Struvite and ethylenediaminedisuccinic acid (EDDS) enhance electrokinetic-biological permeable reactive barrier removal of copper and lead from contaminated loess.

Removal of heavy metals using the electrokinetic (EK) remediation technology is restricted by soils containing a fraction of clay particles above 12%. Furthermore, it is also affected by hydroxide precipitation (focusing phenomenon) close to the cathode. A modified EK reactor containing a permeable reactive barrier (PRB) was proposed herein where the enzyme-induced carbonate precipitation (EICP) treatment was incorporated into the PRB. Despite that, NH4+-N pollution induced by the urea hydrolysis resulting from the EICP treatment causes serious threats to surrounding environments and human health. There were four types of tests applied to the present work, including CP, TS1, TS2, and TS3 tests. CP test neglected the bio-PRB, while TS1 test considered the bio-PRB. TS2 test based on TS1 test tackled NH4+-N pollution using the struvite precipitation technology. TS3 test based on TS2 test applied EDDS to enhance the removal of Cu and Pb. In CP test, the removal efficiency applied to Cu and Pb removals was as low as approximately 10%, presumably due to the focusing phenomenon. The removal efficiency was elevated to approximately 24% when the bio-PRB and the electrolyte reservoir were involved in TS1 test. TS2 test indicated that the rate of struvite precipitation was 40 times faster than the ureolysis rate, meaning that the struvite precipitate had sequestered NH4+ before it started threatening surrounding environments. The chelation between Cu2+ and EDDS took place when EDDS played a part in TS3 test. It made Cu2+ negatively surface charged by transforming Cu2+ into EDDSCu2-. The chelation caused those left in S4 and S4 to migrate toward the bio-PRB, whereas it also caused those left in S1 and S2 to migrate toward the anode. Due to this reason, the fraction of Cu2+ removed by the bio-PRB and the electrolyte reservoir is raised to 32% and 26% respectively, and the fraction of remaining Cu was reduced to 41%. Also, the removal efficiency applied to Pb removal was raised to 50%. Results demonstrate the potential of struvite and EDDS-assisted EK-PRB technology as a cleanup method for Cu- and Pb-contaminated loess.

Applying the first microcapsule-based self-healing microbial-induced calcium carbonate materials to prevent the migration of Pb ions.

Lead (Pb) accumulation can lead to serious threats to surrounding environments and damage to the liver and kidneys. In the past few years, microbial-induced carbonate precipitation (MICP) technology has been widely applied to achieve Pb immobilization due to its environmentally friendly nature. However, harsh pH conditions can cause the instability of the carbonate precipitation to degrade or dissolve, increasing the potential of Pb2+ migration into nearby environments. In this study, microcapsule-based self-healing microbial-induced calcium carbonate (MICC) materials were applied to prevent Pb migration. The highest sporulation rate of 95.8% was attained at 7 g/L yeast extract, 10 g/L NH4Cl, and 3.6 g/L Mn2+. In the germination phase, the microcapsule not only prevented the bacterial spores from being threatened by the acid treatment but secured their growth and reproduction. Micro analysis also revealed that cerussite, calcite, and aragonite minerals were present, while extracellular polymeric substances (EPSs) were identified via Fourier transform infrared spectroscopy (FTIR). These results confirm their involvement in combining Pb2+ and Ca2+. The immobilization efficiency of above 90% applied to MICC materials was attained, while it of below 5% applied to no MICC use was attained. The findings explore the potential of applying microcapsule-based self-healing MICC materials to prevent Pb ion migration when the calcium carbonate degrades under harsh pH conditions.

Study on Cu- and Pb-contaminated loess remediation using electrokinetic technology coupled with biological permeable reactive barrier.

