Optimizing Typha biochar with phosphoric acid modification and ferric chloride impregnation for hexavalent chromium remediation in water and soil.

Considering the persistent and covert nature of heavy metal soil contamination, the sustainable development of ecological environments and food safety is at significant risk. Our study focuses on remediating soils contaminated with chromium (Cr); we introduce an advanced remediation material, iron oxide phosphoric acid-loaded activated biochar (HFBC), synthesized through pyrolysis. This HFBC displays greater microporosity, fewer impurities, and enhanced efficiency for the remediation process. Our research utilized a comprehensive set of analytical techniques, including Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS), alongside adsorption studies to elucidate the Cr removal mechanism. The effectiveness of HFBC in remediation was influenced by several factors: the pH level, dosage of HFBC, the initial concentration of Cr, and the ambient temperature. Our results indicated an optimal chromium (VI) adsorption capacity of 55.5 mg/g by HFBC at a pH of 6.0 and a temperature of 25 °C, with the process adhering to the pseudo-second-order kinetic model and the Langmuir adsorption isotherm, thus suggesting spontaneity in the uptake method. Moreover, this mechanism encompasses both adsorption and reduction reactions. Using HFBC in pot experiments with cabbage indicated not only an increase in soil pH and cation exchange capacity (CEC), but also a surge in bacterial community abundance. Significant reductions in bioavailable chromium were also recorded. Interestingly, HFBC addition bolstered the growth of cabbage, while concurrently diminishing chromium accumulation within the plant, particularly notable as the HFBC application rate increased. In summation, the HFBC produced in our study has demonstrated convincing efficacy in removing chromium from aqueous solutions and soil. Moreover, the positive agronomic implications of its use, such as enhanced plant growth and reduced heavy metal uptake by plants, indicate its high potential for operational value in the domain of environmental remediation of heavy metals.

Genome analysis of Shewanella putrefaciens 4H revealing the potential mechanisms for the chromium remediation.

Microbial remediation of heavy metal polluted environment is ecofriendly and cost effective. Therefore, in the present study, Shewanella putrefaciens stain 4H was previously isolated by our group from the activated sludge of secondary sedimentation tank in a dyeing wastewater treatment plant. The bacterium was able to reduce chromate effectively. The strains showed significant ability to reduce Cr(VI) in the pH range of 8.0 to 10.0 (optimum pH 9.0) and 25-42 ℃ (optimum 30 ℃) and were able to reduce 300 mg/L of Cr(VI) in 72 h under parthenogenetic anaerobic conditions. In this paper, the complete genome sequence was obtained by Nanopore sequencing technology and analyzed chromium metabolism-related genes by comparative genomics The genomic sequence of S. putrefaciens 4H has a length of 4,631,110 bp with a G + C content of 44.66% and contains 4015 protein-coding genes and 3223,  2414, 2343 genes were correspondingly annotated into the COG, KEGG, and GO databases. The qRT-PCR analysis showed that the expression of chrA, mtrC, and undA genes was up-regulated under Cr(VI) stress. This study explores the Chromium Metabolism-Related Genes of S. putrefaciens 4H and will help to deepen our understanding of the mechanisms of Cr(VI) tolerance and reduction in this strain, thus contributing to the better application of S. putrefaciens 4H in the field of remediation of chromium-contaminated environments.

Cr(VI) removal from wastewater using nano zero-valent iron and chromium-reducing bacteria.

