Integrating portable X-ray fluorescence site survey and ArcGIS models for rapid risk assessment and mitigation strategies at an abandoned arsenic mine site: a case study.

Australia's metalliferous abandoned mine sites (MAMSs), pose tangible threats to the environment and human health. To address these concerns, our study utilised state-of-the-art handheld XRF technology to conduct a real-time assessment of the Mole River arsenic mine site. The data revealed notably elevated levels of arsenic and manganese, with the southeast corner of the site identified as a contaminant hotspot. We used a tiered risk assessment approach to compare the detected contaminant concentrations to the Australian health investigation levels (tier 1). This led us to a broader examination of erosion vulnerabilities and the potential migration of contaminants (tier 2). Further, a hydrological assessment (tier 3) identified significant erosion in southern regions, indicating the potential for contaminants to be transported off-site through surface water runoff to Sam's Creek and Mole River. The proximity of a reservoir to these runoff pathways brought forth additional challenges, especially during heavy rainfall events. Subsequent laboratory analysis of water samples reinforced our findings, as they confirmed heightened arsenic concentrations in Mole River downstream, accentuating the potential risks to ecosystems and human health. By integrating the XRF contour map and erosion assessment with the RUSLE model, valuable insights are gained into critical hotspots with high contamination and erosion potential. By directing rehabilitation efforts towards critical hotspots, resources can be allocated more efficiently and cost-effectively.

Contaminant containment for sustainable remediation of persistent contaminants in soil and groundwater.

Contaminant containment measures are often necessary to prevent or minimize offsite movement of contaminated materials for disposal or other purposes when they can be buried or left in place due to extensive subsurface contamination. These measures can include physical, chemical, and biological technologies such as impermeable and permeable barriers, stabilization and solidification, and phytostabilization. Contaminant containment is advantageous because it can stop contaminant plumes from migrating further and allow for pollutant reduction at sites where the source is inaccessible or cannot be removed. Moreover, unlike other options, contaminant containment measures do not require the excavation of contaminated substrates. However, contaminant containment measures require regular inspections to monitor for contaminant mobilization and migration. This review critically evaluates the sources of persistent contaminants, the different approaches to contaminant remediation, and the various physical-chemical-biological processes of contaminant containment. Additionally, the review provides case studies of contaminant containment operations under real or simulated field conditions. In summary, contaminant containment measures are essential for preventing further contamination and reducing risks to public health and the environment. While periodic monitoring is necessary, the benefits of contaminant containment make it a valuable remediation option when other methods are not feasible.

Plant-derived saponin enhances biodegradation of petroleum hydrocarbons in the rhizosphere of native wild plants.

Plant-derived saponins are bioactive surfactant compounds that can solubilize organic pollutants in environmental matrices, thereby facilitating pollutant remediation. Externally applied saponin has potential to enhance total petroleum hydrocarbon (TPH) biodegradation in the root zone (rhizosphere) of wild plants, but the associated mechanisms are not well understood. For the first time, this study evaluated a triterpenoid saponin (from red ash leaves, Alphitonia excelsa) in comparison to a synthetic surfactant (Triton X-100) for their effects on plant growth and biodegradation of TPH in the rhizosphere of two native wild species (a grass, Chloris truncata, and a shrub, Hakea prostrata). The addition of Triton X-100 at the highest level (1000 mg/kg) in the polluted soil significantly hindered the plant growth (reduced plant biomass and photosynthesis) and associated rhizosphere microbial activity in both the studied plants. Therefore, TPH removal in the rhizosphere of both plant species treated with the synthetic surfactant was not enhanced (at the lower level, 500 mg/kg soil) and even slightly decreased (at the highest level) compared to that in the surfactant-free (control) treatment. By contrast, TPH removal was significantly increased with saponin application (up to 60% in C. truncata at 1000 mg/kg due to enhanced plant growth and associated rhizosphere microbial activity). No significant difference was observed between the two saponin application levels. Dehydrogenase activity positively correlated with TPH removal (p < 0.001) and thus this parameter could be used as an indicator to predict the rhizoremediation efficiency. This work indicates that saponin-amended rhizoremediation could be an environmentally friendly and effective biological approach to remediate TPH-polluted soils. It was clear that the enhanced plant growth and rhizosphere microbial activity played a crucial role in TPH rhizoremediation efficiency. The saponin-induced molecular processes that promoted plant growth and soil microbial activity in the rhizosphere warrant further studies.

