Preparation of a novel CSM@ZIF-67 composite microsphere to facilitate Congo red adsorption from dyeing wastewater.

ABSTRACTChitosan (CS) is commonly used as an adsorbent for wastewater treatment because of its low cost, strong adsorption properties, and high availability of raw materials required for its production. However, CS exhibits limited adaptability to pH, poor mechanical properties, and high swelling in aqueous media; these limitations restrict its widespread use. To address these issues, herein, zeolitic imidazolate framework-67 (ZIF-67) is loaded onto crosslinked CS microspheres (CSM) to prepare CSM@ZIF-67, a composite adsorbent. Next, the CSM@ZIF-67 is applied to the treatment of Congo red (CR) dye, which is typically present in printing and dyeing wastewater. The results demonstrate that the in situ synthesis of metal-organic frameworks (MOFs) on CSM improve the dispersion of MOFs and preserve the morphology of the MOFs. The adsorption equilibrium of CSM@ZIF-67 is reached within 150 min, and its adsorption capacity is as high as 538.4 mg/g at a pH of 9 and temperature of 25 °C. The CR adsorption process is consistent with the pseudo-second-order kinetic and Langmuir isotherm models, thus revealing that chemisorption is the primary rate-limiting step, and the pollutants are adsorbed on the adsorbent surface in a monolayer. Experiments on material cycling and regeneration performance reveal that the removal efficiency of CSM@ZIF-67 remains above 90%, even after five rounds of adsorption. CSM@ZIF-67 has abundant functional groups and adsorption sites and can efficiently remove CR through mutual interactions between the metal coordination effect, π-π conjugation, hydrogen bonding, and electrostatic interactions.

From micro to macro: The role of seawater in maintaining structural integrity and bioactivity of granules in treating antibiotic-laden mariculture wastewater.

Granular sludge (GS) has superior antibiotic removal ability to flocs, due to GS's layered structure and rich extracellular polymeric substances. However, prolonged exposure to antibiotics degrades the performance and stability of GS. This study investigated how a seawater matrix might help maintain the structural integrity and bioactivity of granules. The results demonstrated that GS had better sulfadiazine (SDZ) removal efficiency in a seawater matrix (85.6 %) than in a freshwater matrix (57.6 %); the multiple ions in seawater enhanced boundary layer diffusion (kiR1 = 0.0805 mg·g-1·min-1/2 and kiR2 = 0.1112 mg·g-1·min-1/2) and improved adsorption performance by 15 % (0.123 mg/g-SS freshwater vs. 0.141 mg/g-SS seawater). Moreover, multiple hydrogen bonds (1-3) formed between each SDZ and lipid bilayer fortified the adsorption. Beyond S-N and S-C bond hydrolyses that took place in freshwater systems, there was an additional biodegradation pathway for GS to be cultivated in a saltwater system that involved sulfur dioxide extrusion. This additional pathway was attributable to the greater microbial diversity and larger presence of sulfadiazine-degrading bacteria containing SadAC genes, such as Leucobacter and Arthrobacter, in saltwater wastewater. The findings of this study elucidate how seawater influences GS properties and antibiotic removal ability.

Enhancement strategies of aerobic denitrification for efficient nitrogen removal from low carbon-to-nitrogen ratio shale oil wastewater.

The strategy of high reflux ratio and long solids retention time was adopted to realize efficient nitrogen removal from real shale oil wastewater. This was undertaken with a low chemical oxygen demand to total nitrogen (COD/TN) ratio by strengthening aerobic denitrification in an anoxic/aerobic membrane bioreactor (A/O-MBR). The TN removal load climbed from 22 to 25 g N/(kg MLSS·d) as the COD/TN ratio declined from 8 to 3. The abundance of heterotrophic nitrifying and aerobic denitrifying (HNAD) bacteria increased by 13.8 times to 42.5%, displacing anoxic denitrifying bacteria as the predominant bacteria. The abundance of genes involved in denitrification (napAB, narGHI, norBC, nosZ) increased, however the genes related to assimilatory nitrate reduction (nirA, narB, nasC) decreased. The capacity of the dominant HNAD bacteria in an A/O-MBR to efficiently utilize a carbon source is the key to efficient nitrogen removal from shale oil wastewater with a low COD/TN ratio.

Achieving tetracycline removal enhancement with granules in marine matrices: Performance, adaptation, and mechanism studies.