Significant global efforts are currently underway to alleviate the presence of toxic metals in water bodies, aiming to encourage a sustainable environment. Nevertheless, the scientific community has yet to methodically inspect the performance and mechanisms underlying the interaction between nanomaterials and microorganisms in this context. Therefore, this study seeks to address this knowledge gap by developing a novel system that integrates nano zero-valent iron (nZVI) with chromium-reducing bacteria (CrRB) to efficiently remove Cr(VI) from water sources. The combined use of RBC600 and CrRB resulted in a Cr(VI) removal rate of 77.73%, displaying a substantial improvement of 17.61% compared to the use of CrRB alone. The efficacy of Cr(VI) elimination was observed to be affected by several factors within the system, such as the pH value, the quantity of nZVI added, the degree of CrRB inoculation, and the initial concentration of Cr(VI) at the onset of the experiment. When the pH was adjusted to 5, the complete removal of 200 mg/L Cr(VI) was achieved within 36 h. Increasing the dosage of nZVI to above 2 g/L resulted in the complete elimination of Cr(VI) from the solution within 72 h. This can be attributed to the availability of more reaction sites for the reduction of Cr(VI), facilitated by the higher nZVI dose. Additionally, the increased dose of nZVI allowed for the dissolution of more reactive Fe(II) ions. The characterization analysis, high-throughput sequencing, and fluorescence quantitative PCR results have established that CrRB and its extracellular polymer effectively reduce and complex Cr(VI). This process facilitated the dissolution of the passivated layer on the surface of nZVI, thus significantly enhancing the efficiency of nZVI in responding to Cr(VI). Additionally, the presence of nZVI created a favorable living environment for CrRB, resulting in increased richness and diversity within the CrRB community. These findings provide valuable preliminary insights into the mechanism underlying Cr(VI) elimination by the synergistic interaction between nZVI and CrRB. Therefore, this study establishes a solid theoretical foundations for the application of nano-bio synergy in the remediation of Cr(VI).

Efficient removal of Cr(VI) and As(V) from an aquatic system using iron oxide supported typha biochar.

The removal of Cr(VI) and As(V) from aqueous solutions has been a worldwide concern. In this study, Typha biochar (FBC) with magnetic iron oxide was prepared by impregnating Typha with FeCl3 and performing pyrolysis, and the possible mechanism of Cr(VI) and As(V) removal was investigated by combining characterization means and adsorption experiments. The results showed that the modified Typha biochar is rich in pores and has the potential to eliminate Cr and As through processes such as exchange and reduction. The single molecule uptake capacities of FBC for Cr(VI) and As(V) were 32.82 and 21.56 mg g-1, respectively. The adsorption process is spontaneous heat absorption, and the adsorption results are also consistent with the proposed secondary kinetic model. FBC still had >60% removal efficiency in the second and third reuse of Cr(VI), indicating its good recyclability. Therefore, this study confirms that FBC can effectively remove both Cr(VI) and As(V).

Enzyme activities and organic matter mineralization in response to application of gypsum, manure and rice straw in saline and sodic soils.

Saline and alkaline soils are a challenge for sustainable crop production. The use of organic and inorganic amendments is a common practice to increase the fertility of salt-affected soils that can trigger faster carbon (C) and nitrogen (N) cycling. We examined the effects of gypsum (Gyps), farm manure (Manure) and rice straw (Straw) on enzyme activities, organic matter mineralization and CO2 emissions in two salt-affected soils [Solonchak (saline); pH: 8, electrical conductivity (EC): 6.5, sodium adsorption ratio (SAR): 2.5, and Solonetz (alkaline sodic); pH: 8.9, EC: 1.6, SAR: 17]. Gypsum addition decreased soil pH up to 0.62 and 0.30 units, SAR 1.2 and 5.2 units, and EC 2.9 and 1.4 units in Solonchak and Solonetz, respectively. Dissolved organic C, microbial biomass C, dissolved organic N, mineral N (NO3- and NH4+), enzyme activities (urease, invertase, catalase, phosphatase, phenol-oxidase), alkali extractable phenols, and available phosphorous increased with the application of all amendments in both soils. Solonetz released more CO2 than Solonchak, whereas maximum CO2 emissions were common after manure application (3140 mg kg-1 in Solonchak, and 3890 mg kg-1 in Solonetz). We conclude that high SAR and low EC increase CO2 emissions through accelerated C and N cycling and manure decomposition in Solonetz soils.

Remediation of Cr(VI)-Contaminated Soil by Biochar-Supported Nanoscale Zero-Valent Iron and the Consequences for Indigenous Microbial Communities.

