Cr(VI) Reduction and Fe(II) Regeneration by Penicillium oxalicum SL2-Enhanced Nanoscale Zero-Valent Iron.

Nanoscale zero-valent iron (nZVI) faces significant challenges in Cr(VI) remediation through aggregation and passivation. This study identified a Cr(VI)-resistant filamentous fungus (Penicillium oxalicum SL2) for nZVI activation and elucidated the synergistic mechanism in chromium remediation. P. oxalicum SL2 and nZVI synergistically and effectively removed Cr(VI), mainly by extracellular nonenzymatic reduction (89.1%). P. oxalicum SL2 exhibited marked iron precipitate solubilization and Fe(II) regeneration capabilities. The existence of the Fe(II)-Cr(V)-oxalate complex (HCrFeC4O9) indicated that in addition to directly reducing Cr(VI), iron ions generated by nZVI stimulated Cr(VI) reduction by organic acids secreted by P. oxalicum SL2. RNA sequencing and bioinformatics analysis revealed that P. oxalicum SL2 inhibited phosphate transport channels to suppress Cr(VI) transport, facilitated iron and siderophore transport to store Fe, activated the glyoxylate cycle to survive harsh environments, and enhanced organic acid and riboflavin secretion to reduce Cr(VI). Cr(VI) exposure also stimulated the antioxidative system, promoting catalase activity and maintaining the intracellular thiol/disulfide balance. Cr(VI)/Fe(III) reductases played crucial roles in the intracellular reduction of chromium and iron, while nZVI decreased cellular oxidative stress and alleviated Cr(VI) toxicity to P. oxalicum SL2. Overall, the P. oxalicum SL2-nZVI synergistic system is a promising approach for regenerating Fe(II) while reducing Cr(VI).

Overestimate of remediation efficiency due to residual sodium persulfate in PAHs contaminated soil and a solution.

Oxidation remediation is a commonly used technology for PAHs contaminated soil presently, but the overestimate of efficiency due to ongoing remediation by residual oxidants during extraction and testing has not been paid enough attention. In this study, persulfate was activated by Fe(II) to investigate the effects of residual oxidants on PAHs removal during detection process and the elimination effects of adding Na2SO3 and extending sampling time on residual oxidants. Results verified that the residual oxidants removed PAHs in extraction process, making the results lower than the actual values: the detection recovery rate η of ∑PAHs and 3-6 ring PAHs ranged from 24.3% (25% Na2S2O8 treatment) to 87.4% (5% Na2S2O8+4/4Fe2+ treatment), 20.1%-99.0%, 28.9%-87.9%, 20.8%-89.4%, and 18.6%-76.9%, respectively. After adding Na2SO3, the accuracy of detection results increased significantly: the η of ∑PAHs and 3-6 ring PAHs increased to 64.1%-96.5%, 58.8%-95.5%, 73.8%-114.4%, 60.6%-95.6%, and 45.4%-77.1%, respectively. After 49 days of adding oxidants, residual oxidants had no considerable effect on the detection of PAHs, indicating it was appropriate to start soil remediation verification sampling49 days after the remediation was completed. The observed results will help scientific evaluation of the remediation effects of chemical oxidation on organic contaminated soil.

The colonization of Penicillium oxalicum SL2 on rice root surface increased Pb interception capacity of iron plaque and decreased Pb uptake by roots.

The exploration of microbial resources to reduce Pb accumulation in rice attracted great attention. In this study, we found Penicillium oxalicum SL2, a Pb-tolerant strain with good capability of dissolving phosphorus and stabilizing Pb in soil, was able to colonize on the root surface of rice seedlings without additional carbon sources, and promoted the secretion of metabolites related to amino acid metabolism, organic acid metabolism, signal transduction and other pathways in rhizosphere exudates, in which the secretion of oxalate increased by 47.7 %. However, P. oxalicum SL2 increased Fe(II) proportion and Fe availability on the root surface, resulting in iron plaque content decrease. Moreover, by converting root surface Pb from Pb-Fe state to PbC2O4 and Pb-P compounds, P. oxalicum SL2 increased Pb intercept capacity of iron plaque by 118.0 %. Furthermore, P. oxalicum SL2 regulated element distribution on the root surface, and reduced the relative content of Pb on the maturation zone of root tip, which was conducive to reducing Pb uptake by apoplastic pathway and the risk of Pb accumulation in root system. Our findings further revealed the interaction between P. oxalicum SL2 and rice root, providing a theoretical basis for the development and application of microbial agents in Pb-contaminated farmland.

