Metal element-based adsorbents for phosphorus capture: Chaperone effect, performance and mechanism.

Excessive phosphorus (P) enters the water bodies via wastewater discharges or agricultural runoff, triggering serious environmental problems such as eutrophication. In contrast, P as an irreplaceable key resource, presents notable supply-demand contradictions due to ineffective recovery mechanisms. Hence, constructing a system that simultaneously reduce P contaminants and effective recycling has profound theoretical and practical implications. Metal element-based adsorbents, including metal (hydro) oxides, layered double hydroxides (LDHs) and metal-organic frameworks (MOFs), exhibit a significant chaperone effect stemming from strong orbital hybridization between their intrinsic Lewis acid sites and P (Lewis base). This review aims to parse the structure-effect relationship between metal element-based adsorbents and P, and explores how to optimize the P removal properties. Special emphasis is given to the formation of the metal-P chemical bond, which not only depends on the type of metal in the adsorbent but also closely relates to its surface activity and pore structure. Then, we delve into the intrinsic mechanisms behind these adsorbents' remarkable adsorption capacity and precise targeting. Finally, we offer an insightful discussion of the prospects and challenges of metal element-based adsorbents in terms of precise material control, large-scale production, P-directed adsorption and effective utilization.

Microalgae-bacteria tandem-type ponds simultaneously removing ammonia nitrogen and phosphorus towards municipal wastewater advanced treatment.

Low C/N municipal wastewater is difficult to be treated effectively via traditional biological methods, leading to concentrations of pollutants in effluent far exceeding increasingly strict standards. In this work, we propose a novel microalgae-bacteria tandem-type process to simultaneously remove ammonia nitrogen (NH4+-N) and phosphorus (P) from municipal wastewater. A 4.5 L microalgae-bacteria tandem-type reactor was constructed and operated stably for 40 days. The removal efficiencies of NH4+-N and P reached 97.5% and 92.9%, respectively, effluent concentrations were 0.53 and 0.17 mg/L on average, which met the Environmental quality standards for surface water in China (GB 3838-2002). Remarkably, microalgae ponds accounted for 69.3% and 76.3% of the overall NH4+-N and P removal via microalgae assimilation. Furthermore, 16 S rRNA gene amplicon sequencing revealed the abundance of bacteria changed, suggesting that the presence of microalgae leads to some species extinction and low-abundance bacteria increase. This work demonstrated that the microalgae-bacteria tandem-type processes can be efficient and widely applied in the advanced treatment of municipal wastewater.

Corncob biocarriers with available carbon release for Chlamydopodium sp. microalgae towards enhanced nitrogen removal from low C/N rare earth element tailings (REEs) wastewater.

Low nitrogen (N) removal efficiency limits the potential of microalgae technology for the treatment of high nitrogen and low carbon rare earth tailings (REEs) wastewater. In this study, waste corncob was utilized as a biocarrier immobilizing Chlamydopodium sp. microalgae to realize high-efficient treatment of the REEs wastewater. In only 2.5 d, corncob-immobilized microalgae allowed the residual concentrations of N lower than the emission standards, and ammonia nitrogen (NH4+-N) removal rate is 83.3 mg L-1·d-1, total inorganic nitrogen (TIN) removal rate is 86.7 mg L-1·d-1, which was 18.5 times that of the previously-reported microalgae (4.68 mg L-1·d-1). Compared with other microalgae immobilization carriers, corncob possesses the ability to release available carbon sources for microalgae. Composition analysis and sugar verification experiments showed that the main content of TOC released by corncob was monosaccharide, and in a certain range, the removal rate of N was positively correlated with the TOC concentration. The utilization of biomass wastes with dual functions as biological carriers has great potential to improve the performance of microalgae, and is conducive to the development of engineering applications.

Resourceful treatment of harsh high-nitrogen rare earth element tailings (REEs) wastewater by carbonate activated Chlorococcum sp. microalgae.

The discharge of rare earth element (REE) tailings wastewater results in serious ecological deterioration and health risk, due to high ammonia nitrogen, and strong acidity. The low C/N ratio makes it recalcitrant to biodegradation. Recently it has been shown that microalgal technology has a promising potential for the simultaneous harsh wastewater treatment and resource recovery. However, the low nitrogen removal rate and less biomass of microalgae restricted its development. In this work, Chlorococcum sp. was successfully isolated from the rare earth mine effluent. The microalgae was capable of enhancing nitrogen contaminants removal from REEs wastewater due to the carbonate addition, which simulated the activity increase of carbonic anhydrase (CA). The total inorganic nitrogen (TIN) removal rate reached 4.45 mg/L h-1, which compared to other microalgal species, the nitrogen removal rate and biomass yield were 7.8- and 4.9-fold higher, respectively. Notably, high lipid contents (mainly triglycerides, 43.85% of dry weight) and a high biomass yield were obtained. Meanwhile, the microalgae had an excellent settleability attributed to higher extracellular polymeric substance (EPS) formation, leading to easier resource harvest. These results were further confirmed in a continuous-flow photobioreactor with a stable operation for more than 30 days, indicating its potential for application.