Using the aerobic granular sludge (AGS) to improve tetracycline (TET) removal in the treatment of mariculture wastewater was investigated in the present study. The AGS rapidly adapted to and was sustained in seawater matrices with a robust granule strength (k = 0.0014) and a more stable sludge yield than the activated sludge (AS) (0.14 vs 0.11 g-VSS/g-CODrem). The compact structure provided the AGS with an anoxic environment, which favored the growth of N (37.3 %) and P removal bacteria (30.4 %) and the expression of functional genes (nos, nor, and nar), resulting in more than 62 % TN and TP removals, respectively. Similar abundances of aromatic compound-degrading bacteria (∼34 %) in both reactors (AGS and AS) led to comparable TET biodegradation efficiencies (∼0.045 mg/g-VSS). The greater size and surface area of the AGS expanded the boundary layer diffusion region, leading to 16 % increases in the granule's TET adsorption capacity.

Enhancement of humic acid on plant growth in a Cd-contaminated matrix: performance, kinetics, and mechanism.

Phytoremediation of heavy metal-contaminated sites has been widely used. Nonetheless, the destruction of chloroplasts and plant growth enzymes by heavy metals leads to a low germination rate and high mortality of plants. To address these issues, an experiment was conducted in which plants were grown with (SHC) and without humic acid (SC) in actual Cd-contaminated soil from the site of an industrial pollution source. The results showed that the average germination rates of SC and SHC samples were 94.17% and 98.33%, respectively, and the plant heights were approximately 5 and 7 cm after 42 days of planting, respectively. It was discovered that humic acid (HA) enhanced plant growth by increasing urease and invertase content of the soil. The Shannon index and Venn diagram revealed that SHC had the richer population diversity. High-throughput analysis demonstrated that HA increased the content of plant growth-promoting bacteria in the soil from 5.01 to 34.27%. The experimental results revealed that HA increased microbial activity and diversity, thereby providing a favorable environment for plants to thrive. This study develops an effective method to enhance the phytoremediation performance of heavy metal-contaminated soils.

Removal of tetracycline by aerobic granular sludge from marine aquaculture wastewater: A molecular dynamics investigation.

Although biological treatment of marine aquaculture wastewater is promising, the fundamental principles driving the adsorption of tetracycline to microbial cell membrane are not well understood. Using a combination of experiments and molecular dynamics (MD) simulations, the mechanism underlying the biological removal of tetracycline from seawater was investigated. More than 90% tetracycline removal was achieved in an aerobic granular sludge system, with degradation accounting for 30% of total removal. A model of the tetracycline-dipalmitoylphosphatidylcholine lipid bilayers was established to elucidate the transport mechanism of tetracycline from bulk solution to microorganisms' cell membrane. 62% of the driving force for tetracycline adsorption on the cell membrane originated from electrostatic attraction. The electrophilic groups on tetracycline (amino and aromatic groups) were attracted to the phosphate groups in the cell membrane. Sodium ions, which are abundant in seawater, decreased the interaction energy between tetracycline and the cell membrane.

Can a compact biological system be used for real hydraulic fracturing wastewater treatment?

Hydraulic fracturing wastewater (HFW), a byproduct of hydraulic fracturing oil extraction, contains a complex mixture of oil, aldehydes, and benzene compounds. Efficient and eco-friendly HFW treatment means are critical for the oil extraction industry, particularly in developing countries. In this study, two biological processes namely an anaerobic/anoxic/moving bed biofilm reactor (A2-MBBR) and an A2-MBBR with a microfiltration membrane (A2-MFMBBR) were established, and assessed for the real HFW treatment. Removal efficiencies of chemical oxygen demand (COD) and NH4+-N were over 92% and 95%, respectively, in both processes with a hydraulic retention time of 72 h. The majority of organic compounds in both systems identified by GC-MS were degraded in the anaerobic units. In comparison, A2-MFMBBR demonstrated higher removal efficiencies for oil, total suspended solids, and complex compounds. The average relative abundances of refractory compound degrading bacteria were 43.4% and 51.6% in the A2-MBBR and A2-MFMBBR, respectively, which was consistent with the COD and oil removal, and suggested that the MBR could maintain a high diversity of microorganisms and contribute to deep recalcitrant organics degradation. This study sheds light on the potential of using a compact biological process for the real HFW treatment.

Potentially toxic elements in weathered waste-rocks of Fushun western opencast mine: distribution, source identification, and contamination assessment.