Tooeleite Transformation and Coupled As(III) Mobilization Are Induced by Fe(II) under Anoxic, Circumneutral Conditions.

Tooeleite [FeIII6(AsIIIO3)4SO4(OH)4.4H2O] is an important As(III) host phase in diverse mining-impacted environments. Tooeleite has also received attention as a target phase for immobilizing As(III) in environmental and engineered settings. However, little is known regarding tooeleite's environmental stability, with no previous research examining the possible role of Fe(II) in inducing tooeleite transformation (as occurs for Fe(III) oxide minerals). We investigated shifts in solid-phase Fe and As speciation and associated As mobilization into the aqueous phase during exposure of tooeleite to aqueous Fe(II) under anoxic conditions at pH 4 to 8. Our results demonstrate that environmentally relevant concentrations of aqueous Fe(II) (i.e., 1 to 10 mM) induce significant mobilization of As(III) from tooeleite under near-neutral pH conditions, with greater As(III) mobilization occurring at higher pH. Extended X-ray absorption fine structure spectroscopy at both the As and Fe K-edge reveals that the observed As(III) mobilization was coupled with partial Fe(II)-induced transformation of tooeleite to As(III)-bearing ferrihydrite at pH 6 to 8. These results provide new insights into the environmental stability of tooeleite and demonstrate a novel pathway for As(III) mobilization in tooeleite-bearing systems.

Remediation of Pb-contaminated soil using modified bauxite refinery residue.

This study examines amendment of Pb-contaminated soil with modified bauxite refinery residue (MBRR) to decrease soil Pb mobility and bioaccessibility. Amendment experiments were conducted using four soils contaminated with Pb from various sources, including smelting, shooting-range activities and Pb-based paint waste. Lead L3-edge X-ray absorption spectroscopy (XAS) indicated that Pb speciation in these soils was a mixture of Pb sorbed to Fe (hydr)oxide and clay minerals, along with Pb bound to organic matter. Amendment with MBRR decreased water-soluble Pb and/or Toxicity Characteristic Leachate Procedure (TCLP) Pb concentrations. Lead L3-edge XAS and X-ray diffraction (XRD) indicated that Pb retention by MBRR occurred via sorption to Fe- and Al-(hydr)oxides at low Pb loadings, in addition to formation of hydrocerussite (Pb3(CO3)2(OH)2) at high loadings. Soil amendment with MBRR had relatively little effect on gastric-phase Pb bioaccessibility; as quantified via the Solubility/Bioavailability Research Consortium, SBRC, in vitro assay. In contrast, amendment with MBRR caused substantial decreases in relative intestinal-phase Pb bioaccessibility (Rel-SBRC-I) due to increased Pb sorption by MBRR's Fe- and Al-hydr(oxide) minerals as simulated GI tract conditions shifted from the gastric- to the intestinal-phase. These decreases in Rel-SBRC-I point to the potential efficacy of using amendment with MBRR to decrease soil Pb bioavailability.

Antimony speciation, phytochelatin stimulation and toxicity in plants.