Successful isolation of a tolerant co-flocculating microalgae towards highly efficient nitrogen removal in harsh rare earth element tailings (REEs) wastewater.

Acidic rare earth element tailings (REEs) wastewater with high nitrogen and low COD is the most serious and yet unsolved environmental issue in the rare earth mining industry. The effective and cheap remediation of NH4+-N and NO3--N from the REEs wastewater is still a huge challenge. This harsh wastewater environment results in the difficulty for common microbes and microalgae to be survived. In this work, a novel highly tolerant co-flocculating microalgae (the combination of Scenedesmus sp. and Parachlorella sp.) was successfully isolated from the rare earth mine effluent through three-year cultivation. The removal efficiency of total inorganic nitrogen (TIN) by the co-flocculating microalgae cultivation was as high as 90.9%, which is 1.9 times than the average removal efficiency (47.9%) of previously-reported microalgae species in the wastewater with COD/N ratio ranging from 0 to 1. Thus, the residual concentrations of NH4+-N and TIN could reach the Emission Standards of Pollutants from Rare Earths Industry (GB 26451-2011). Along with the high N removal performance, other related characteristics of the co-flocculating microalgae were also revealed, such as high tolerance towards high NH4+-N and strong acid, rapid growth and sedimentation, and simultaneous removal of NH4+-N and NO3--N. These algae characteristics were ascribed to the specific co-flocculating community structure covered by extracellular polymeric substances.

Simultaneous determination of flavonoid and alkaloid compounds in Citrus herbs by high-performance liquid chromatography-photodiode array detection-electrospray mass spectrometry.

The major active biological constituents in Citrus herbs are flavonoids, especially hesperidin, naringin and alkaloids, mainly synephrine, with beneficial medical effects on human health. They are used as the markers to control the quality of Citrus herbs. In this paper, a new ion pairing chromatographic method was developed to exclude the most polar solute (synephrine) from the viod volume and to maintain selectivity between the two other solutes (hesperidin and naringin). Perfluorinated carboxylic acids, which are appropriate for MS detection due to their volatility, were used as ion-pairing agents. The problems of the synephrine separation, such as band tailing and low retention, were solved successfully by using perfluorinated carboxylic acids. The effect of heptafluorobutyric acid (HFBA) was the best in the three investigated perfluorinated carboxylic acids. For the flavanone glycosides, the influence of the perfluorinated acids on retention time was rather weak. The two different kinds of the analytes were separated satisfactorily in one run using an isocratic eluent and the total analysis time takes less than 10 min. The abundance of pseudomolecular ions was recorded using selected ion monitoring (SIM) mode of m/z 135.1, 273.1 and 303.1 for synephrine, naringin and hesperidin, respectively. The contents of hesperidin, naringin and synephrine in several Citrus herbs were simultaneously determined by the proposed method.

Simultaneous determination of nine aristolochic acid analogues in medicinal plants and preparations by high-performance liquid chromatography.

By optimizing the extraction, separation and analytical conditions, a simple, reliable and effective high-performance liquid chromatography method coupled with photodiode array detector (HPLC-DAD) is presented for simultaneous determination of nine aristolochic acid (AA) analogues, i.e., AA I, AA II, AA C, AA D, 7-OH AA I, aristolic acid, AL II, AL III and AL IV, in twelve medicinal herbs and two preparations. The separation was completed on a C18 column with aqueous methanol containing 0.2% (V/V) acetic acid as mobile phase. Linearities of around two orders of magnitude were obtained with correlation coefficients exceeding 0.9950. Satisfactory intra-day and inter-day precisions were achieved with R.S.D.s less than 4.35%, and the average recovery factors obtained were in the range of 88.4-98.8%. The proposed method appears to be suitable for use as a tool for safety assurance and quality control for commercially available suspect samples containing aristolochic acid analogues.

Determination of octopamine, synephrine and tyramine in Citrus herbs by ionic liquid improved 'green' chromatography.

