Defluorination of perfluorooctanoic acid and perfluorooctane sulfonic acid by heterogeneous catalytic system of Fe-Al2O3/O3: Synergistic oxidation effects and defluorination mechanism.

In this study, catalytic ozonation by Fe-Al2O3 was used to investigate the defluorination of PFOA and PFOS, assessing the effects of different experimental conditions on the defluorination efficiency of the system. The oxidation mechanism of the Fe-Al2O3/O3 system and the specific degradation and defluorination mechanisms for PFOA and PFOS were determined. Results showed that compared to the single O3 system, the defluorination rates of PFOA and PFOS increased by 2.32- and 5.92-fold using the Fe-Al2O3/O3 system under optimal experimental conditions. Mechanistic analysis indicated that in Fe-Al2O3, the variable valence iron (Fe) and functional groups containing C and O served as important reaction sites during the catalytic process. The co-existence of 1O2, OH, O2- and high-valence Fe(IV) constituted a synergistic oxidation system consisting of free radicals and non-radicals, promoting the degradation and defluorination of PFOA and PFOS. DFT theoretical calculations and the analysis of intermediate degradation products suggested that the degradation pathways of PFOA and PFOS involved Kolbe decarboxylation, desulfonation, alcoholization and intramolecular cyclization reactions. The degradation and defluorination pathways of PFOA and PFOS consisted of the stepwise removal of -CF2-, with PFOS exhibiting a higher defluorination rate than PFOA due to its susceptibility to electrophilic attack. This study provides a theoretical basis for the development of heterogeneous catalytic ozonation systems for PFOA and PFOS treatment.

High-efficiency treatment of electroless nickel plating effluent using core-shell MnFe2O4-C@Al2O3 combined with ozonation: Performance and mechanism.

Heterogeneous catalytic ozonation (HCO) has been widely applied for the treatment of wastewater. In order to maintain the structural stability and surface catalytic activity of heterogeneous catalysts during the HCO treatment of electroless nickel plating effluent (ENPE), a MnFe2O4-C@Al2O3 catalyst with a core-shell structure was synthesized. MnFe2O4-C@Al2O3 was characterized and applied in the removal of total nickel (TNi) and organic contaminants from actual ENPE, using a coupled system of HCO combined with a magnetic dithiocarbamate chelating resin (MnFe2O4-C@Al2O3/O3-MDCR). Results show that embedding Al2O3 with C and MnFe2O4 significantly increased the TNi removal efficiency (99.3%), enhanced the O3-utilization efficiency and improved the generation of reactive oxygen species (ROS). The reaction rate (k = 0.7641 min-1) and O3-utilization efficiency established for TNi removal (ΔTNi/ΔO3 =0.221) by the MnFe2O4-C@Al2O3/O3-MDCR system, were 220% and 140% higher than the Al2O3/O3-MDCR system, respectively. Catalytic mechanism analysis demonstrated that surface hydroxyl groups, oxygen vacancy, metals, the carbon surface and its functional groups, can all potentially serve as catalytic active sites, with 1O2 and •OH considered to the predominant ROS. Overall, these findings verify that the synthesized MnFe2O4-C@Al2O3 catalyst possesses excellent catalytic capabilities and outstanding structural stability, making it suitable for practical application in the treatment of wastewater effluent.

Feasibility of reduced iron species for promoting Li and Co recovery from spent LiCoO2 batteries using a mixed-culture bioleaching process.

The recovery of metals from spent LiCoO2 batteries (SLBs) is essential to avoid resource wastage and the production of hazardous waste. However, the major challenge in regard to recovering metals from SLBs using traditional bioleaching is the low Co yield. To overcome this issue, a mixed culture of Acidithiobacillus caldus and Sulfobacillus thermosulfidooxidans was designed for use in SLBs leaching in this study. With the assistance of Fe2+ as a reductant, 99% of Co and 100% of Li were leached using the above mixed-culture bioleaching (MCB) process, thus solving the problem of low metal leaching efficiency from SLBs. Analysis of the underlying mechanism revealed that the effective extraction of metals from SLBs by the Fe2+-MCB process relied on Fe2+-releasing electrons to reduce refractory Co(III) to Co(II) that can be easily bioleached. Finally, the hazardous SLBs was transformed into a non-toxic material after treatment utilizing the Fe2+-MCB process. However, effective SLBs leaching was not achieved by the addition of Fe0 to the MCB system. Only 25% Co and 31% Li yields were obtained, as the addition of Fe0 caused acid consumption and bacterial apoptosis. Overall, this study revealed that reductants that cause acid consumption and harm bacteria should be ruled out for use in reductant-assisted bioleaching processes for extracting metals from SLBs.