More effective than direct contact: Nano hydroxyapatite pre-treatment regulates the growth and Cd uptake of rice (Oryza sativa L.) seedlings.

Cd contamination in rice urgently needs to be addressed. Nano hydroxyapatite (n-HAP) is an eco-friendly material with excellent Cd fixation ability. However, due to its own high reactivity, innovative application of n-HAP in the treatment of Cd contamination in rice is needed. In this study, we proposed a new application, namely n-HAP pre-treatment, which can effectively reduce Cd accumulation in rice and alleviate Cd stress. The results showed that 80 mg/L n-HAP pre-treatment significantly reduced Cd content in rice shoot by 35.1%. Biochemical and combined transcriptomic-proteomic analysis revealed the possible molecular mechanisms by which n-HAP pre-treatment promoted rice growth and reduced Cd accumulation. (1) n-HAP pre-treatment regulated gibberellin and jasmonic acid synthesis-related pathways, increased gibberellin content and decreased jasmonic acid content in rice root, which promoted rice growth; (2) n-HAP pre-treatment up-regulated gene CATA1 expression and down-regulated gene OsGpx1 expression, which increased rice CAT activity and GSH content; (3) n-HAP pre-treatment up-regulated gene OsZIP1 expression and down-regulated gene OsNramp1 expression, which reduced Cd uptake, increased Cd efflux from rice root cells.

Penicillium oxalicum SL2-enhanced nanoscale zero-valent iron effectively reduces Cr(VI) and shifts soil microbiota.

Most current researches focus solely on reducing soil chromium availability. It is difficult to reduce soil Cr(VI) concentration below 5.0 mg kg-1 using single remediation technology. This study introduced a sustainable soil Cr(VI) reduction and stabilization system, Penicillium oxalicum SL2-nanoscale zero-valent iron (nZVI), and investigated its effect on Cr(VI) reduction efficiency and microbial ecology. Results showed that P. oxalicum SL2-nZVI effectively reduced soil total Cr(VI) concentration from 187.1 to 3.4 mg kg-1 within 180 d, and remained relatively stable at 360 d. The growth curve of P. oxalicum SL2 and microbial community results indicated that γ-ray irradiation shortened the adaptation time of P. oxalicum SL2 and facilitated its colonization in soil. P. oxalicum SL2 colonization activated nZVI and its derivatives, and increased soil iron bioavailability. After restoration, the negative effect of Cr(VI) on soil microorganisms was markedly alleviated. Cr(VI), Fe(II), bioavailable Cr/Fe, Eh, EC and urease (SUE) were the key environmental factors of soil microbiota. Notably, Penicillium significantly stimulated the growth of urease-positive bacteria, Arthrobacter, Pseudarthrobacter, and Microvirga, synergistically reducing soil chromium availability. The combination of P. oxalicum SL2 and nZVI is expected to form a green, economical and long-lasting Cr(VI) reduction stabilization strategy.

Fe-biochar for simultaneous stabilization of chromium and arsenic in soil: Rational design and long-term performance.