Without adding any volatile organic solvents, aqueous solutions of room temperature ionic liquids (RTILs) were used as 'green' mobile phases to determine octopamine, synephrine and tyramine by liquid chromatography. The problems of the adrenergic amines separation, such as band tailing, low retention and low resolution were solved successfully by using RTIL. The effect of 1-ethyl-3-methylimidazolium tertafluoroborate ([EMIM][BF4]) was the best in the six investigated RTILs. The concentration of [EMIM][BF4], mobile phase pH and column temperature, which influenced the chromatographic behaviors of the analytes, were investigated in detail. The change of retention factors caused by pH shift was obviously suppressed by [EMIM][BF4]. The sensitivity, accuracy and repeatability of this method were found to be satisfactory. The contents of adrenergic amines in several Citrus herbs and extracts, such as Fructus aurantii immaturus, were simultaneously determined by this 'green' chromatographic method.

A simple and sensitive method of nonaqueous capillary electrophoresis with laser-induced native fluorescence detection for the analysis of chelerythrine and sanguinarine in Chinese herbal medicines.

Laser-induced fluorescence (LIF) is a highly sensitive detection method for capillary electrophoresis (CE). However, it usually requires analyte to be derivatized, unless the wavelength of native fluorescence of analyte matches the laser's. That limits its application in drug analysis. In this work, we introduced a rapid, simple and sensitive method of nonaqueous capillary electrophoresis with laser-induced native fluorescence (NACE-LIF) detection for the analysis of chelerythrine and sanguinarine for the first time. As these two alkaloids have some native fluorescence, they were directly detected using a commercially available Ar(+) laser without troublesome fluorescent derivatization. The fluorescence was enhanced by nonaqueous media. Compared with previously reported UV detection method, lower limit of detection (LOD) is achieved thanks to the high sensitivity of LIF detection (2.0ng/mL for chelerythrine and 6.3ng/mL for sanguinarine). Moreover, with NACE, the baseline separation of these alkaloids is finished within 3.5min. This method is successfully applied to determine the contents of chelerythrine and sanguinarine in Macleaya cordata (Willd.) R. Br. and Chelidonium majus L.

Simultaneous analysis of protoberberine, indolequinoline and quinolone alkaloids in coptis-evodia herb couple and the Chinese herbal preparations by high-performance liquid chromatography-electrospray mass spectrometry.

A new and sensitive method has been developed for analysis of protoberberine, indolequinoline and quinolone alkaloids in coptis-evodia herb couple and the Chinese herbal preparations by using HPLC in combination with electrospray mass spectrometry (ESI-MS). Different LC and cone voltages have been optimized prior to this in order to obtain better results and sensitivity. The method was carried out by using a spherigel C(18) analytical column with a gradient solvent system of acetate buffer-acetonitrile-methanol. The contents of alkaloids were measured by pseudomolecule ion on the selective ion recording (SIR) mode. Linearity of around three orders in the magnitude of concentration was generally obtained and limits of detection for these compounds were in the range of 9-30pg.

Simultaneous analysis of theanine, chlorogenic acid, purine alkaloids and catechins in tea samples with the help of multi-dimension information of on-line high performance liquid chromatography/electrospray-mass spectrometry.

A reverse phase high performance liquid chromatography (RP-HPLC) separation coupled with photo diode array detection (DAD) and electrospray ionization mass spectrometry (ESI-MS) detection was established for the analyzing of multiple bioactive compounds in tea and tea extracts. Theanine, chlorogenic acid, purine alkaloids and catechins were identified with authentic standard compounds and with MS-spectra. The content of theanine and catechins was measured by employing DAD and caffeine, chlorogenic acid, theobromine and theopylline by protonated molecular ion on selective ion recording (SIR) mode. The unity of LC/ESI-MS provides more qualitative and quantitative information comparing with general HPLC in the analysis of multi-components in tea, and complex extraction or sample pretreatment is unnecessary. The chromatogram acquired by using this method can be used as a bioactive components fingerprint for the quality control of tea and its extracts. With the help of multi-dimension information of HPLC-DAD-ESIMS, the compounds owning different chemical structure such as amino acid, catechins, etc. in tea and its extracts could be identified and determined in one run successfully.

Simultaneous analysis of caffeic acid derivatives and alkamides in roots and extracts of Echinacea purpurea by high-performance liquid chromatography-photodiode array detection-electrospray mass spectrometry.

High-performance liquid chromatography (HPLC) coupled with UV photodiode-array detection and electrospray ionization mass spectrometry was developed for the simultaneous analysis of caffeic acid derivatives and alkamides in the roots and extracts of Echinacea purpurea. Caffeic acid derivatives and alkamides produced very abundant peaks in the total ion current chromatogram during negative and positive cone voltage switching. Cichoric acid and the isomer pair, dodeca-2E,4E,8Z,10E/Z-tetraenoic acid isobutylamide, were used as a standard for quantification of caffeic acid derivatives and alkamides in E. purpurea. This novel method surpasses previously published ones in product quality control and providing the HPLC chromatographic fingerprints of biological active components in E. purpurea.