A designed moderately thermophilic consortia with a better performance for leaching high grade fine lead-zinc sulfide ore.

Unwieldy fine sulfide ores are produced during mining; without being appropriately disposed of, they can cause environmental pollution and waste resources. This study investigated the leaching performance of a moderately thermophilic consortia (Leptospirillum ferriphilum + Acidithiobacillus caldus + Sulfobacillus benefaciens) for fine lead-zinc sulfide raw ore. The results showed this microbial community created a low pH, high ORP, and high cell concentration environment for mineral leaching, improving bioleaching efficiency. Under the action of this consortia, the zinc leaching rate reached 96.44 in 8 days, and reached 100% after 12 days. EPS analysis indicated that the consortia could mediate the secretion of more polysaccharides to ensure leaching efficiency. EPS levels and amino acids were the main factors affecting bioleaching. An analysis of mineral surface characteristics showed the consortia effectively leached pyrite and sphalerite from the fine sulfide ore, and prevented the mineral surface forming the jarosite that could hinder bioleaching. This study found that bioleaching reduced the potential environmental toxicity of the minerals, providing an important reference for guiding the bioleaching of unwieldy fine sulfide raw ore.

Effect of diurnal temperature range on bioleaching of sulfide ore by an artificial microbial consortium.

Temperature is considered to be one of the main factors affecting bioleaching, but few studies have assessed the effects of diurnal temperature range (DTR) on the bioleaching process. This study investigates the effects of different bioleaching temperatures (30 and 40 °C) and DTR on the bioleaching of metal sulfide ores by microbial communities. The results showed that DTR had an obvious inhibitory effect on the bioleaching efficiency of the artificial microbial community, although this effect was mainly concentrated in the early and middle stages (0-18 days) of exposure, gradually decreasing until almost disappearing in the late stage (18-24 days). Extracellular polymeric substance (EPS) analysis showed that DTR did not change the composition of the EPS matrix (humic acid-like substances, polysaccharides and protein-like substances), but had a significant effect on the generative behavior of EPS, inhibiting the secretion of EPS during the early and middle stages of the bioleaching process. However, the continual increase in EPS secretion in the bioleaching system gradually reduced the adverse effects of DTR on mineral dissolution. X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Scanning electron microscopy- energy dispersive spectrometry (SEM-EDS) analysis of the bioleached residue showed that DTR had no obvious effect on the mineralogical characteristics of sulfide ore. Therefore, in industrial sulfide ore bioleaching applications, in order to accelerate the artificial microbial community start-up process, temperature control measures should be increased in the bioleaching process to reduce the adverse effects of DTR on mineral dissolution.

Detection and Phylogenetic Analysis of a Novel Tick-Borne Virus in Yunnan and Guizhou Provinces, Southwestern China.

Dabieshan tick virus (DTV) is a novel tick-borne virus with the potential to infect both animals and humans. It has been confirmed that DTV is widely distributed in Shandong and Zhejiang Provinces. In this study, a total of 389 ticks were sampled from Honghe city of Yunnan Province and Bijie city of Guizhou Province, and then divided into 148 pools according to the location and species. QRT-PCR and nested PCR were performed to confirm the presence of DTV. The results showed a minimum infection rate of 2.43% (5/206) in Yunnan Province and 3.28% (6/183) in Guizhou Province, respectively. Interestingly, DTV was identified in Rhipicephalusmicroplus for the first time besides Haemaphysalis longicornis. Phylogenetic analysis showed that DTV from Yunnan and Guizhou Provinces shared over 94% identity with isolates derived from Hubei and Shandong Provinces, and DTV was relatively conservative in evolutionary dynamics. These findings provide molecular evidence of Dabieshan tick virus in different species of ticks from unrecognized endemic regions and suggest that DTV may be widely prevalent in southwestern China.

