charged) and AS. Due to the poor extractability of chloroform, the procedure is complicated, time-consuming, and subject to anionic interferences. A mixture of methyl isobutyl ketone (MIBK)-1,2-dichloroethane (DCE) at a 3:1 ratio of MIBK:DCE proved to be a robust solvent for AS extraction for a wide range of samples under various chemical conditions. The objectives of this research were to set the washing protocol to eliminate the anionic interferences in the MIBK-DCE extraction and to develop a new simplified analytical method for AS analysis using the MIBK-DCE (3:1) extractant. The suitability of the proposed MIBK-DCE method was validated based on quality control and assurance criteria, such as selectivity, accuracy, precision, method detection limit (MDL), limit of quantification (LOQ), and sensitivity. Various water samples, such as freshwater, wastewater, and seawater, were used for the method development and validation. Interferences by inorganic and organic anions were evident in the reference chloroform method but were eliminated in the MIBK-DCE procedure with a two-step process that consisted of washing with a carbonate/bicarbonate solution at pH 9.2 and a mixture of silver sulfate (Ag2SO4) and potassium alum (AlK(SO4)2). The simplified MIBK-DCE method for sodium dodecyl sulfate (SDS) analysis consisted of (i) sample pre-treatment, (ii) MIBK-DCE extraction, (iii) washing and filtration, and (iv) absorbance measurement. The MIBK-DCE method was accurate, precise, selective, and sensitive for AS analysis and showed MDL of 0.0001 mg/L, LOQ of 0.0005 mg/L, relative standard deviation (RSD) of 0.1%, and recovery of 99.0%. All these criteria were superior to those of the chloroform method. Sensitivity analysis showed highly significant correlations in AS analyses between the MIBK-DCE and chloroform methods for domestic wastewater, industrial wastewater, and seawater. The MIBK-DCE method is simple, rapid, robust, reproducible, and convenient, when compared to the chloroform method. Results demonstrate that the simplified MIBK-DCE method can be employed for AS analysis in a wide range of environmental waters including seawater.

Analysis of Major Bacteria and Diversity of Surface Soil to Discover Biomarkers Related to Soil Health.

The discovery of biomarkers for assessing soil health requires the exploration of organisms that can explain the core functions of soil and identification of species with major roles in these functions. However, identifying specific keystone markers within the soil microbiota is challenging. Next-generation sequencing (NGS)-based molecular-biological methods have revealed information on soil biodiversity; however, whether this biodiversity is related to soil health remains unclear. In this study, we performed NGS on grassland surface soil to compare the prokaryotic and eukaryotic genetic diversity to determine the chemical soil quality and examined markers associated with soil health. Microorganisms associated with the nitrogen cycle, bioremediation, plant pathogenicity, antibiotic production, and material degradation showed potential for use as markers. To propose a framework for soil health assessment, we not only used traditional indicators, such as chemical and physical measures, but also assessed metagenomics data of soil by land use to identify the major factors influencing the microbial structure in soil. Moreover, major keystone species were identified. Furthermore, the microbial genetic diversity of generally healthy surface soil, such as forests, farmland, and parks, was determined. These findings provide basic data for exploring soil health-related biomarkers.

Screening of a Novel Solvent for Optimum Extraction of Anionic Surfactants in Water.

Anionic surfactants (AS) are detrimental aquatic pollutants due to their well-characterized toxicity to aquatic organisms. The concentration of AS in aquatic environments is increasing because of their extensive use in many industries and households. The standard reference method for AS analysis is to determine a methylene blue active substance (MBAS) complex formed between AS and the methylene blue (MB) cation by using chloroform. However, chloroform has a low AS extraction efficiency and other limiting properties, such as a high density and volatility, which make the conventional AS analytical method time-consuming and labor-intensive. In an effort to replace the use of chloroform, this study was carried out to screen novel solvents for their ability to extract AS in water samples. Criteria were based on AS extraction efficiency, physicochemical properties, and the stability of the solvent under different environmental conditions. Organic solvents, such as methyl isobutyl ketone (MIBK), 1,2-dichloroethane (DCE), dichloromethane, benzene, and n-hexane, were assessed. In extraction of the anionic surfactant sodium dodecyl sulfate (SDS), the mixture of MIBK-DCE (3:1) proved to be an optimum solvent as an alternative to chloroform. It not only enhanced SDS extractability but also improved properties, such as having a lower volatility, a lower density than water, and a quicker phase separation. Among solvents screened, no one single solvent in SDS extraction could meet such criteria. The performance of the MIBK-DCE (3:1) mixture in SDS extraction was stable, irrespective of pH and ionic strength of the SDS solution, washing process, and presence of cations. Anionic interference from halogen and polyatomic and organic anions in SDS extraction by MIBK-DCE (3:1) existed only at an elevated concentration, which is not occurring in the natural aquatic environment. Results demonstrated that a MIBK-DCE (3:1) mixture solvent could be used in AS analysis for a wide range of aquatic samples and it could be the basis for the development of a new analytical method to replace conventional chloroform.