Biochar/nano-zero-valent iron (BC-nZVI) composites are currently of great interest as an efficient remediation material for contaminated soil, but their potential to remediate Cr-contaminated soils and effect on soil microecology is unclear. The purpose of this study was to investigate the effect of BC-nZVI composites on the removal of Cr(VI) from soil, and indigenous microbial diversity and community composition. The results showed that after 15 days of remediation with 10 g/kg of BC-nZVI, 86.55% of Cr(VI) was removed from the soil. The remediation of the Cr-contaminated soil with BC-nZVI resulted in a significant increase in OTUs and α-diversity index, and even a significant increase in the abundance and diversity of indigenous bacteria and unique bacterial species in the community by reducing the toxic concentration of Cr, changing soil properties, and providing habitat for survival. These results confirm that BC-nZVI is effective in removing Cr(VI) and stabilizing Cr in soil with no significant adverse effects on soil quality or soil microorganisms.

Impregnating biochar with Fe and Cu by bioleaching for fabricating catalyst to activate H2O2.

Biochar is an excellent support material for heterogeneous catalyst in Fenton reaction. However, fabrication of heterogeneous catalyst supported by biochar normally adopts chemical impregnation which is costly and difficult in post-treatment. Here, impregnation by bioleaching driven by Acidithiobacillus ferrooxidans was developed. Bioleaching was particularly effective in loading iron to biochar. Iron loading amount was 225.5 mg/g after 10-g biochar was treated in bioleaching containing 40-g FeSO4·7H2O for 60 h. When copper was added into bioleaching, simultaneous impregnation with iron and copper could be achieved. Impregnation mechanism for iron was jarosite formation on biochar surface and adsorption for copper. For the high metal content, after pyrolysis, the final composites could activate hydrogen peroxide to decolorize dye effectively. With 15 mg as-synthesized Cu-Fe@biochar containing 254.3 mg/g iron and 33.4 mg/g copper, 50 mg/L reactive red 3BS or methylene blue could be decolorized completely in 20 min in a 100-mL solution by 16-mM H2O2 at pH 2.5. Compared with existing impregnation methods, bioleaching was facile, cheap and green, and deserved more concern. KEY POINTS: • High amount of Fe is loaded to biochar uniformly as jarosite by bioleaching. • Cu is adsorbed onto biochar during bioleaching. • Synthesized Cu-Fe@biochar is an excellent photo-Fenton catalyst.

Synthesis, Crystal Structures and Urease Inhibition of 4-Bromo-N'-(1-(pyridin-2-yl)ethylidene)benzohydrazide and Its Dinuclear Copper(II) Complex.

A new dinuclear copper(II) complex [Cu2(µ-Br)2L2]·0.5MeOH with the benzohydrazone ligand 4-bromo-N'-(1-(pyridin-2-yl)ethylidene)benzohydrazide (HL) has been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopic studies. Single crystal structures of the complex and the benzohydrazone compound were studied. The Cu atoms in the complex are coordinated by two benzohydrazone ligands and two Br bridging groups, forming square pyramidal coordination. The complex has good inhibitory activity on Jack bean urease, with IC50 value of 1.38 µmol·L-1.

Efficient Removal of Hexavalent Chromium from an Aquatic System Using Nanoscale Zero-Valent Iron Supported by Ramie Biochar.

In this study, ramie biochar (RBC) was used to activate nano zero-valent iron (nZVI) to enhance hexavalent chromium (Cr(VI)) removal. The best results were obtained at a pyrolysis temperature of 600 °C, a biochar particle size of < 150 µm, and an iron to carbon ratio = 1:1. Under the optimal conditions, the removal of Cr(VI) by RBC600-nZVI (98.69%) was much greater than that of RBC600 (12.42%) and nZVI (58.26%). Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) revealed that the reaction mechanism at the Fe and Cr interface was a multiple interaction mechanism with reduction dominated, adsorption, and co-precipitation simultaneously. The enhanced performance of RBC600-nZVI resulted from the effective dispersion of nZVI on the surface of RBC600, therefore increasing the adsorption activity sites. At the same time, RBC600 and nZVI exerted a synergistic influence on the composite structure, which jointly promoted the reduction reaction of Cr(VI) and removed more Cr(VI). This study shows that RBC-nZVI is a potentially valuable remediation material that not only provides a new idea for the utilization of ramie waste, but also effectively overcomes the limitations of nZVI, thus, achieving efficient and rapid remediation of Cr(VI).