Dewaterability improvement and environmental risk mitigation of waste activated sludge using peroxymonosulfate activated by zero-valent metals: Fe0 vs. Al0.

The stabilization and dewaterability of waste activated sludge (WAS) are essential factors for downstream disposal or reuse. Herein, two types of zero-valent metals, zero-valent iron (Fe0) and zero-valent aluminum (Al0), were compared for their ability to activate peroxymonosulfate (PMS) during the WAS conditioning process, with the effects of PMS activation by these two metals on WAS dewaterability and the potential environmental risks evaluated. Results showed that compared to Al0/PMS treatment, Fe0/PMS treatment achieved superior WAS dewaterability and reduced operational costs. Using PMS combined with Fe0 and Al0 treatments under optimal conditions, the water content (Wc) of dewatered sludge decreased to 55.7 ± 2.7 wt% and 59.4 ± 1.3 wt%, respectively. Meanwhile, application of the Fe0/PMS treatment system reduced the total annual cost by approximately 33.1%, compared to the Al0/PMS treatment. Analysis of the dewatering mechanism demonstrated that in the Fe0/PMS treatment, Fe3+/Fe2+ flocculation played an important role in the enhancement of WAS dewatering, while sulfate radical (SO4•-) oxidation was the dominant factor for WAS dewaterability improvement in Al0/PMS treatment. The greater enhancement of WAS dewaterability by Fe0/PMS treatment, was mainly attributed to more efficient reduction of hydrophilic extracellular polymeric substances (EPS) and an increase in surface charge neutralization. Environmental risk evaluation results indicated that Fe0/PMS and Al0/PMS treatments both effectively alleviated the environmental risks of heavy metals and faecal coliforms in dewatered sludge. Overall, this study proposes a novel perspective for the selection of an optimal PMS activator in sludge treatment.

Decomplexation of heterogeneous catalytic ozonation assisted with heavy metal chelation for advanced treatment of coordination complexes of Ni.

Following the conventional physicochemical treatment of electroless nickel (Ni) plating wastewater (ENPW) in electroplating wastewater treatment plants, highly stable and recalcitrant coordination complexes of Ni (CCN) still remain. This results in various technical problems, leading to the treatment difficulty, poor wastewater biochemistry, and failure to meet effluent standards. Therefore, an efficient decomplexation system involving heterogeneous catalytic ozonation assisted with heavy metal chelation (O3/SAO3II-MDCR) was proposed in this study for the advanced treatment of CCN. The catalyst SAO3II was characterized by various methods, which revealed the mechanism of catalytic ozonation. Hydroxyl radicals (OH) and other reactive oxygen species (ROS) groups were detected, proving that catalytic ozonation was a complicated reaction process and also a foundation process of the entire system. These ROS are vital for decomplexation via heterogeneous catalytic ozonation of the system. During the catalytic decomplexation process via ozonation, CCN first underwent gradual decomposition from a highly stable macromolecular state to a volatile micromolecular state (or even completely mineralized state). Then Ni was chelated to form an insoluble and stable chelate via competitive coordination. The optimum conditions for the O3/SAO3II-MDCR system were determined by single factor static experiments. After treatment with the O3/SAO3II-MDCR system, the effluent concentration of total Ni was found to be <0.1 mg L-1, exhibiting a removal rate of up to 95.6% and achieving effective removal of total Ni from ENPW and stably meeting the discharge standard. O3/SAO3II-MDCR system can easily and hopefully be extended to practical engineering applications.

A new strategy on biomining of low grade base-metal sulfide tailings.

This study investigated the effect of designed microbial consortia on biomining of low grade base-metal sulfide tailings. The results show the amount of recycled metals were equal if the tailings were leached by mixed cultures of Leptospirillum ferriphilum and Acidithiobacillus thiooxidans at three different ratios or by pure culture of L. ferriphilum, which was better than the pure culture of Acidithiobacillus ferrooxidans. qPCR (quantitative polymerase chain reaction) demonstrated only L. ferriphilum functioned in the mixtures at initial stage. The results of extracellular polymeric substances (EPS) via three-dimensional excitation-emission matrix combined with parallel factor analysis (3DEEM-PARAFAC) collected from mixed or pure cultures indicated there were no interactions between two strains. Secondary minerals were formed, but did not influence the leaching process. A new strategy for tailings biomining was proposed: only ferrous oxidizers should be added during the initial and middle biomining stage, while sulfur oxidizers should be added at the end.