A direct contact bioassay using sulfur-oxidizing bacteria (SOB) for toxicity assessment of contaminated field soils.

In this study, 11 low/uncontaminated (including Lufa 2.2) and 9 contaminated field soils with varying geophysical and physicochemical characteristics were evaluated for toxicities based on oxygen consumption of sulfur-oxidizing bacteria (SOB). Oxygen consumption of the low/uncontaminated soils ranged between 7.9 mL and 9.5 mL, while contaminated soils ranged between 0.4 mL and 5.4 mL. Inherent test variability (CVi), variation due to soil natural properties (CVns) and minimal detectable difference (MDD) values ranged 1.2%-3.9%, 3.5%-16.9%, and 2.1%-4.3%, respectively. The toxicity threshold of 20% was established for soil toxicity based maximal tolerable inhibition (MTI). All the contaminated soils were found to be toxic and showed inhibition between 42% and 100% above the 20% threshold value. Increased proportions of clay and slit enhanced the of inhibitory effect of contaminants on SOB by reducing the oxygen consumption. Current study provides a suitable method for the rapid toxicity assessment of contaminated field soils with the advantages of ease of handling and rapidity without employing elutriates and sophisticated equipments and tools.

Metagenomic Analysis for Evaluating Change in Bacterial Diversity in TPH-Contaminated Soil after Soil Remediation.

Soil washing and landfarming processes are widely used to remediate total petroleum hydrocarbon (TPH)-contaminated soil, but the impact of these processes on soil bacteria is not well understood. Four different states of soil (uncontaminated soil (control), TPH-contaminated soil (CS), after soil washing (SW), and landfarming (LF)) were collected from a soil remediation facility to investigate the impact of TPH and soil remediation processes on soil bacterial populations by metagenomic analysis. Results showed that TPH contamination reduced the operational taxonomic unit (OTU) number and alpha diversity of soil bacteria. Compared to SW and LF remediation techniques, LF increased more bacterial richness and diversity than SW, indicating that LF is a more effective technique for TPH remediation in terms of microbial recovery. Among different bacterial species, Proteobacteria were the most abundant in all soil groups followed by Actinobacteria, Acidobacteria, and Firmicutes. For each soil group, the distribution pattern of the Proteobacteria class was different. The most abundant classed were Alphaproteobacteria (16.56%) in uncontaminated soils, Deltaproteobacteria (34%) in TPH-contaminated soils, Betaproteobacteria (24%) in soil washing, and Gammaproteobacteria (24%) in landfarming, respectively. TPH-degrading bacteria were detected from soil washing (23%) and TPH-contaminated soils (21%) and decreased to 12% in landfarming soil. These results suggest that soil pollution can change the diversity of microbial groups and different remediation techniques have varied effective ranges for recovering bacterial communities and diversity. In conclusion, the landfarming process of TPH remediation is more advantageous than soil washing from the perspective of bacterial ecology.

Biologically produced sulfur as a novel adsorbent to remove Cd2+ from aqueous solutions.

Biological desulfurization processes of landfill gas yield an enormous amount of biologically produced S (BPS) as a byproduct. Capability of BPS to remove Cd2+ from aqueous solutions was tested and its removal efficiency was compared to that of granular activated carbon (GAC). Kinetics of Cd2+ removal by BPS was a two-stage process with an initial rapid adsorption showing 45% of initial Cd2+ was removed within 5 min, followed by a slower adsorption. Cadmium adsorption onto the BPS fitted the Langmuir isotherm model and maximum adsorption capacity of the BPS (63.3 mg g-1) was 1.8 times higher than that of GAC (36.1 mg g-1). Thermodynamic parameters showed that Cd2+ adsorption by BPS was favorable and endothermic. Data from XPS proved the main adsorption mechanism to be complexation of Cd2+ with sulfides in the BPS. Results demonstrated that BPS can be recycled as a novel adsorbent for Cd2+ removal from wastewater.