Although the electrokinetic (EK) remediation has drawn great attention because of its good maneuverability, the focusing phenomenon near the cathode and low removal efficiency remain to be addressed. In this study, a novel EK reactor was proposed to remediate Cu and Pb contaminated loess where a biological permeable reactive barrier (bio-PRB) was deployed to the middle of the EK reactor. For comparison, three test configurations, namely, CG, TG-1, and TG-2, were available. CG considered the multiple enzyme-induced carbonate precipitation (EICP) treatments, while TG-1 considered both the multiple EICP treatments and pH regulation. TG-2 further considered NH4+ recovery based on TG-1. CG not only improved Cu and Pb removals by the bio-PRB but also depressed the focusing phenomenon. TG-1 causes more Cu2+ and Pb2+ to migrate toward the bio-PRB and aggravates Cu and Pb removals by the bio-PRB, depressing the focusing phenomenon. TG-2 depressed the focusing phenomenon the most because Cu2+ and Pb2+ can combine with not only CO32- but PO43-. The removal efficiency of Cu and Pb is 34% and 36%, respectively. A NH4+ recovery of about 100% is attained.

A Naphthalenediimide-Based Metal-Organic Framework and Thin Film Exhibiting Photochromic and Electrochromic Properties.

A multifunctional metal-organic framework, NBU-3, has been explored as a 2D three-connected network based on a naphthalenediimide-based ligand. The NBU-3 crystals display photochromic properties, and NBU-3 thin films on FTO substrates exhibit electrochromic properties. NBU-3 is the first example of MOF materials containing both photochromic and electrochromic properties, which can be desirable for thin film devices.

Deterioration phenomenon of Pb-contaminated aqueous solution remediation and enhancement mechanism of nano-hydroxyapatite-assisted biomineralization.

Modern metallurgical and smelting activities discharge the lead-containing wastewater, causing serious threats to human health. Bacteria and urease applied to microbial-induced carbonate precipitation (MICP) and enzyme-induced carbonate precipitation (EICP) are denatured under high Pb2+ concentration. The nano-hydroxyapatite (nHAP)-assisted biomineralization technology was applied in this study for Pb immobilization. Results showed that the extracellular polymers and cell membranes failed to secure the urease activity when subjected to 60 mM Pb2+. The immobilization efficiency dropped to below 50% under MICP, whereas it due to a lack of extracellular polymers and cell membranes dropped to below 30% under EICP. nHAP prevented the attachment of Pb2+ either through competing with bacteria and urease or promoting Ca2+/Pb2+ ion exchange. Furthermore, CO32- from ureolysis replaced the hydroxyl (-OH) in hydroxylpyromorphite to encourage the formation of carbonate-bearing hydroxylpyromorphite of higher stability (Pb10(PO4)6CO3). Moreover, nHAP application overcame an inability to provide nucleation sites by urease. As a result, the immobilization efficiency, when subjected to 60 mM Pb2+, elevated to above 80% under MICP-nHAP and to some 70% under EICP-nHAP. The findings highlight the potential of applying the nHAP-assisted biomineralization technology to Pb-containing water bodies remediation.

Nano-hydroxyapatite-assisted enzyme-induced carbonate precipitation enhances Pb-contaminated aqueous solution and loess remediation.

Intensive agricultural activities could cause lead (Pb) bioaccumulation, threatening human health. Although the enzyme-induced carbonate precipitation (EICP) technology has been applied to tackle the aforesaid problem, the urease may denature or even lose its activity when subjected to a significant Pb2+ toxicity effect. To this end, the nano-hydroxyapatite (nHAP)-assisted EICP was proposed to reduce the mobility of Pb2+. Results indicated that a below 30% immobilization efficiency at 60 mM Pb2+ was attained under EICP. nHAP adsorbed the majority of Pb2+, preventing Pb2+ attachment to urease. Further, hydroxylphosphohedyphane or hydroxylpyromorphite was formed at 60 mM Pb2+, followed by the formation of cerussite, allowing hydroxylphosphohedyphane or hydroxylpyromorphite to be wrapped by cerussite. By contrast, carbonate-bearing hydroxylpyromorphite of higher stability (Pb10(PO4)6CO3) was developed at 20 mM Pb2+ as CO3 2- substituted the hydroxyl group in hydroxylpyromorphite. Moreover, nHAP helped EICP to form nucleated minerals. As a result, the EICP-nHAP technology raised the immobilization efficiency at 60 mM Pb2+ up to 70%. The findings highlight the potential of applying the EICP-nHAP technology to Pb-containing water bodies remediation.

Immobilizing lead in aqueous solution and loess soil using microbially induced carbonate/phosphate precipitation (MICP/MIPP) under harsh pH environments.