Excess chromium (Cr) and arsenic (As) coexist in soil such as chromated copper arsenate (CCA) contaminated sites, leading to high risks of pollution. Fe-biochar with adjustable redox activity offers the possibility of simultaneous stabilization of Cr and As. Here, a series of Fe-biochar with distinct Fe/C structure were rationally produced for the remediation of Cr and As contaminated soil (BCX-Fe, X represented the biomass/Fe ratio). Adsorption tests showed that maximal adsorption of BC5-Fe for Cr(VI) and As(III) reached 73.7 and 81.3 mg/g. A 90-day soil remediation experiment indicated that the introduction of 3% (w/w) Fe-biochar reduced the leaching state of Cr(VI) by 93.8-99.7% and As by 75.2-95.6%. Under simulated groundwater erosion for 10 years and acid rain leaching for 7.5 years, the release levels of Cr(VI) and As in the BC5-Fe remediated soil could meet the groundwater class IV standard in China (Cr(VI)<0.1 mg/L, As<0.05 mg/L). Accelerated aging tests demonstrated that BC5-Fe had long-term Cr and As stabilization ability. The quenching experiment, EPR, and XPS suggested that the corrosion products of Fe dominated the adsorption and redox reactions, while the O groups acted as electron transfer stations and constituted redox microcirculation in the synchronous uptake of Cr/As. Based on these insights, we believe that our study will provide meaningful information about the application potential of Fe-biochar for the heavy metal contaminated soil remediation.

Toluene-mercuric modified USEPA Method 3060A to eliminate interference of sulfide-based reductants with Cr(VI) determination.

The validity of USEPA Method 3060A as universal Cr(VI) analysis method for remediated soil is controversial. We investigated soil Cr(VI) remediation performance by commonly used reductants (FeSO4, CaSx, Na2S) under different operating conditions (dosage, curing time and degree of mixing) using Method 3060A, and developed modified 3060A specific for sulfide-based reductants. Results showed that Cr(VI) was primarily removed during analysis stage rather than remediation stage. Thereinto, chemical dosage played a much more important role than curing time and degree of mixing. Besides, soil Cr(VI) concentration decreased to below the detection limit with residual reductant content increasing. Comparing standard and toluene-mercuric modified 3060A, Cr(VI) removal efficiency decreased from 100 % to 38.9-45.4 %, 67.1-68.8 % and 94.1-96.3 %, corresponding to mixing degree of 33 %, 67 % and 100 %, for treated soil using 1× and 2× the molar stoichiometric ratio of CaSx. Subsequently, the optimization mechanism was revealed. Elemental sulfur, remediation product of sulfide-based reductants, was removed from soil by toluene preventing its disproportionation to sulfide at Method 3060A stage. Sulfide was fixed by mercuric oxide in species of mercuric sulfide. This method also proved suitable for different types of soils. Therefore, an effective way for scientific evaluation of soil Cr(VI) remediation was provided in this study.

Nano hydroxyapatite pre-treatment effectively reduces Cd accumulation in rice (Oryza sativa L.) and its impact on paddy microbial communities.

Cadmium (Cd) contamination in paddy soil has become a worldwide concern and severely endangered human health. Nano hydroxyapatite (n-HAP) is a practical material to manage paddy Cd pollution, but its dosage should not be excessive. Based on previous studies, we validated the effect of n-HAP pre-treatment on rice Cd uptake in pot and field experiments. The results indicated that n-HAP pre-treatment effectively restricted Cd translocation in the soil-rice system. In pot experiment, when soil n-HAP concentration was 5000 mg/kg, the Cd content in the grains of n-HAP pre-treated rice was 0.171 mg/kg, decreased by 29.3% compared with normal rice (0.242 mg/kg). In field experiment, when soil n-HAP concentration was 20,000 mg/kg, the Cd content in the grains of n-HAP pre-treated rice was 0.156 mg/kg, decreased by 35.3% compared with normal rice (0.241 mg/kg). The primary mechanism was that n-HAP pre-treatment altered the formation and composition of iron plaque and therefore enhanced the Cd binding ability of iron plaque. The available N and P content and urease activity in paddy field were increased. We further investigated the impact of n-HAP on the diversity and structure of paddy microbial communities. The Chao1 and Shannon diversity indices showed no significant difference. The relative abundance of Actinobacteria and Proteobacteria was significantly decreased by n-HAP, indicating that Cd pollution might be alleviated. Desulfobacterota, Gemmatimonadota, and Geobacteraceae were significantly enriched by n-HAP. The declining relative abundance of Basidiomycota and the increasing relative abundance of other fungal taxa also suggested that n-HAP could alleviate Cd toxicity in soil.