Antimony (Sb) is a toxic metalloid that has been listed as a priority pollutant. The environmental impacts of Sb have recently attracted attention, but its phytotoxicity and biological transformation remain poorly understood. In this study, Sb speciation and transformation in plant roots was quantified by Sb K-edge X-ray absorption spectroscopy. In addition, the phytotoxicity of antimonate (SbV) on six plant species was assessed by measuring plant photosynthesis, growth, and phytochelatin production induced by SbV. Linear combination fitting of the Sb K-edge X-ray absorption near-edge structure (XANES) spectra indicated reduction of SbV was limited to ∼5-33% of Sb. The data confirmed that Sb-polygalacturonic acid was the predominant chemical form in all plant species (up to 95%), indicating Sb was primarily bound to the cell walls of plant roots. Shell fitting of Sb K-edge X-ray absorption fine-structure (EXAFS) spectra confirmed Sb-O and Sb-C were the dominant scattering paths. The fitting indicated that SbV was bound to hydroxyl functional groups of cell walls, via development of a local coordination environment analogous to Sb-polygalacturonic acid. This is the first study to demonstrate the key role of plant cell walls in Sb metabolism.

Soil washing of arsenic from mixed contaminated abandoned mine soils and fate of arsenic after washing.

Arsenic contamination in abandoned soils is a global concern which warrants an effective method of remediation. In this study, two organic acids and one biodegradable chelating agent were used to treat arsenic (As) contaminated abandoned mine soils. The concentration of As was 19,100 and 75,350 (mg/kg) for Webbs Consols (WC) and Mole River (MR) samples, respectively. X-ray diffraction and scanning electron microscopy confirmed that tooeleite, arsenopyrite, scorodite and quartz were the major minerals in these soils. A major portion of the As was composed of amorphous and crystalline oxides of Fe and Al determined by sequential extraction. Among the three washing reagents (oxalic acid, citric acid and EDDS) oxalic acid showed the best performance for extracting As. Based on the batch experiment, 0.5 M oxalic acid and 3 h of washing was the most efficient treatment to extract As and other trace elements. Extraction of As, Fe, and Pb was 70, 55, and 48% respectively for WC, while 68, 45 and 63% respectively for MR soil. Oxalic acid extracted 75 and 83% of As and Fe, respectively from tooeleite. Leachability and bioaccessibility of As and Fe in the treated soil was reduced due to washing. However, bioaccessibility and leachability of Pb in soil and Fe and As in tooeleite increased in washed samples. Though the leachability and bioaccessibility of As and Fe in soil was reduced in the treated soil, As still exceeded the USEPA criteria (5 mg/L) which is needed to successfully remediate soil by washing. Soil washing and subsequent solidification/stabilization could be an alternative option to remediate extremely contaminated abandoned mine soil.

Adsorption-Desorption Behavior of Arsenate Using Single and Binary Iron-Modified Biochars: Thermodynamics and Redox Transformation.

Arsenic (As) is a dangerous contaminant in drinking water which displays cogent health risks to humans. Effective clean-up approaches must be developed. However, the knowledge of adsorption-desorption behavior of As on modified biochars is limited. In this study, the adsorption-desorption behavior of arsenate (AsV) by single iron (Fe) and binary zirconium-iron (Zr-Fe)-modified biosolid biochars (BSBC) was investigated. For this purpose, BSBC was modified using Fe-chips (FeBSBC), Fe-salt (FeCl3BSBC), and Zr-Fe-salt (Zr-FeCl3BSBC) to determine the adsorption-desorption behavior of AsV using a range of techniques. X-ray photoelectron spectroscopy results revealed the partial reduction of pentavalent AsV to the more toxic trivalent AsIII form by FeCl3BSBC and Zr-FeCl3BSBC, which was not observed with FeBSBC. The Langmuir maximum AsV adsorption capacities were achieved as 27.4, 29.77, and 67.28 mg/g when treated with FeBSBC (at pH 5), FeCl3BSBC (at pH 5), and Zr-FeCl3BSBC (at pH 6), respectively, using 2 g/L biochar density and 22 ± 0.5 °C. Co-existing anions reduced the AsV removal efficiency in the order PO4 3- > CO3 2- > SO4 2- > Cl- > NO3 -, although no significant inhibitory effects were observed with cations like Na+, K+, Mg2+, Ca2+, and Al3+. The positive correlation of AsV adsorption capacity with temperature demonstrated that the endothermic process and the negative value of Gibbs free energy increased (-14.95 to -12.47 kJ/mol) with increasing temperature (277 to 313 K), indicating spontaneous reactions. Desorption and regeneration showed that recycled Fe-chips, Fe-salt, and Zr-Fe-salt-coated biochars can be utilized for the effective removal of AsV up to six-repeated cycles.