Analysis of the relationship of extracellular polymeric substances to the dewaterability and rheological properties of sludge treated by acidification and anaerobic mesophilic digestion.

The initial pH value of sludge affects sludge anaerobic digestion and dewatering performance. In order to determine the suitable pH value and decrease the sludge digestion time, in this study, the effect and the mechanism of combined acidification and anaerobic mesophilic digestion (acid-AMD) on sludge dewaterability were investigated. The changes and relationships among the extracellular polymeric substances (EPS), physicochemical properties, and rheological behavior of the treated sludge were analyzed. The results indicated that the combined acid-AMD treatment improved sludge dewaterability approximately 36.08% and 30.28% compared to the acid conditioning and AMD treatment, respectively. The factors improving sludge dewaterability include a lower sludge pH value and appropriate duration of AMD, changes in particle size, surface properties and distribution of the EPS fractions. The acid-AMD treatment hydrolyzed the EPS, loosening the sludge structure. These changes reflected in the rheological properties of the sludge. After the treatment, the network strength and colloid force of the sludge weakened. The linear viscoelastic region contracted, and the sludge system became sensitive to shear. These results demonstrated that rheological analysis can help explain the sludge dewatering mechanism. The acid-AMD treatment effectively changed the distribution of EPS that play a vital role in sludge dewaterability.

Research on magnetic separation for complex nickel deep removal and magnetic seed recycling.

This study investigated the deep removal of complex nickel from simulated wastewater using magnetic separation and magnetic seed recycling. Nano-magnetite (Fe3O4) was used as the magnetic seed. The flocculant applied was N,N-bis-(dithiocarboxy) ethanediamine (EDTC), a highly efficient heavy metal chelating agent included in dithiocarbamate (DTC). Important investigated parameters included hydraulic retention time, magnetic seed dosage, and magnetic field strength. The study also explored the magnetic flocculation mechanism involved in the reaction. The result indicated that the residual Ni concentration was reduced to less than 0.1 mg/L from the initial concentration of 50 mg/L under optimal conditions. Magnetic seed recovery reached 76.42% after a 3-h stirring period; recycled magnetic seeds were analyzed using scanning electron microscope (SEM) and X-ray diffraction (XRD). The zeta potential results illustrated that magnetic seeds firmly combined with flocs when the pH ranged from 6.5 to 7.5 due to the electrostatic attraction. When the pH was less than 7, magnetic seeds and EDTC were also combined due to electrostatic attraction. Particle size did affect microfloc size; it decreased microfloc size and increased floc volume through magnetic seed loading. The effective binding sites between flocs and magnetic seeds increased when adding the magnetic seeds. This led the majority of magnetic flocs to be integrated with the magnetic seeds, which served as a nucleus to enhance the flocculation property and ultimately improve the nickel complex removal rate.

Evolutionary association of stomatal traits with leaf vein density in Paphiopedilum, Orchidaceae.

BACKGROUND: Both leaf attributes and stomatal traits are linked to water economy in land plants. However, it is unclear whether these two components are associated evolutionarily. METHODOLOGY/PRINCIPAL FINDINGS: In characterizing the possible effect of phylogeny on leaf attributes and stomatal traits, we hypothesized that a correlated evolution exists between the two. Using a phylogenetic comparative method, we analyzed 14 leaf attributes and stomatal traits for 17 species in Paphiopedilum. Stomatal length (SL), stomatal area (SA), upper cuticular thickness (UCT), and total cuticular thickness (TCT) showed strong phylogenetic conservatism whereas stomatal density (SD) and stomatal index (SI) were significantly convergent. Leaf vein density was correlated with SL and SD whether or not phylogeny was considered. The lower epidermal thickness (LET) was correlated positively with SL, SA, and stomatal width but negatively with SD when phylogeny was not considered. When this phylogenetic influence was factored in, only the significant correlation between SL and LET remained. CONCLUSION/SIGNIFICANCE: Our results support the hypothesis for correlated evolution between stomatal traits and vein density in Paphiopedilum. However, they do not provide evidence for an evolutionary association between stomata and leaf thickness. These findings lend insight into the evolution of traits related to water economy for orchids under natural selection.