Synergy among extracellular adsorption, bio-precipitation and transmembrane transport of Penicillium oxalicum SL2 enhanced Pb stabilization.

As a potential bioremediation strain for Pb contamination, Penicillium oxalicum SL2 sometimes has secondary activation of Pb, so it is crucial to clarify its effect on Pb morphology and its intracellular response to Pb stress. We investigated the effect of P. oxalicum SL2 in medium on Pb2+ and Pb availability in eight minerals, and revealed the prioritization of Pb products. (i)Pb was stabilized within 30 days as Pb3(PO4)2 or Pb5(PO4)3Cl with sufficient phosphorus (P); (ii) under P deficiency but sulfur (S) sufficient, Pb was stabilized mainly in the form of PbSO4; (iii) under conditions of P and S deficiency, Pb was stabilized mainly in the form of PbC2O2. With the help of proteomic and metabolomics analysis, a total of 578 different proteins and 194 different metabolites were found to be matched in 52 pathways. Among them, the activation of chitin synthesis, oxalate production, sulfur metabolism and transporters improved the Pb tolerance of P. oxalicum SL2, and promoted the synergistic effect of extracellular adsorption, bio-precipitation and transmembrane transport on Pb stabilization. Our results fill the gap in the intracellular response of P. oxalicum SL2 to Pb and provide new insights into the development of bioremediation agent and technology for Pb contamination.

Long-term and high-bioavailable potentially toxic elements (PTEs) strongly influence the microbiota in electroplating sites.

Multiple potentially toxic elements (PTEs) wastes are produced in the process of electroplating, which pollute the surrounding soils. However, the priority pollutants and critical risk factors in electroplating sites are still unclear. Hence, a typical demolished electroplating site (operation for 31 years) in the Yangtze River Delta was investigated. Results showed that the soil was severely polluted by Cr(VI) (1711.3 mg kg-1), Ni (6754.0 mg kg-1) and Pb (2784.4 mg kg-1). The spatial distribution of soil PTEs performed by ArcGIS illustrated that the soil pollution varied with plating workshops. Hard Cr electroplating workshops (HCE), decorative Cr electroplating workshops (DCE) and sludge storage station (SS) were the hot spots in the site. Besides, the toxicity characteristic leaching procedure (TCLP) - extractable Cr and Ni contents in different workshops were significantly related (P < 0.05) to their bioavailable fractions (exchangeable fraction (F1) + bound to carbonate fraction (F2)), which pose potential risk to humans. Although the soil total Pb concentration was high, its mobility was very low (<0.007%). Moreover, the soil microbial community dynamics under the stress of long term and high contents of PTEs were further revealed. The soil microbiota was significantly disturbed by long term and high concentration of PTEs. A bit of bacteria (Caulobacter) and fungi (Cladosporium and Monocillium) showed tolerance potential to multiple metals. Furthermore, the canonical correspondence analysis (CCA) showed that the bioavailable fractions (F1 + F2) of Cr and Ni were the most critical environmental variables affecting microbiota. Therefore, remediation strategies are required urgently to reduce the bioavailability of soil Cr and Ni. The results of this study provide an overview of the pollution distribution and microbial dynamics of a typical plating site, laying a foundation for ecological remediation of electroplating sites in Yangtze River Delta of China.

Derivation of empirical model to predict the accumulation of Pb in rice grain.