Rare earth elements (REE) for the removal and recovery of phosphorus: A review.

There is little doubt that 'rock phosphate' reserves are decreasing, with phosphorus (P) peak to be reached in the coming decades. Hence, removal and recovery of phosphorus (P) from alternative nutrient-rich waste streams is critical and of great importance owing to its essential role in agricultural productivity. Adsorption technique is efficient, cost-effective, and sustainable for P recovery from waste streams which otherwise can cause eutrophication in receiving waters. As selective P sorption using rare earth elements (REE) are gaining considerable attention, this review extensively focuses on P recovery by utilising a range of REE-incorporated adsorbents. The review briefly provides existing knowledge of P in various waste streams, and examines the chemistry and behaviour of REE in soil and water in detail. The impact of interfering ions on P removal using REE, adsorbent regeneration for reuse, and life cycle assessment of REE are further explored. While it is clear that REE-sorbents have excellent potential to recover P from wastewaters and to be used as fertilisers, there are gaps to be addressed. Future studies should target recovery and reuse of REE as P fertilisers using real wastewaters. More field trials of synthesized REE-sorbents are highly recommended before practical application.

Phosphorus application enhances alkane hydroxylase gene abundance in the rhizosphere of wild plants grown in petroleum-hydrocarbon-contaminated soil.

This study assessed the ability of phosphorus (P) fertilizer to remediate the rhizosphere of three wild plant species (Banksia seminuda, a tree; Chloris truncata, a grass; and Hakea prostrata, a shrub) growing in a soil contaminated with total (aliphatic) petroleum hydrocarbon (TPH). Plant growth, photosynthesis (via chlorophyll fluorescence), soil microbial activity, alkane hydroxylase AlkB (aliphatic hydrocarbon-degrading) gene abundance, and TPH removal were evaluated 120 days after planting. Overall, although TPH served as an additional carbon source for soil microorganisms, the presence of TPH in soil resulted in decreased plant growth and photosynthesis. However, growth, photosynthesis, microbial activities, and AlkB gene abundance were enhanced by the application of P fertilizer, thereby increasing TPH removal rates, although the extent and optimum P dosage varied among the plant species. The highest TPH removal (64.66%) was observed in soil planted with the Poaceae species, C. truncata, and amended with 100 mg P kg-1 soil, while H. prostrata showed higher TPH removal compared to the plant belonging to the same Proteaceae family, B. seminuda. The presence of plants resulted in higher AlkB gene abundance and TPH removal relative to the unplanted control. The removal of TPH was associated directly with AlkB gene abundance (R2 > 0.9, p < 0.001), which was affected by plant identity and P levels. The results indicated that an integrated approach involving wild plant species and optimum P amendment, which was determined through experimentation using different plant species, was an efficient way to remediate soil contaminated with TPH.

Arsenic bioaccessibility and fractionation in abandoned mine soils from selected sites in New South Wales, Australia and human health risk assessment.

Understanding the transport behaviour of arsenic (As) from soils to humans is critical when undertaking human health risk assessment and contamination control. This research examined As bioaccessibility in different As fractions and particle size fractions of As-enriched mine soils using different extractions. Bioaccessibility of As ranged from 0.24% to 32% for Solubility Bioaccessibility Research Consortium (SBRC) and Physiologically Based Extraction Test (PBET) methods, with extractable As (using 0.43 M HNO3) being 1.3-24.9%. The highest As bioaccessibility (19-32%) was consistently observed in the fine particle size fraction (< 53 µm) of all three extractions. Sequential extractions revealed that As fractions were mostly associated with crystalline (30-73%) and amorphous (9-59%) Fe/Al oxyhydroxides. The bioaccessibility of As in the gastric phase of SBRC and PBET methods highlighted a positive correlation (R2 = 0.83-0.88, p < 0.01) with exchangeable, surface and amorphous- bound As fractions, while the intestinal phase showed a strong positive correlation (R2 = 0.85-0.89, p < 0.01) with exchangeable and surface bound fractions. The study revealed that As bioaccessibility in soils can potentially be determined using the 0.43 M HNO3 extraction procedure. Health risk assessment confirmed that there was a strong increase in chronic daily intake, hazard quotient and cancer risk, with a reduction in particle size.