To understand the current status of the contamination of potentially toxic elements (PTEs) after closing the Fushun Western Opencast Mine, this study has focused on the concentration, contamination assessment, and source identification of eight PTEs in weathered waste-rocks in four distinct areas of the mine. The mean concentrations of Ni, Cr, Zn, Cu, Pb, Hg, Cd, and As were 79.4, 86.3, 126, 64.8, 16.9, 1.04, 1.94, and 6.27 mg kg-1, respectively. The results demonstrated that Ni, Cr, Zn, Cu, Pb, Hg, Cd, and As were contaminated to different extents in different weathered waste-rocks and waste-rocks, among which there was considerable Cd contamination. Coal gangue area (CGA) exhibited the most polluted weathered waste-rocks, which can be attributed to severe pollution and moderate ecological hazards. Self-combustion gangue (SCG) contamination of waste-rocks was considerably serious and caused severe pollution and considerable ecological harm. Health risk assessments demonstrated that Hg had the highest non-carcinogenic risk. Ingestion of PTEs was found to be a primary route of exposure, while dermal and inhalation exposure was negligible. Principal component analysis (PCA) demonstrated that there were roughly three sources of PTEs in the weathered waste-rocks of the mine, natural sources related to the weathering of parent rocks, and human sources, including industrial emissions, mining activities, and atmospheric dust deposition and resuspension. This study advances our knowledge of PTEs in mines and provides policymakers with a reference for designing strategies to protect mine-based ecosystems.

Atomic Modulation Triggering Improved Performance of MoO3 Nanobelts for Fiber-Shaped Supercapacitors.

Asymmetric supercapacitors (ASCs) are emerging as a new class of energy storage devices that could potentially meet the increasing power and energy demand for next-generation portable and flexible electronics. Yet, the energy density of ASC is severely limited by the low capacitance of the anode side, which commonly uses the carbon-based nanomaterials. Here, the demonstration of sulfur-doped MoO3- x nanobelts (denoted as S-MoO3- x ) as the anode for high-performance fiber-shaped ASC are reported. The Mo sites in MoO3 are intentionally modulated at the atomic level through sulfur doping, where sulfur could be introduced into the MoO6 octahedron to intrinsically tune the covalency character of bonds around Mo sites and thus boost the charge storage kinetics of S-MoO3- x . Moreover, the oxygen defects are occurring along with sulfur-doping in MoO3 , enabling efficient electron transport. As expected, the fiber-shaped S-MoO3- x achieves outstanding capacitance with good rate capability and long cycling life. More impressively, the fiber-shaped ASC based on S-MoO3- x anode delivers extremely high volumetric capacitance of 6.19 F cm-3 at 0.5 mA cm-1 , which makes it promising as one of the most attractive candidates of anode materials for high-performance fiber-shaped ASCs.

Effects of a pulsed electric field on nitrogen removal through the ANAMMOX process at room temperature.

This study explored the effect of a pulsed electric field (PEF) on the anaerobic ammonium oxidation (ANAMMOX) process at room temperature (20 ±â€¯1 °C). The influences of different modes of PEF (R1), a direct current electric field (R2) and a control reactor (R3) were determined through long-term tests. The results showed that R1 shortened the start-up time and led to excellent nitrogen removal. At this stage, the activities of key enzymes of R1 were much higher than those of R3. The high-throughput sequencing results showed that the relative abundance of functional bacteria in R1 was higher than that in R2 and R3. The mechanism by which the PEF enhanced ANAMMOX might be the improvement of the speed of ion and molecular migration that occurred by changing the permeability of the cell membrane under the PEF.

[Determination of 63 compounds illegally added in tea, substitute tea and beverage foods by ultra-high performance liquid chromatography-tandem mass spectrometry].

A method based on ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of 63 compounds illegally added in tea, substitute tea, and beverage products. The samples were extracted by ultrasonic extraction using methanol, and the analytes were separated on the Thermo Acclaim RSLC C18 chromatographic column (100 mm×2.1 mm, 2.2 µm) by gradient elution using 5 mmol/L ammonium formate solution containing 0.1% (v/v) formic acid and 0.1% (v/v) formic acid acetonitrile as the mobile phase. The electrospray ion source was operated in the positive ion mode using the dynamic multi-reaction monitoring (dMRM) method, and the results were quantified by the external standard method. The correlation coefficients (R2) of the linear calibration curves were greater than 0.99 in the corresponding mass concentration ranges, and the limits of quantification (LOQs) for the analytes were 0.10-2.50 mg/kg. The average recoveries at three spiked levels ranged from 62.4% to 129.4%. The RSDs of the injection precision and the repeatability of samples were in the range 0.3%-9.6% (n=6). Thus, the proposed method is simple, rapid, accurate, reliable, and applicable for the detection of the illegal addition of antipyretic and analgesic affect compounds in tea, substitute tea and beverage food.