Bottom Ash Modification via Sintering Process for Its Use as a Potential Heavy Metal Adsorbent: Sorption Kinetics and Mechanism.

Heavy metal pollution in the environment is a critical issue, engendering ecosystem deterioration and adverse effects on human health. The main objective of this study was to evaluate heavy metal adsorbents by modifying industrial byproducts. The bottom ash was sintered and evaluated for Cd and Pb sorption. Three adsorbents (bottom ash, sintered bottom ash (SBA), and SBA mixed with microorganisms (SBMA)) were tested to evaluate the sorption kinetics and mechanism using a lab-scale batch experiment. The results showed that the highest sorption efficiency was observed for Cd (98.16%) and Pb (98.41%) with 10% SBA. The pseudo-second-order kinetic model (R2 > 0.99) represented the sorption kinetics better than the pseudo-first-order kinetic model for the SBA and SBMA, indicating that chemical precipitation could be the dominant sorption mechanism. This result is supported by X-ray photoelectron spectroscopy analysis, demonstrating that -OH, -CO3, -O, and -S complexation was formed at the surface of the sintered materials as Cd(OH)2 and CdCO3 for Cd and PbO, and PbS for Pb. Overall, SBA could be utilized for heavy metal sorption. Further research is necessary to enhance the sorption capacity and longevity of modified industrial byproducts.

Phytoavailability-based threshold values for cadmium in soil for safer crop production.

The phytoavailability of heavy metals in soils is important for both food safety and environmental management. Hence soil metal phytoavailability threshold values need to be established based on a firm scientific basis. In this study, optimal Cd phytoavailability threshold values, were determined for bean, rice and sesame cultivated in 100 soils varying widely in soil chemical characteristics by comparing the soil Cd phytoavailability obtained using three commonly used extraction procedures. Subsequently, the transfer functions derived in this study, were used to establish soil Cd phytoavailability threshold value standard limits for each specific crop. In addition, independent experimental data were used to supplement the obtained soil phytoavailable Cd threshold value for rice. Soil phytoavailable Cd concentrations extracted by 1 M NH4NO3, 0.05 M EDTA and Mehlich3 solutions were each more significantly correlated with plant Cd concentrations than total soil Cd concentrations. Thus, the soil Cd phytoavailability threshold values proposed in this study provide a more effective means of ensuring safer agricultural food production. Therefore, it is recommended that current agricultural soil heavy metal management policy; which is based on total concentrations; should be changed to embrace soil metal phytoavailability for safer agricultural food production.

A DOC coagulant, gypsum treatment can simultaneously reduce As, Cd and Pb uptake by medicinal plants grown in contaminated soil.

The efficiency of gypsum, as a dissolved organic carbon (DOC) coagulator, for the simultaneous immobilization of two heavy metals (Cd and Pb) and one metalloid (As) in agricultural soils near an abandoned mining site was examined. The agricultural soil was defined as long-term contaminated as As (1540mgkg-1), Cd (55mgkg-1) and Pb (1283mgkg-1) concentrations exceeded the Korean guideline values for As (25mgkg-1), Cd (4mgkg-1), and Pb (200mgkg-1). Gypsum was incorporated into the contaminated soil at 3% (w/w). In comparison two commonly using immobilizing agents (lime and compost), together with a mixture (lime+gypsum) were also included in the pot trial for the cultivation of two medical plants (A. gigas and A. macrocephala) and to evaluate the effectiveness of gypsum on As, Cd and Pb immobilization. The results showed that even though pH change-induced immobilizing agents such as lime were more effective than gypsum at immobilizing Cd and Pb, addition of gypsum also effectively reduced heavy metal phytoavailability as indicated by decreases in the concentration of Cd and Pb in medicinal plants. Furthermore, gypsum and gypsum+ lime were also most effective in reducing As concentrations in both plants studied. This was mainly attributed to significant decreases in soil DOC (48-64%) when gypsum and gypsum+lime were applied to the soil. Consequently, it was concluded that enhanced DOC coagulation with gypsum, could be considered as a promising technique for the immobilization of both metals (Cd and Pb) and metalloids (As) in agricultural soils.

Influence of Road Proximity on the Concentrations of Heavy Metals in Korean Urban Agricultural Soils and Crops.