The bioaccumulation of heavy metals due to metallurgical and smelting activities threatens human health. Although microbial-induced carbonate/phosphate precipitation (MICP/MIPP) technology has been applied to heavy metal remediation, the relative merits of MICP and MIPP, especially under extreme pH environments, have not yet been documented. In this study, Sporosarcina pasteurii (SP)-based MICP and Bacillus megaterium (BM)-based MIPP were applied to immobilize lead (Pb) in aqueous solution and loess soil. The results showed that the BM retained a strong phosphorolysis ability when under strongly acidic conditions, while the ureolysis ability of SP approached zero. Furthermore, the bioprecipitates obtained under BM-based MIPP had a denser appearance, presumably due to the enrichment of calcite and apatite crystals. The results also showed that Pb immobilization was achieved through bacterial adsorption, the chelate function of sodium glycerophosphate (SGP), large organic matter complexation, and biomineralization through the MICP/MIPP mechanism. Under SP-based MICP, SP and large organic matter immobilized Pb2+ at rates of 17.6 % and 31.7 %, respectively, while under BM-based MIPP, BM, organic matter, and SGP immobilized Pb2+ at rates of 21.5 %, 23.4 %, and 48.5 % respectively. The MICP and MIPP mechanisms dominated Pb immobilization at rates of 78.6 % and 99.6 %, respectively.

Immobilization of Pb(II) by Bacillus megaterium-based microbial-induced phosphate precipitation (MIPP) considering bacterial phosphorolysis ability and Ca-mediated alleviation of lead toxicity.

Inappropriate handling of lead (Pb)-containing wastewater that is produced as a result of smelting activities threatens the surrounding environment and human health. The microbial-induced phosphate precipitation (MIPP) technology was applied to immobilize Pb2+ in an aqueous solution considering bacterial phosphorolysis ability and Ca-mediated alleviation of lead toxicity. Pb immobilization was accompanied by sample characterization in order to explore the inherent mechanism that affected the immobilization efficiency. Results showed that Ca2+ use elevated the immobilization efficiency through the prevention of bacterial physisorption and chemisorption, an enhancement to the phosphatase activity and the degree of SGP hydrolysis, and the provision of nucleation sites for Pb2+ to attach. The formation of the Pb-GP complex helped the bacteria to maintain its activity at the commencement of catalyzing SGP hydrolysis. The nucleated minerals that were precipitated in a columnar shape through a directional stacking manner under MIPP featured higher chemical stability compared to non-nucleated minerals. As a result, there were three pathways, namely, bacterial physisorption, bacterial chemisorption, and substrate chelation, applied for Pb immobilization. The immobilization efficiency of 99.6% is achieved by precipitating bioprecipitates including Pb5(PO4)3Cl, Pb10(PO4)6Cl2, and Ca2Pb3(PO4)3Cl. The findings accentuate the potential of applying the MIPP technology to Pb-containing wastewater remediation.

Immobilizing copper in loess soil using microbial-induced carbonate precipitation: Insights from test tube experiments and one-dimensional soil columns.

Biomineralization as an alternative to traditional remediation measures has been widely applied to remediate copper (Cu)-contaminated sites due to its environmental-friendly nature. Immobilizing Cu is, however, a challenging task as it inevitably causes inactivation of ureolytic bacteria. In the present work, a series of test tube experiments were conducted to derive the relationships of Cu immobilization efficiency versus pH conditions. The Cu speciation transformation that is invisible in the test tube experiments was investigated via numerical simulations. Apart from that, the one-dimensional soil column tests, accompanied by the X-ray diffraction (XRD) and Raman spectroscopy analysis, mainly aimed not only to investigate the variations of Cu immobilization efficiency with the depth but to reveal the underlying mechanisms affecting the Cu immobilization efficiency. The results of the test tube experiments highlight the necessity of narrowing pH ranges to as close as 7 by introducing an appropriate bacterial inoculation proportion. The coordination adsorption of Cu, while performing the one-dimensional soil column tests, is encouraged by alkaline environments, which differs from the test tube experiments where Cu2+ is capsulized by carbonate precipitates to prevent their migration. The findings highlight the potential of applying the microbial-induced carbonate precipitation (MICP) technology to Cu-rich water bodies and Cu-contaminated sites remediation.

Investigating immobilization efficiency of Pb in solution and loess soil using bio-inspired carbonate precipitation.