Synthesis, X-Ray Crystal Structure of Oxidovanadium(V) Complex Derived from 4-Bromo-N’-(2-hydroxybenzylidene) benzohydrazide with Catalytic Epoxidation Property.

A new oxidovanadium(V) complex, [VOL(OCH3)(CH3OH)], where H2L = 4-bromo-N'-(2-hydroxybenzylidene)benzohydrazide, has been synthesized and fully characterized on the basis of CHN elemental analysis, FT-IR, UV-Vis, 1H and 13C NMR spectroscopy. Structures of the free hydrazone and the complex were further characterized by single crystal X-ray diffraction, which indicates that the V atom in the complex adopts octahedral coordination, and the hydrazone ligand behaves as a tridentate ligand. The catalytic epoxidation property of the complex was investigated.

N’-(2-Hydroxybenzylidene)-3-Methylbenzohydrazide and its Copper(II) Complex: Syntheses, Characterization, Crystal Structures and Biological Activity.

The hydrazone compound N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide (H2L) was prepared. With H2L and copper acetate a new copper complex [Cu(HL)(NCS)]·CH3OH was synthesized. Both the hydrazone and the copper complex were characterized by physico-chemical methods and single crystal X-ray diffraction techniques. The complex is a thiocyanato-coordinated copper(II) species. The Cu atom in the complex is in square planar geometry. The complex is a promising urease inhibitor.

Syntheses, Crystal Structures and Catalytic Property of Oxidovanadium(V) Complexes Derived from Tridentate Hydrazone Ligands.

Two new ethyl maltolato coordinated mononuclear oxidovanadium(V) complexes [VOLa(emt)]·DMF (1) and [VOLb(emt)] (2), where H2La = N'-(4-bromo-2-hydroxybenzylidene)-3-hydroxybenzohydrazide, H2Lb = N'-(4-bromo-2-hydroxybenzylidene)benzohydrazide, Hemt = ethyl maltol, have been synthesized and characterized on the basis of CHN elemental analysis, FT-IR and UV-Vis spectroscopy and powder XRD analysis. Structures of the complexes were further characterized by single crystal X-ray diffraction, which indicated that the V atoms in the complexes adopt octahedral coordination. The hydrazones behave as NOO tridentate ligands. The catalytic epoxidation properties on cyclooctene of the complexes were investigated.

Restoring effect of soil acidity and Cu on N2O emissions from an acidic soil.

Heavy metals are believed to impact soil processes by influencing microbial communities, nutrient cycling or exchanging for essential plant nutrients. Soil pH adjustment highly influences the bio-availability of nutrients and microbial processes. We examined the effect of soil pH manipulation and copper (Cu as CuCl2.2H2O) application on nitrogen (N) cycling and nitrous oxide (N2O) emissions from an acid soil. Increasing amounts of Cu (0, 250, 500 and 1000 mg kg-1) were added to an acidic soil (pH = 5.44) that was further amended with increasing amounts of dolomite [CaMg(CO3)2] to increase soil pH. Dolomite increased soil pH values, which reached a maximum without Cu application (-Cu) at day 42 of the experiment. The soil pH values decreased with increasing dose of Cu, and remained low as compared with both control and dolomite amended soil. Ammonium (NH4+-N) concentrations were higher in Cu contaminated soil as compared with the control and dolomite treated soil. Nitrate (NO3--N) concentrations increased in dolomite treated soil when compared with the +Cu alone treatments and control. Microbial biomass carbon (MBC) and nitrogen (MBN) contents were higher in dolomite treated soil as compared with the +Cu treatments and control. The application of increasing amounts of Cu progressively decreased soil MBC and MBN. Nitrous oxide emissions were higher (p ≤ 0.01) in +Cu soil as compared with the control, and increased with increasing Cu concentration in soil. Application of dolomite highly suppressed soil N2O emissions in both +Cu and -Cu soils. The results indicate that the effects of heavy metal contamination (specifically Cu contamination) can increase N2O emissions, but this can be effectively mitigated through increasing soil pH, also decreasing potential toxic effects on soil microorganisms.

