Speciation, phytoavailability, and accumulation of toxic elements and sulfur by humic acid-fertilized lemongrass and common sage in a sandy soil treated with heavy oil fly ash: A trial for management of power stations wastes.

Globally, power stations generate huge amounts of the hazardous waste heavy oil fly ash (HOFA), which is rich in Ni, V, Fe, S, and dumped into landfills. Thus, exploring new approaches for a safe recycling and sustainable management of HOFA is needed and of great environmental interest. The potential application of HOFA as an amendment to sandy soils has not been studied yet. This is the first research investigating the potentiality of using HOFA as a soil conditioner. To this end, we conducted a greenhouse experiment in order to investigate the impacts of HOFA addition (1.2, 2.4, 3.6 t ha-1) to sandy soil on the total and available content of nutrients (e.g., S, Fe, Mn, Cu, Zn) and toxic elements (TEs; e.g., Cd, Co, Cr, Ni, Pb, V) in the soil and their phytoextraction and translocation by lemongrass (Cymbopogon citratus) and common sage (Salvia officinalis). We also assessed the impact of humic acid (HA) foliar application (50 and 100 l ha-1) on the growth and elements accumulation by the two plants. The studied HOFA was acidic and highly enriched in S (43,268.0), V (3,527.0), Ni (1774.0), and Fe (15,159.0) (units in mg kg-1). The X-ray absorption near edge structure (XANES) data showed that V in HOFA was composed primarily of V(IV) sorbed onto goethite, V(V) sorbed onto humic substances, in the forms of V2O3, and VCl4. Addition of the lower doses of HOFA (1.2 and 2.4 t ha-1) did not change significantly soil pH, salinity, and the total and available elements content compared to the unamended soil. Although the elements content in the 3.6 t ha-1 HOFA-treated soil was significantly higher than the untreated, the total content of all elements (except for Ni) was lower than the maximum allowable concentrations in soils. HOFA addition, particularly in the highest dose (3.6 t ha-1), decreased significantly the growth and biomass of both plants. Common sage accumulated more elements than lemongrass; however, the elements content in the plants was lower than the critical concentrations for sensitive plants. The foliar application of humic acid enhanced significantly the plant growth and increased their tolerance to the HOFA-induced stress. We conclude that the addition of HOFA up to 2.4 t ha-1 in a single application as amendment to sandy soils is not likely to create any TE toxicity problems to plants, particularly if combined with a foliar application of humic acid; however, repeated additions of HOFA may induce toxicity. These findings should be verified under field conditions.

Accumulation and bio-oxidation of arsenite mediated by thermoacidophilic Cyanidiales: innate potential biomaterials toward arsenic remediation.

Addressing geogenic and anthropogenic arsenic (As) pollution is critical for environmental health. This study explored arsenite [As(III)] removal using Cyanidiales, particularly Cyanidium caldarium (Cc) and Galdieria partita (Gp), under acidic to neutral pH, and determined As(III) detoxification mechanisms in relation to As speciation and protein secondary structure in Cyanidiales. Regarding As(III) sorption amounts, Cc outperformed Gp, reaching 83.2 mg g-1 of removal at pH 5.0. Wherein, 23.5 % of sorbed As on Cc presented as arsenate [As(V)] complexation with polysaccharides, alongside other predominant species including As(III)-cysteine (41.2 %) and As(III)-polysaccharides (35.3 %) complexes. This suggested that As(III) was directly transported into cells, rather than As(V). Coupled with the formation of As(III)-cysteine complexes within cells, these mechanisms may be key to efficiently accumulating As(III) in Cyanidiales during the 6-h incubation. These results highlight the potential of Cyanidiales for sustainable As(III) remediation and provide new insights into managing As(III) toxicity.

Thiol-functionalized black carbon as effective and economical materials for Cr(VI) removal: Simultaneous sorption and reduction.

Hazardous Cr(VI) continues to pose critical concerns for environmental and public health, demanding the development of effective remediation methods. In this study, thiol-functionalized black carbon (S-BC) was proposed for Cr(VI) removal by mixing thioglycolic acid (TGA) with black carbon (BC) derived from rice straw residue at 80 °C for 8 h. Using a 1:40 (g mL-1) BC-to-TGA ratio, the resulting S-BC40 sample demonstrated significantly enhanced Cr(VI) sorption capacities of 201.23, 145.78, and 106.60 mg g-1 at pH 3.5, 5.5, and 7.5, surpassing its BC counterpart by 2.0, 2.3, and 2.2 times. Additionally, S-BC40 converted all sorbed Cr into Cr(III) species at pH ≥ 5.5, resulting in an equal distribution of Cr(OH)3 and organic Cr(III) complexes. However, approximately 13% of Cr sorbed on BC remained as Cr(VI) at pH 3.5 and 7.5. Both C-centered and S-centered thiyl radicals might contribute to Cr(VI) reduction; however, sufficient C-S groups replenished via thiol-functionalization was the key for the complete Cr(VI) reduction on S-BC samples as pH ≥ 5.5. Thanks to the exceptional Cr(VI) sorption capacity, affordability, and accessibility, thiol-functionalization stands out as a promising modification method for BC. It presents a distinct opportunity to concurrently achieve the objectives of efficient Cr(VI) remediation and waste recycling.