Lead (Pb) metal accumulation in surrounding environments can cause serious threats to human health, causing liver and kidney function damage. This work explored the potential of applying the MICP technology to remediate Pb-rich water bodies and Pb-contaminated loess soil sites. In the test tube experiments, the Pb immobilization efficiency of above 85% is attained through PbCO3 and Pb(CO3)2(OH)2 precipitation. Notwithstanding that, in the loess soil column tests, the Pb immobilization efficiency decreases with the increase in depth and could be as low as approximately 40% in the deep ground. PbCO3 and Pb(CO3)2(OH)2 precipitation has not been detected as the majority of Pb2+ combines with -OH (hydroxyl group) when subjected to 500 mg/kg Pb2+. The alkaline front promotes the chemisorption of Pb2+ with CO32- reducing the depletion of quartz mineral close to the surface. However, OH- is in shortage in the deep ground retarding the Pb immobilization. The Pb immobilization efficiency thus decreases with the increase in depth. Quartz and albite minerals, when subjected to 16,000 mg/kg Pb2+, appear not to intervene in the chemisorption with Pb2+ where the chemisorption of Pb2+ with CO32- plays a major role in the Pb immobilization. Compared to the nanoscale urease applied to the enzyme-induced carbonate precipitation (EICP) technology, the micrometer scale ureolytic bacteria penetrate into the deep ground with difficulty. The 'size' issue remains to be addressed in near future.

Biopolymer-assisted enzyme-induced carbonate precipitation for immobilizing Cu ions in aqueous solution and loess.

Wastewater, discharged in copper (Cu) mining and smelting, usually contains a large amount of Cu2+. Immobilizing Cu2+ in aqueous solution and soils is deemed crucial in preventing its migration into surrounding environments. In recent years, the enzyme-induced carbonate precipitation (EICP) has been widely applied to Cu immobilization. However, the effect of Cu2+ toxicity denatures and even inactivates the urease. In the present work, the biopolymer-assisted EICP technology was proposed. The inherent mechanism affecting Cu immobilization was explored through a series of test tube experiments and soil column tests. Results indicated that 4 g/L chitosan may not correspond to a higher immobilization efficiency because it depends as well on surrounding pH conditions. The use of Ca2+ not only played a role in further protecting urease and regulating the environmental pH but also reduced the potential for Cu2+ to migrate into nearby environments when malachite and azurite minerals are wrapped by calcite minerals. The species of carbonate precipitation that are recognized in the numerical simulation and microscopic analysis supported the above claim. On the other hand, UC1 (urease and chitosan colloid) and UC2 (urea and calcium source) grouting reduced the effect of Cu2+ toxicity by transforming the exchangeable state-Cu into the carbonate combination state-Cu. The side effect, induced by 4 g/L chitosan, promoted the copper-ammonia complex formation in the shallow ground, while the acidic environments in the deep ground prevented Cu2+ from coordinating with soil minerals. These badly degraded the immobilization efficiency. The Raman spectroscopy and XRD test results tallied with the above results. The findings shed light on the potential of applying the biopolymer-assisted EICP technology to immobilizing Cu ions in water bodies and sites.

Immobilizing lead and copper in aqueous solution using microbial- and enzyme-induced carbonate precipitation.

Inappropriate irrigation could trigger migration of heavy metals into surrounding environments, causing their accumulation and a serious threat to human central nervous system. Traditional site remediation technologies are criticized because they are time-consuming and featured with high risk of secondary pollution. In the past few years, the microbial-induced carbonate precipitation (MICP) is considered as an alternative to traditional technologies due to its easy maneuverability. The enzyme-induced carbonate precipitate (EICP) has attracted attention because bacterial cultivation is not required prior to catalyzing urea hydrolysis. This study compared the performance of lead (Pb) and copper (Cu) remediation using MICP and EICP respectively. The effect of the degree of urea hydrolysis, mass and species of carbonate precipitation, and chemical and thermodynamic properties of carbonates on the remediation efficiency was investigated. Results indicated that ammonium ion (NH4 +) concentration reduced with the increase in lead ion (Pb2+) or copper ion (Cu2+) concentration, and for a given Pb2+ or Cu2+ concentration, it was much higher under MICP than EICP. Further, the remediation efficiency against Cu2+ is approximately zero, which is way below that against Pb2+ (approximately 100%). The Cu2+ toxicity denatured and even inactivated the urease, reducing the degree of urea hydrolysis and the remediation efficiency. Moreover, the reduction in the remediation efficiency against Pb2+ and Cu2+ appeared to be due to the precipitations of cotunnite and atacamite respectively. Their chemical and thermodynamic properties were not as good as calcite, cerussite, phosgenite, and malachite. The findings shed light on the underlying mechanism affecting the remediation efficiency against Pb2+ and Cu2+.