Impacts of earthworm activity on the fate of straw carbon in soil: a microcosm experiment.

Earthworms not only facilitate carbon (C) stabilization, but also accelerate organic matter mineralization by enhancing microbial respiration. However, the fate (mineralization vs stabilization) of newly added C by straw returning in arable lands with earthworm activity is still unclear. In the present 40 days incubation study, we incorporated artificially 13C-labeled straw into soil with and without presence of earthworms (Metaphire guillelmi). Flux measurements of CO2 from soil (mineralization) were taken regularly, while straw-derived C remaining in the soil (stabilization) was measured at the end of the incubation. There was no significant difference of the cumulative CO2 emission between earthworm presence and absence treatment. However, earthworm presence significantly decreased straw-derived cumulative CO2-C emission when compared with the treatment without earthworm. Besides, earthworm incubation led to a significantly low light fraction organic carbon (LFOC) content and straw-derived LFOC proportion. Relative to the non-earthworm treatment, straw-derived C content significantly decreased in micro-aggregates (< 0.25 mm), but increased in large macro-aggregates (> 2 mm) in the earthworm treatment. In total, only 3.8% of added straw C was assimilated by earthworm within 40 days, while most of the straw C remained in the soil. Earthworms decreased straw-derived CO2-C emission from 10.0 to 8.1% when compared with the non-earthworm treatment. In the present short period incubation experiment, compared with the soil without earthworms, the presence of Metaphire guillelmi (1) resulted a higher soil CO2 emissions, which may mainly evolved from the older SOC, and (2) stabilized more residue-derived C in the soil aggregates. We therefore propose that Metaphire guillelmi may increase soil organic carbon pool turnover rates in the short term after straw returning by replacement of older SOC with newly added straw C.

Reduction in soil N2O emissions by pH manipulation and enhanced nosZ gene transcription under different water regimes.

Several studies have been carried out to examine nitrous oxide (N2O) emissions from agricultural soils in the past. However, the emissions of N2O particularly during amelioration of acidic soils have been rarely studied. We carried out the present study using a rice-rapeseed rotation soil (pH 5.44) that was amended with dolomite (0, 1 and 2 g kg-1 soil) under 60% water filled pore space (WFPS) and flooding. N2O emissions and several soil properties (pH, NH4+N, NO3--N, and nosZ gene transcripts) were measured throughout the study. The increase in soil pH with dolomite application triggered soil N transformation and transcripts of nosZ gene controlling N2O emissions under both water regimes (60% WFPS and flooding). The 60% WFPS produced higher soil N2O emissions than that of flooding, and dolomite largely reduced N2O emissions at higher pH under both water regimes through enhanced transcription of nosZ gene. The results suggest that ameliorating soil acidity with dolomite can substantially mitigate N2O emissions through promoting nosZ gene transcription.

Influence of ameliorating soil acidity with dolomite on the priming of soil C content and CO2 emission.

Lime or dolomite is commonly implemented to ameliorate soil acidity. However, the impact of dolomite on CO2 emissions from acidic soils is largely unknown. A 53-day laboratory study was carried out to investigate CO2 emissions by applying dolomite to an acidic Acrisol (rice-rapeseed rotation [RR soil]) and a Ferralsol (rice-fallow/flooded rotation [RF soil]). Dolomite was dosed at 0, 0.5, and 1.5 g 100 g-1 soil, herein referred to as CK, L, and H, respectively. The soil pH(H2O) increased from 5.25 to 7.03 and 7.62 in L and H treatments of the RR soil and from 5.52 to 7.27 and 7.77 in L and H treatments of the RF soil, respectively. Dolomite application significantly (p ≤ 0.001) increased CO2 emissions in both RR and RF soils, with higher emissions in H as compared to L dose of dolomite. The cumulative CO2 emissions with H dose of dolomite were greater 136% in the RR soil and 149% in the RF soil as compared to CK, respectively. Dissolved organic carbon (DOC) and microbial biomass carbon (MBC) increased and reached at 193 and 431 mg kg-1 in the RR soil and 244 and 481 mg kg-1 in the RF soil by H treatments. The NH4--N and NO3--N were also increased by dolomite application. The increase in C and N contents stimulated microbial activities and therefore higher respiration in dolomite-treated soil as compared to untreated. The results suggest that CO2 release in dolomite-treated soils was due to the priming of soil C content rather than chemical reactions.