Lead contamination in soil has become a worldwide threat on food security and human health. To assess the Pb bioavailability and evaluate the safe use of low Pb polluted soil for food production, the speciation of Pb in 19 types of paddy soil were investigated by chemical extraction and X-ray absorption near-edge structure (XANES), and the uptake and accumulation characteristics of Pb in different soil-rice systems were investigated. Moreover, an empirical model was established to predict the content of Pb in rice grain, and field validation was conduct to evaluate model performance. Results showed that the proportion of available Pb in different soil satisfied normal distribution N (0.47, 0.23). Pb(CH3COO)2, GSH-Pb, PbO, PbHPO4 and Pb3(PO4)2 performed well in characterizing the speciation of Pb in different rhizosphere soils, and PbHPO4 accounted for more than 70%. The exceedance of Pb in grain in CK, 0.5X and 1X treatment were 10.5%, 36.1% and 42.1%, respectively, and the accumulation of Pb in grain was significantly related with Pb content in root. Carbonate and organic bound Pb in rhizosphere soil were two major Pb species that influenced the accumulation of Pb in rice. Moreover, content of total Pb, clay and SOM performed well in predicting the Pb content in grain, both for pot and field samples. Above all, our predicting model worked well in evaluating Pb accumulation in rice grain among low polluted paddy farmland (Total Pb < 300 mg/kg).

Simultaneous removal of multiple heavy metals from soil by washing with citric acid and ferric chloride.

The remediation of soil contaminated with multiple heavy metals is a matter of great concern due to its serious threat to the ecosystem and human health. Batch and slurry reactor soil washing experiments were conducted to explore the removal of Cd, Cr, Pb and Zn using 7 agents. Citric acid (CA) and ferric chloride (FeCl3) exhibited an obvious synergistic effect on the removal of heavy metals. Furthermore, the concentration of heavy metals in different soil particle size fractions was closely related to the soil element concentrations. Fine sand (0.05-0.25 mm) had a strong adsorption capacity for Cr and Pb because of the high Mn concentration. Notably, heavy metals in smaller-size soil particles could be efficiently removed by CA and FeCl3. After remediation, the bioavailability of heavy metals in soil decreased. The potential ecological risk of heavy metals in soil reduced from an extremely high level to a low level. Moreover, some elements (e.g. Al, Mn and Fe) and organic matter in soil were dissolved by CA and FeCl3, which accelerated the desorption of heavy metals from the soil. In a slurry reactor experiment, the removal efficiencies of Cd, Cr, Pb and Zn were 94.8%, 79.5%, 92.7% and 97.2%, respectively. The combination of CA and FeCl3 is a feasible practice to remediate soil contaminated by multiple heavy metals.

Ca2+ and SO42- accelerate the reduction of Cr(VI) by Penicillium oxalicum SL2.

Some ions in soils may affect the growth and metabolism of microorganisms and subsequently alter the remediation efficiency of Cr(VI). Here, the effects of different Ca2+ and SO42- levels on the reduction of Cr(VI) by Penicillium oxalicum SL2 were investigated. The results showed that Cr(VI) reduction by P. oxalicum SL2 in potato dextrose liquid (PDL) medium was accelerated by the presence of exogenous Ca2+ and SO42-. The Cr(VI) reduction rates were increased by 52.5% (200 mg L-1 Ca2+ treated) and 55.9% (2000 mg L-1 SO42- treated), respectively. High concentration of Ca2+ in medium resulted in the production of calcium oxalate crystals, which was contributed to the adsorption of chromium. In addition, X-ray absorption near-edge spectroscopy (XANES) analysis showed that P. oxalicum SL2 could reduce the toxicity of Cr(VI) by synthesizing cysteine (Cys) and reduced glutathione (GSH). The decrease of thiol compounds (Cys and GSH) in P. oxalicum SL2 mycelia treated with SO42- proved the alleviation of oxidative stress. In conclusion, exogenous Ca2+ could reduce the damage of Cr(VI) to P. oxalicum SL2 by maintaining the integrity of cell wall, and the addition of SO42- alleviated the Cr(VI) toxicity to P. oxalicum SL2, thus accelerating the reduction of Cr(VI).