Research on the enhancement of biological nitrogen removal at low temperatures from ammonium-rich wastewater by the bio-electrocoagulation technology in lab-scale systems, pilot-scale systems and a full-scale industrial wastewater treatment plant.

In cold areas, nitrogen removal performance of wastewater treatment plants (WWTP) declines greatly in winter. This paper systematically describes the enhancement effect of a periodic reverse electrocoagulation technology on biological nitrogen removal at low temperatures. The study showed that in the lab-scale systems, the electrocoagulation technology improved the biomass amount, enzyme activity and the amount of nitrogen removal bacteria (Nitrosomonas, Nitrobacter, Paracoccus, Thauera and Enterobacter). This enhanced nitrification and denitrification of activated sludge at low temperatures. In the pilot-scale systems, the electrocoagulation technology increased the relative abundance of cold-adapted microorganisms (Luteimonas and Trueperaceae) at low temperatures. In a full-scale industrial WWTP, comparison of data from winter 2015 and winter 2016 showed that effluent chemical oxygen demand (COD), NH4+-N, and NO3--N reduced by 10.37, 3.84, and 136.43 t, respectively, throughout the winter, after installation of electrocoagulation devices. These results suggest that the electrocoagulation technology is able to improve the performance of activated sludge under low-temperature conditions. This technology provides a new way for upgrading of the performance of WWTPs in cold areas.

Performance and microbial community analysis of bio-electrocoagulation on simultaneous nitrification and denitrification in submerged membrane bioreactor at limited dissolved oxygen.

A pair of Fe-C electrodes was installed in a traditional submerged membrane bioreactor (MBR, Rc), and a novel asynchronous periodic reversal bio-electrocoagulation system (Re) was developed. The simultaneous nitrification and denitrification (SND) performance was discussed under limited dissolved oxygen (DO). Results showed that electrocoagulation enhanced total nitrogen (TN) removal from 59.48% to 75.09% at 1.2 mg/L DO. Additionally, Fe electrode could increase sludge concentration, particle size, and enzyme activities related to nitrogen removal. The enzyme activities of Hydroxylamine oxidoreductase (HAO), Nitrate Reductase (NAR), nitric oxide reductase NOR and nitrous oxide reductase (N2OR) in Re were 38.35%, 21.59%, 89.96% and 38.64% higher than Rc, respectively. Moreover, electrocoagulation was advantageous for nitrite accumulation, indicating partial nitrification and denitrification were more easily achieved in Re. Besides, results from high throughput sequencing analysis revealed that electrocoagulation increased the relative abundance of most genera related to nitrogen removal, including Nitrosomonas, Comamonadaceae_unclassified, Haliangium and Denitratisoma.

Influence of electric field and iron on the denitrification process from nitrogen-rich wastewater in a periodic reversal bio-electrocoagulation system.

This study proposed a periodic reversal bio-electrocoagulation system (PRBES) with Fe-C electrodes and three other control systems and explored their denitrification mechanism. The experimental results illustrated that iron ions contributed to increasing biomass and denitrifying bacteria and that the electric field may enhance the nitrogen transfer rate and enzyme activities. The dominant bacterial genera in the four systems were the Enterobacter (32.75%), Thauera (9.29%), Paracoccus (8.54%), Hyphomicrobium (5.01%) and Saccharibacteria_genera (10.57%). The sum of the relative abundance of the first four bacteria, which were the major microorganisms in the denitrification process in this study, was 64.61%, 55.40%, 61.19% and 47.08%, respectively, in PRBES and the three other control systems at 10 °C. Additionally, compared to the conventional SBR, there was a 65.48% decrease in N2O in PRBES at 10 °C. This study provided a meaningful and significant understanding of denitrification in PRBES when treating nitrogen-rich wastewater.

Exploration of the Kinetics of Toehold-Mediated Strand Displacement via Plasmon Rulers.