Effects of dicyandiamide and dolomite application on N2O emission from an acidic soil.

Soil acidification is a major problem for sustainable agriculture since it limits productivity of several crops. Liming is usually adopted to ameliorate soil acidity that can trigger soil processes such as nitrification, denitrification, and loss of nitrogen (N) as nitrous oxide (N2O) emissions. The loss of N following liming of acidic soils can be controlled by nitrification inhibitors (such as dicyandiamide). However, effects of nitrification inhibitors following liming of acidic soils are not well understood so far. Here, we conducted a laboratory study using an acidic soil to examine the effects of dolomite and dicyandiamide (DCD) application on N2O emissions. Three levels of DCD (0, 10, and 20 mg kg(-1); DCD0, DCD10, and DCD20, respectively) were applied to the acidic soil under two levels of dolomite (0 and 1 g kg(-1)) which were further treated with two levels of N fertilizer (0 and 200 mg N kg(-1)). Results showed that N2O emissions were highest at low soil pH levels in fertilizer-treated soil without application of DCD and dolomite. Application of DCD and dolomite significantly (P ≤ 0.001) reduced N2O emissions through decreasing rates of NH4 (+)-N oxidation and increasing soil pH, respectively. Total N2O emissions were reduced by 44 and 13% in DCD20 and dolomite alone treatments, respectively, while DCD20 + dolomite reduced N2O emissions by 54% when compared with DCD0 treatment. The present study suggests that application of DCD and dolomite to acidic soils can mitigate N2O emissions.

Dolomite application to acidic soils: a promising option for mitigating N2O emissions.

Soil acidification is one of the main problems to crop productivity as well as a potent source of atmospheric nitrous oxide (N2O). Liming practice is usually performed for the amelioration of acidic soils, but the effects of dolomite application on N2O emissions from acidic soils are still not well understood. Therefore, a laboratory study was conducted to examine N2O emissions from an acidic soil following application of dolomite. Dolomite was applied to acidic soil in a factorial design under different levels of moisture and nitrogen (N) fertilizer. Treatments were as follows: dolomite was applied as 0, 1, and 2 g kg(-1) soil (named as CK, L, and H, respectively) under two levels of moisture [i.e., 55 and 90 % water-filled pore space (WFPS)]. All treatments of dolomite and moisture were further amended with 0 and 200 mg N kg(-1) soil as (NH4)2SO4. Soil properties such as soil pH, mineral N (NH4 (+)-N and NO3 (-)-N), microbial biomass carbon (MBC), dissolved organic carbon (DOC), and soil N2O emissions were analyzed throughout the study period. Application of N fertilizer rapidly increased soil N2O emissions and peaked at 0.59 µg N2O-N kg(-1) h(-1) under 90 % WFPS without dolomite application. The highest cumulative N2O flux was 246.32 µg N2O-N kg(-1) under 90 % WFPS without dolomite addition in fertilized soil. Addition of dolomite significantly (p ≤ 0.01) mitigated N2O emissions as soil pH increased, and H treatment was more effective for mitigating N2O emissions as compared to L treatment. The H treatment decreased the cumulative N2O emissions by up to 73 and 67 % under 55 and 90 % WFPS, respectively, in fertilized soil, and 60 and 68 % under 55 and 90 % WFPS, respectively, in unfertilized soil when compared to those without dolomite addition. Results demonstrated that application of dolomite to acidic soils is a promising option for mitigating N2O emissions.