Biofilms Enhance the Adsorption of Toxic Contaminants on Plastic Microfibers under Environmentally Relevant Conditions.

Microplastics (MPs) exposed to the natural environment provide an ideal surface for biofilm formation, which potentially acts as a reactive phase facilitating the sorption of hazardous contaminants. Until now, changes in the contaminant sorption capacity of MPs due to biofilm formation have not been quantified. This is the first study that compared the capacity of naturally aged, biofilm-covered microplastic fibers (BMFs) to adsorb perfluorooctane sulfonate (PFOS) and lead (Pb) at environmentally relevant concentrations. Changes in the surface properties and morphology of aged microplastic fibers (MF) were studied by surface area analysis, infrared spectroscopy, and scanning electron microscopy. Results revealed that aged MFs exhibited higher surface areas because of biomass accumulation compared to virgin samples and followed the order polypropylene>polyethylene>nylon>polyester. The concentrations of adsorbed Pb and PFOS were 4-25% and 20-85% higher in aged MFs and varied among the polymer types. The increased contaminant adsorption was linked with the altered surface area and the hydrophobic/hydrophilic characteristics of the samples. Overall, the present study demonstrates that biofilms play a decisive role in contaminant-plastic interactions and significantly enhance the vector potential of MFs for toxic environmental contaminants. We anticipate that knowledge generated from this study will help refine the planetary risk assessment of MPs.

Petroleum hydrocarbon rhizoremediation and soil microbial activity improvement via cluster root formation by wild proteaceae plant species.

Rhizoremediation potential of different wild plant species for total (aliphatic) petroleum hydrocarbon (TPH)-contaminated soils was investigated. Three-week-old seedlings of Acacia inaequilatera, Acacia pyrifolia, Acacia stellaticeps, Banksia seminuda, Chloris truncata, Hakea prostrata, Hardenbergia violacea, and Triodia wiseana were transplanted in a soil contaminated with diesel and engine oil as TPH at pollution levels of 4,370 (TPH1) and 7,500 (TPH2) mg kg-1, and an uncontaminated control (TPH0). After 150 days, the presence of TPH negatively affected the plant growth, but the growth inhibition effect varied between the plant species. Plant growth and associated root biomass influenced the activity of rhizo-microbiome. The presence of B. seminuda, C. truncata, and H. prostrata significantly increased the TPH removal rate (up to 30% compared to the unplanted treatment) due to the stimulation of rhizosphere microorganisms. No significant difference was observed between TPH1 and TPH2 regarding the plant tolerance and rhizoremediation potentials of the three plant species. The presence of TPH stimulated cluster root formation in B. seminuda and H. prostrata which was associated with enhanced TPH remediation of these two members of Proteaceae family. These results indicated that B. seminuda, C. truncata, and H. prostrata wild plant species could be suitable candidates for the rhizoremediation of TPH-contaminated soil.

Antimonate sequestration from aqueous solution using zirconium, iron and zirconium-iron modified biochars.