Removal and concurrent reduction of Cr(VI) by thermoacidophilic Cyanidiales: a novel extreme biomaterial enlightened for acidic and neutral conditions.

Thermoacidophilic Cyanidiales maintain a competitive edge in inhabiting extreme environments enriched with metals. Here, species of Cyanidioschyzon merolae (Cm), Cyanidium caldarium (Cc), and Galdieria partita (Gp) were exploited to remove hexavalent chromium [Cr(VI)]. Cm and Gp could remove 168.1 and 93.7 mg g-1 of Cr(VI) at pH 2.0 and 7.0, respectively, wherein 89% and 62% of sorbed Cr on Cm and Gp occurred as trivalent chromium [Cr(III)]. Apart from surface-sorbed Cr(VI), the in vitro Cr(III) bound with polysaccharide and in vivo chromium(III) hydroxide [Cr(OH)3] attested to the reduction capability of Cyanidiales. The distribution of Cr species varied as a function of sorbed Cr amount, yet a relatively consistent proportion of Cr(OH)3, irrespective of Cr sorption capacity, was found only on Cm and Cc at pH 2.0. In conjunction with TXM (transmission X-ray microscopy) images that showed less impaired cell integrity and possible intracellular Cr distribution on Cm and Cc at pH 2.0, the in vivo Cr(OH)3 might be the key to promoting the Cr sorption capacity (≥ 152 mg g-1). Cyanidiales are promising candidates for the green and sustainable remediation of Cr(VI) due to their great removal capacity, the spontaneous reduction under oxic conditions, and in vivo accumulation.

Phosphate Removal in Relation to Structural Development of Humic Acid-Iron Coprecipitates.

Precipitation of Fe-hydroxide (FH) critically influences the sequestration of PO4 and organic matter (OM). While coatings of pre-sorbed OM block FH surfaces and decrease the PO4 adsorption capacity, little is known about how OM/Fe coprecipitation influences the PO4 adsorption. We aimed to determine the PO4 adsorption behaviors on humic acid (HA)-Fe coprecipitates in relation to surface and structural characteristics as affected by HA types and C/(C + Fe) ratios using the Fe and P X-ray absorption spectroscopy. With increasing C/(C + Fe) ratios, the indiscernible changes in the proportion of near-surface C for coprecipitates containing HA enriched in polar functional groups implied a relatively homogeneous distribution between C and Fe domains. Wherein PO4 adsorbed on FH dominated the P inventory on coprecipitates, yielding PO4 sorption properties nearly equivalent to that of pure FH. Structural disruptions of FH caused by highly associations with polar functional groups of HA enhanced the C solubilisation. While polar functional groups were limited, coprecipitates consisted of core FH with surface outgrowth of HA. Although surface-attached HA that was vulnerable to solubilisation provided alternatively sites for PO4 via ternary complex formation with Fe bridges, it also blocked FH surfaces, leading to a decrease in PO4 adsorption.

Capacity and recycling of polyoxometalate applied in As(III) oxidation by Fe(II)-Amended zero-valent aluminum.

Arsenic remediation is often initiated by oxidizing As(III) to As(V) to alleviate its toxicity and mobility. Due to the easy availability, zero-valent Al (ZVAl) like Al can was considered as potential alternatives to facilitate As(III) oxidation. This study determined the capability and recycling of polyoxometalate (POM) to catalyze As(III) oxidation in Fe(II)-amended ZVAl systems. POM acquired electrons from ZVAl more effectively at pH 1 than at pH 2. While 76% of the reduced POM [POM(e-)] reacted with O2(g) to generate H2O2 at pH 1, only 60% of POM(e-) was used to produce H2O2 at pH 2. The remaining POM(e-) was oxidized by the generated H2O2. Such additional consumption of POM(e-) and H2O2 led to the incomplete As(III) oxidation in the system without residual ZVAl and emphasized the need for a continuous electron supply from ZVAl to compensate the depletion of POM(e-). After the hydrolyzation at pH 6.0, the XANES data evidenced that not only As(V) but WO4 released from the POM retained on surfaces of Al/Fe hydroxides. The competition for sorption sites on Al/Fe hydroxides between As(V) and WO4 led to the incomplete As removal. Despite the loss of WO4, the POM re-polymerized at pH 1 still showed the comparable capability to catalyze As(III) oxidation with original POM. This study revealed electron transfer pathways from ZVAl to As(III) as catalyzed by POM and evidenced the effective POM recycling after As removal, which lowers the cost of POM application and turns the ZVAl/Fe(II)/POM/O2 system into a practical strategy for As remediation.