DNA/RNA strand displacement is one of the most fundamental reactions in DNA and RNA circuits and nanomachines. In this work, we reported an exploration of the dynamic process of the toehold-mediated strand displacement via core-satellite plasmon rulers at the single-molecule level. Applying plasmon rulers with unlimited lifetime, single-strand displacement triggered by the invader that resulted in stepwise leaving of satellite from the core was continuously monitored by changes of scattering signal for hours. The kinetics of strand displacement in vitro with three different toehold lengths have been investigated. Also, the study revealed the difference in the kinetics of strand displacement between DNA/RNA and DNA/DNA duplexes. For the kinetics study in vivo, influence from the surrounding medium has been evaluated using both phosphate buffer and cell lysate. Applying core-satellite plasmon rulers with high signal/noise ratio, kinetics study in living cells proceeded for the first time, which was not possible by conventional methods with a fluorescent reporter. The plasmon rulers, which are flexible, easily constructed, and robust, have proven to be effective tools in exploring the dynamical behaviors of biochemical reactions in vivo.

Effect of iron ions and electric field on nitrification process in the periodic reversal bio-electrocoagulation system.

This study explored the nitrification mechanism of a periodic reversal bio-electrocoagulation system with Fe-C electrodes. The ammonia nitrogen removal was compared in four identical cylindrical sequencing bath reactors. Two of them were reactors with Fe-C electrodes (S1) and C-C electrodes (S2), respectively. The other two were a reactor with iron ions (S3) and a traditional SBR (S4), respectively. The results demonstrated that the effect on enhancing nitrification in S1 was the best among all four SBRs, followed by S3, S2 and S4. Iron ions increased the biomass, and electric field improved the proton transfer and enzyme activity. The dominant bacterial genera in the four SBRs were Hyphomicrobium, Thauera, Nitrobacter, Nitrosomonas, Paracoccus and Hydrogenophaga. The iron ions may increase the levels of Nitrosomonas and Nitrobacter, both of which were the main microbes of the nitrification process. This study provided a significant and meaningful understanding of nitrification in a bio-electrocoagulation system.

Single-molecule imaging of telomerase activity via linear plasmon rulers.

Plasmon rulers (PRs) exploit the potential of plasmon coupling between individual pairs of noble metal nanoparticles in biological processes, especially single-molecule detection. Herein, for the first time, we report a strategy based on Ag PRs for in situ monitoring of the extension process of telomerase primer (TSP) activated by a single telomerase.

Distance mediated electrochemiluminescence enhancement of CdS thin films induced by the plasmon coupling of gold nanoparticle dimers.

Gold nanoparticle dimers assembled on the surface of CdS QD thin films served as nano-antennas to mediate the distance-dependent plasmon enhanced electrochemiluminescence of QDs.

Plasmonic nanohalo optical probes for highly sensitive imaging of survivin mRNA in living cells.

A strategy is designed for sensitive detection of tumor biomarker survivin mRNA based on resonance Rayleigh scattering of a single AuNP nanohalo probe that couples large gold nanoparticles (L-AuNPs, 52 nm) with small AuNPs (S-AuNPs, 18 nm) through the affinity interaction between streptavidin and biotin. This core-satellite plasmon ruler is further applied to imaging survivin mRNA in living cells.

Quality evaluation of Huaijiao pill by chromatographic fingerprint and simultaneous determination of its major bioactive components.

For quality control purpose, an approach of combining chromatographic fingerprint of Huaijiao pill (HP) and simultaneous determination of its major bioactive components was developed using high performance liquid chromatography coupled with diode array detector (HPLC--DAD). For fingerprint analysis, 16 peaks were selected as the characteristic peaks to evaluate the similarities of different samples collected from different batches of three manufacturers. The similarities of 17 Huaijiao pill samples were beyond 0.966, indicating that samples from different batches and manufacturers were, to some extent, consistent. Additionally, simultaneous quantification of seven bioactive markers, namely sophoricoside, baicalin, naringin, genistein, rutin, quercetin and 5-O-methylvisammioside, in HP was performed to interpret the quality consistency. The validation of the proposed approach was acceptable, with the accuracy of 90.2%-106.9% in recovery test. The intra-day and inter-day precisions of the method were evaluated and the RSD values were less than 2.81%. The results from the quantitative data showed that the contents of six marker compounds (except for 5-O-methylvisammioside) were quite consistent between batches produced by one manufacturer and significantly distinctive among different manufacturers. The proposed approach was expected to be developed as a powerful tool for the quality control of HP.