Antimony (Sb) is increasingly being recognized as an important contaminant due to its various industrial applications and mining operations. Environmental remediation approaches for Sb are still lacking, as is the understanding of Sb environmental chemistry. In this study, biosolid biochar (BSBC) was produced and utilized to remove antimonate (Sb(V)) from aqueous solution. Zirconium (Zr), Zirconium-iron (Zr-Fe) and Fe-O coated BSBC were synthesized for enhancing Sb(V) sorption capacities of BSBC. The combined results of specific surface area, FTIR, SEM-EDS, TEM-EDS, and XPS confirmed that Zr and/or Zr-Fe were successfully coated onto BSBC. The effects of reaction time, pH, initial Sb(V) concentration, adsorbate doses, ionic strength, temperature, and the influence of major competitive co-existing anions and cations on the adsorption of Sb(V) were investigated. The maximum sorption capacity of Zr-O, Zr-Fe, Zr-FeCl3, Fe-O, and FeCl3 coated BSBC were 66.67, 98.04, 85.47, 39.68, and 31.54 mg/g respectively under acidic conditions. The XPS results revealed redox transformation of Sb(V) species to Sb(III) occurred under oxic conditions, demonstrating the biochar's ability to behave as an electron shuttle during sorption. The sorption study suggests that Zr-O and Zr-O-Fe coated BSBC could perform as favourable adsorbents for mitigating Sb(V) contaminated waters.

Mitigation of petroleum-hydrocarbon-contaminated hazardous soils using organic amendments: A review.

The term "Total petroleum hydrocarbons" (TPH) is used to describe a complex mixture of petroleum-based hydrocarbons primarily derived from crude oil. Those compounds are considered as persistent organic pollutants in the terrestrial environment. A wide array of organic amendments is increasingly used for the remediation of TPH-contaminated soils. Organic amendments not only supply a source of carbon and nutrients but also add exogenous beneficial microorganisms to enhance the TPH degradation rate, thereby improving the soil health. Two fundamental approaches can be contemplated within the context of remediation of TPH-contaminated soils using organic amendments: (i) enhanced TPH sorption to the exogenous organic matter (immobilization) as it reduces the bioavailability of the contaminants, and (ii) increasing the solubility of the contaminants by supplying desorbing agents (mobilization) for enhancing the subsequent biodegradation. Net immobilization and mobilization of TPH have both been observed following the application of organic amendments to contaminated soils. This review examines the mechanisms for the enhanced remediation of TPH-contaminated soils by organic amendments and discusses the influencing factors in relation to sequestration, bioavailability, and subsequent biodegradation of TPH in soils. The uncertainty of mechanisms for various organic amendments in TPH remediation processes remains a critical area of future research.

Sorption of PFOS in 114 Well-Characterized Tropical and Temperate Soils: Application of Multivariate and Artificial Neural Network Analyses.

The influence of soil properties on PFOS sorption are not fully understood, particularly for variable charge soils. PFOS batch sorption isotherms were conducted for 114 temperate and tropical soils from Australia and Fiji, that were well-characterized for their soil properties, including total organic carbon (TOC), anion exchange capacity, and surface charge. In most soils, PFOS sorption isotherms were nonlinear. PFOS sorption distribution coefficients (Kd) ranged from 5 to 229 mL/g (median: 28 mL/g), with 63% of the Fijian soils and 35% of the Australian soils showing Kd values that exceeded the observed median Kd. Multiple linear regression showed that TOC, amorphous aluminum and iron oxides contents, anion exchange capacity, pH, and silt content, jointly explained about 53% of the variance in PFOS Kd in soils. Variable charge soils with net positive surface charges, and moderate to elevated TOC content, generally displayed enhanced PFOS sorption than in temperate or tropical soils with TOC as the only sorbent phase, especially at acidic pH ranges. For the first time, two artificial neural networks were developed to predict the measured PFOS Kd (R2 = 0.80) in the soils. Overall, both TOC and surface charge characteristics of soils are important for describing PFOS sorption.

The influence of long-term ageing on arsenic ecotoxicity in soil.