Slow photosynthetic induction and low photosynthesis in Paphiopedilum armeniacum are related to its lack of guard cell chloroplast and peculiar stomatal anatomy.

Paphiopedilum and Cypripedium are close relatives in the subfamily Cypripedioideae. Cypripedium leaves contain guard cell chloroplasts, whereas Paphiopedilum do not. It is unclear whether the lack of guard cell chloroplasts affects photosynthetic induction, which is important for understory plants to utilize sunflecks. To understand the role of guard cell chloroplasts in photosynthetic induction of Paphiopedilum and Cypripedium, the stomatal anatomy and photosynthetic induction of Paphiopedilum armeniacum and Cypripedium flavum were investigated at different ratios of red to blue light. The highest stomatal opening and photosynthesis of intact leaves in P. armeniacum were induced by irradiance enriched with blue light. Its stomatal opening could be induced by red light 250 µmol m⁻² s⁻¹, but the magnitude of stomatal opening was lower than those at the other light qualities. However, the stomatal opening and photosynthesis of C. flavum were highly induced by mixed blue and red light rather than pure blue or red light. The two orchid species did not differ in stomatal density, but P. armeniacum had smaller stomatal size than C. flavum. The stomata of P. armeniacum were slightly sunken into the leaf epidermis, while C. flavum protruded above the leaf surface. The slower photosynthetic induction and lower photosynthetic rate of P. armeniacum than C. flavum were linked to the lack of guard cell chloroplasts and specific stomatal structure, which reflected an adaptation of Paphiopedilum to periodic water deficiency in limestone habitats. These results provide evidence for the morphological and physiological evolution of stomata relation for water conservation under natural selection.

Leaf anatomical structures of Paphiopedilum and Cypripedium and their adaptive significance.

Paphiopedilum and Cypripedium are closely related in phylogeny, but have contrasting leaf traits and habitats. To understand the divergence in leaf traits of Paphiopedilum and Cypripedium and their adaptive significance, we analyzed the leaf anatomical structures, leaf dry mass per area (LMA), leaf lifespan (LL), leaf nitrogen concentration (N (mass)), leaf phosphorus concentration (P (mass)), mass-based light-saturated photosynthetic rate (A (mass)), water use efficiency (WUE), photosynthetic nitrogen use efficiency (PNUE) and leaf construction cost (CC) for six species. Compared with Cypripedium, Paphiopedilum was characterized by drought tolerance derived from its leaf anatomical structures, including fleshy leaves, thick surface cuticles, huge adaxial epidermis cells, lower total stoma area, and sunken stomata. The special leaf structures of Paphiopedilum were accompanied by longer LL; higher LMA, WUE, and CC; and lower N (mass), P (mass), A (mass), and PNUE compared with Cypripedium. Leaf traits in Paphiopedilum helped it adapt to arid and nutrient-poor karst habitats. However, the leaf traits of Cypripedium reflect adaptations to an environment characterized by rich soil, abundant soil water, and significant seasonal fluctuations in temperature and precipitation. The present results contribute to our understanding of the divergent adaptation of leaf traits in slipper orchids, which is beneficial for the conservation of endangered orchids.

SEQOPTICS: a protein sequence clustering system.

BACKGROUND: Protein sequence clustering has been widely used as a part of the analysis of protein structure and function. In most cases single linkage or graph-based clustering algorithms have been applied. OPTICS (Ordering Points To Identify the Clustering Structure) is an attractive approach due to its emphasis on visualization of results and support for interactive work, e.g., in choosing parameters. However, OPTICS has not been used, as far as we know, for protein sequence clustering. RESULTS: In this paper, a system of clustering proteins, SEQOPTICS (SEQuence clustering with OPTICS) is demonstrated. The system is implemented with Smith-Waterman as protein distance measurement and OPTICS at its core to perform protein sequence clustering. SEQOPTICS is tested with four data sets from different data sources. Visualization of the sequence clustering structure is demonstrated as well. CONCLUSION: The system was evaluated by comparison with other existing methods. Analysis of the results demonstrates that SEQOPTICS performs better based on some evaluation criteria including Jaccard coefficient, Precision, and Recall. It is a promising protein sequence clustering method with future possible improvement on parallel computing and other protein distance measurements.