Catalyzing urea hydrolysis using two-step microbial-induced carbonate precipitation for copper immobilization: Perspective of pH regulation.

Microbial induced carbonate precipitation (MICP) has recently applied to immobilize heavy metals toward preventing their threats to public health and sustainable development of surrounding environments. However, for copper metallurgy activities higher copper ion concentrations cause the ureolytic bacteria to lose their activity, leading to some difficulty in forming carbonate precipitation for copper immobilization (referred to also as "biomineralization"). A series test tube experiments were conducted in the present work to investigate the effects of bacterial inoculation and pH conditions on the copper immobilization efficiency. The numerical simulations mainly aimed to compare with the experimental results to verify its applicability. The copper immobilization efficiency was attained through azurite precipitation under pH in a 4-6 range, while due to Cu2+ migration and diffusion, it reduced to zero under pH below 4. In case pH fell within a 7-9 range, the immobilization efficiency was attained via malachite precipitation. The copper-ammonia complexes formation reduced the immobilization efficiency to zero. The reductions were attributed either to the low degree of urea hydrolysis or to inappropriate pH conditions. The findings shed light on the necessity of securing the urease activity and modifying pH conditions using the two-step biomineralization approach while applying the MICP technology to remedy copper-rich water bodies.

A Prognostic Survival Model of Pancreatic Adenocarcinoma Based on Metabolism-Related Gene Expression.

Accurately predicting the survival prospects of patients suffering from pancreatic adenocarcinoma (PAAD) is challenging. In this study, we analyzed RNA matrices of 182 subjects with PAAD based on public datasets obtained from The Cancer Genome Atlas (TCGA) as training datasets and those of 63 subjects obtained from the Gene Expression Omnibus (GEO) database as the validation dataset. Genes regulating the metabolism of PAAD cells correlated with survival were identified. Furthermore, LASSO Cox regression analyses were conducted to identify six genes (XDH, MBOAT2, PTGES, AK4, PAICS, and CKB) to create a metabolic risk score. The proposed scoring framework attained the robust predictive performance, with 2-year survival areas under the curve (AUCs) of 0.61 in the training cohort and 0.66 in the validation cohort. Compared with the subjects in the low-risk cohort, subjects in the high-risk training cohort presented a worse survival outcome. The metabolic risk score increased the accuracy of survival prediction in patients suffering from PAAD.

[Study on the gene mutation of quinolone-resistant Mycobacterium tuberculosis isolated from Sichuan Province].

OBJECTIVE: To investigate the molecular mechanism of quinolone-resistance of M. tuberculosis and characterize the gene mutation in Sichuan Province. METHODS: Susceptibility of the clinical isolates to quinolones (ofloxacin, ciprofloxacin and sparfloxacin) was tested by the absolute concentration method. GyrA gene quinolone reasistance-determining region (QRDR) mutations M. tuberculosis were detected with PCR-SSCP and DNA sequencing. RESULTS: Of 68 clinical isolates of M. tuberculosis, 25 high-resistant, 11 low-resistant and 10 sensitive isolates were noted to have abnormal gyrA SSCP profile and different gyrA sequences from the standard strain H37Rv, and 14 sensitive and 8 low-resistant isolates were found with no mutation of gyrA gene. DNA sequencing unveiled Ser-->Thr mutation at codon 95, Asp-->Gly at codon 94, Ala-->Val at codon 90, and Ala-->Val at codon 83. CONCLUSION: This study confirmed the strong correlation between the quinolone-resistance and the mutation of gyrA gene, which might be a major molecular mechanism of quinolone-resistance in M. tuberculosis. The types of mutations exhibit no difference between Sichuan Province and other areas in China.