The urban agricultural (UA) environment near active roadways can be degraded by traffic-related particles (i.e., exhaust gases and road dust), which may contain heavy metals. The current study investigated changes in heavy-metal [cadmium (Cd), copper (Cu), chromium (Cr) nickel (Ni), lead (Pb) and zinc (Zn)] concentrations in soils located near highly trafficked roads in Korea and the subsequent uptake of these metals by Chinese cabbage. Heavy-metal plant concentrations were determined in both washed and unwashed plant leaves to determine whether foliar deposition played any role in plant metal uptake. Soil concentrations of Cd, Cu, Pb, and Zn were all lower than the Korean standard soil limits and showed no significant influence from road traffic. In contrast, both Ni and Cr concentrations in soils collected within 10 m of the road were 4 and 5 times greater, respectively, than those in soils collected 70 m from the road. Heavy-metal concentrations in unwashed Chinese cabbage leaf collected at 5 m from the road were consistently greater than those of washed leaf samples, thus indicating the deposition of traffic-related particles on the plant surface. With the exception of Cu, all heavy-metal concentration in washed plant samples collected at 5 m also showed greater accumulation compared with samples collected further away. This was mainly attributed to increased total soil heavy-metal concentrations and increased metal phytoavailability induced by decreases in soil pH near the road. However, overall heavy-metal soil concentrations were well lower than the allowable concentrations, and the levels observed in plants collected in this study were considered not to currently pose a significant risk to human health. However, some traffic-related heavy metals, in particular Cr and Ni, were being accumulated in the roadside UA environment, which may warrant some caution regarding the environment and/or health issues in the future.

An integrated approach to safer plant production on metal contaminated soils using species selection and chemical immobilization.

In order to examine the species specific accumulation of heavy metals in medicinal crops, seven different common medicinal plants were cultivated on a Cd (55mgkg(-1)) and Pb (1283mgkg(-1)) contaminated soil. Subsequently, the effect of various immobilizing agents, applied in isolation and in combination, on Cd and Pb uptake by two medicinal plant species was examined. Cadmium and Pb root concentrations in medicinal plants grown in the control soil varied between 0.5 and 2.6mgkg(-1) for Cd and 3.2 and 36.4mgkg(-1) for Pb. The highest accumulation occurred in Osterici Radix (Ostericum koreanum) and Ginger (Zingiber officinale) and the lowest in Yam (Dioscorea batatas). Application of immobilizing agents significantly reduced both Cd and Pb concentrations in all medicinal plants examined, where the most effective single immobilizing agent was lime fertilizer (LF). Application of combination treatments involving sorption agents such as compost together with lime further decreased Cd and Pb concentrations from 1.3 and 25.3mgkg(-1) to 0.2 and 4.3mgkg(-1), respectively, which was well below the corresponding WHO guidelines. Thus appropriate immobilizing agents in combination with species selection can be practically used for safer medicinal plant production.

Effect of biochar on reclaimed tidal land soil properties and maize (Zea mays L.) response.

Reclaimed tidal land soil (RTLS) often contains high levels of soluble salts and exchangeable Na that can adversely affect plant growth. The current study examined the effect of biochar on the physicochemical properties of RTLS and subsequently the influence on plant growth performance. Rice hull derived biochar (BC) was applied to RTLS at three different rates (1%, 2%, and 5% (w/w)) and maize (Zea mays L.) subsequently cultivated for 6weeks. While maize was cultivated, 0.1% NaCl solution was supplied from the bottom of the pots to simulate the natural RTLS conditions. Biochar induced changes in soil properties were evaluated by the water stable aggregate (WSA) percentage, exchangeable sodium percentage (ESP), soil organic carbon contents, cation exchange capacity, and exchangeable cations. Plant response was measured by growth rate, nutrient contents, and antioxidant enzyme activity of ascorbate peroxidase (APX) and glutathione reductase (GR). Application of rice hull derived biochar increased the soil organic carbon content and the percentage of WSA by 36-69%, while decreasing the ESP. The highest dry weight maize yield was observed from soil which received 5% BC (w/w), which was attributed to increased stability of water-stable aggregates and elevated levels of phosphate in BC incorporated soils. Moreover, increased potassium, sourced from the BC, induced mitigation of Na uptake by maize and consequently, reduced the impact of salt stress as evidenced by overall declines in the antioxidant activities of APX and GR.