The ageing of a contaminant in soil influences the bioavailability and toxicity of environmental pollutants. Yet, despite arsenic (As) being an important terrestrial contaminant, the effect of As ageing on phytotoxicity has received relatively little research. Research to date has reported predominantly short term (< 0.5 years) experiments. Here, we studied the influence of ageing over 0.25 and 5 years on the phytotoxicity of As (as arsenate) on Cucumis sativus L. (cucumber). The study showed that increasing ageing time of As from 0.25 to 5 years increased the EC10 and EC50 values by 4.0 and 1.76 fold, respectively. The dependence of ageing on soil properties was also examined, although only Freundlich sorption parameters were correlated to the ageing factor (r = 0.68, P = 0.028). Soils with high adsorption capacity also showed the greatest change in toxicity over 5 years. In addition, data was compiled from relevant literature to develop a model for As ecotoxicity. The combined model (n = 54) showed no relationship with pH but was correlated to the oxalate extractable iron content and %clay. Arsenate ecotoxicity (EC50, mg/kg) in the multivariate model was related to oxalate iron content, %clay and ageing time. Thus, the results of this study have significant implications for risk assessment of long-term As contaminated soils.

Arsenic geochemistry and mineralogy as a function of particle-size in naturally arsenic-enriched soils.

Naturally arsenic (As) enriched agricultural soils represent a significant global human health risk. In this study, As fractionation and mineralogy were investigated in naturally As-enriched agricultural soils and their corresponding sand, silt and clay fractions. Median As increased generally in the order (mg/kg)∶ silt (280) < bulk (314) < sand (323)

Removal of arsenate from contaminated waters by novel zirconium and zirconium-iron modified biochar.

A novel biochar metal oxide composite was synthesized for effective removal of arsenate (As(V)) from aqueous solution. The materials synthesized for As(V) removal was based on a biosolid-derived biochar (BSBC) impregnated with zirconium (Zr) and zirconium-iron (Zr-Fe). The synthesized materials were comprehensively characterized with a range of techniques including Brunauer-Emmett-Teller (BET-N2) surface area, zeta potential, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results confirmed that loading of Zr and Zr-Fe onto the biochar surface was successful. The influence of pH, biochar density, ionic strength, As(V) dose rate, major anions and cations on As(V) removal was also investigated. Under all pH and reaction conditions the Zr-Fe composite biochar removed the greatest As(V) from solution of the materials tested. The maximum sorption capacity reached 15.2 mg/g for pristine BSBC (pH 4.0), while modified Zr-BSBC and Zr-FeBSBC composites achieved 33.1 and 62.5 mg/g (pH 6), respectively. The thermodynamic parameters (Gibbs free energy, enthalpy, and entropy) suggested that the adsorption process is spontaneous and endothermic. The ZrBSBC and Zr-FeBSBC showed excellent reusability and stability over four cycles. Unmodified biochar resulted in partial reduction of As(V) under oxic conditions, whilst modified biochars did not influence the oxidation state of As. All results demonstrated that the Zr and Zr-Fe BSBC composites could perform as promising adsorbents for efficient arsenate removal from natural waters.

Rhizoremediation as a green technology for the remediation of petroleum hydrocarbon-contaminated soils.

Rhizoremediation is increasingly becoming a green and sustainable alternative to physico-chemical methods for remediation of contaminated environments through the utilization of symbiotic relationship between plants and their associated soil microorganisms in the root zone. The overall efficiency can be enhanced by identifying suitable plant-microbe combinations for specific contaminants and supporting the process with the application of appropriate soil amendments. This approach not only involves promoting the existing activity of plants and soil microbes, but also introduces an adequate number of microorganisms with specific catabolic activity. Here, we reviewed recent literature on the main mechanisms and key factors in the rhizoremediation process with a particular focus on soils contaminated with total petroleum hydrocarbon (TPH). We then discuss the potential of different soil amendments to accelerate the remediation efficiency based on biostimulation and bioaugmentation processes. Notwithstanding some successes in well-controlled environments, rhizoremediation of TPH under field conditions is still not widespread and considered less attractive than physico-chemical methods. We catalogued the major pitfalls of this remediation approach at the field scale in TPH-contaminated sites and, provide some applicable situations for the future successful use of in situ rhizoremediation of TPH-contaminated soils.