Mineral-associated soil organic matter: characteristics and behavior under diagenesis

The main part of soil organic matter (OM) is mineral-associated: 88 ± 11% of С and even more – 93 ± 9% of N. The aims of the given study were: 1 – to demonstrate experimentally the adsorption selectivity of organic compounds towards minerals with different physico-chemical properties (palygorskite vs montmorillonite); 2 – to characterize mineral-associated OM of buried Late Holocene palaeosols and estimate its diagenetic transformations; 3 – to investigate the OM of humin from modern soils of different genesis and Pleistocene and Holocene palaeosols and estimate its diagenetic transformations. The basic soil properties were determined using standard methods. Clay fractions (<2 um) – natural organo-mineral complexes (OMC) were obtained by sedimentation, their mineralogy was studied by XRD. The elemental composition of OM was studied with CNS-analyzer. The structural characteristics of organic matter were determined with the solid-state 13C-NMR-spectroscopy and FTIR-spectroscopy, isotopic composition of C and N – by mass-spectrometry. The obtained results show that the characteristics of mineral-associated OM depends on the properties of mineral “filter” as well as the fate of OM under diagenesis: how long, in what quantity and quality it will persist. It was shown that palygorskite adsorbed predominantly O-alkyls, which are chemically strongly bound. As a result, the age of fulvic type humus in palygoskite palaeosols can reach 300 My. From other side humus of smectitic paleosols of the same age is present by deeply transformed aromatic structures (“coal”). Mineral-associated OM of buried under kurgans Holocene palaeosols contains more alkyls and carboxylic groups, is less aromatic in a comparison with OM of the respective soils. The specific feature of mineral-associated OM is its enrichment in N-compounds. The later are present by both vegetal and microbial compounds, and demonstrate the large affinity towards the mineral surfaces. The formation of chemical bounds between them provides the persistence of OM in OMC. E.g. H2O2 treatment results in preferential destruction of C-rich compounds and oxidized OM demonstrates larger C/N values. Mineral-associated OM of buried Holocene soils keeps the decreased values of C/N (7–14 vs 14–21 for OM of whole soils). Additionally they are characterized by heavier isotopic composition of δ15N in a comparison with the respective soils (5–11‰ vs 6–9‰). It could be explained either by the accumulation of microbial N, or increasing of the humification degree – the loss of aliphatic C and increasing of aromaticity. Humin is the considerable part of soil humus. Experimentally shown that OM of humins both of soils and OMC is enriched in O-alkyls and C of acetal groups. OM of humins are not homogeneous, and consists from at least two groups: mineral-associated OM and partly mineralized plant fragments. As a consequence, the content of humin in OMC is smaller in a comparison with respective soils. It is concluded that mineral-associated OM and humin as well as soil humus represent dynamic soil systems.

Preparation and selectivity evaluation of grafted temperature-responsive imprinted composite polyvinylidene fluoride resin membranes for selective adsorption of ReO4−

Purpose A novel grafted temperature-responsive ReO4− Imprinted composite membranes (Re-ICMs) was successfully prepared by using polyvinylidene fluoride (PVDF) resin membranes as substrates, this study aimed to separate and purify ReO effectively. Design/methodology/approach Re-ICMs were synthesized by PVDF resin membranes as the substrate, acrylic acid (AA), acrylamide (AM), ethylene glycol dimethacrylate (EGDMA) were functional monomers. The morphology and structure of Re-ICMs were characterized by scanning electron microscope and Fourier transform infrared spectroscopy. Findings The maximum adsorption capacity toward ReO4− was 0.1,163 mmol/g and the separation decree had relation to MnO4− was 19.3. The optimal operation conditions were studied detailedly and the results as follows: the molar ratios of AA, AM, EGDMA, ascorbic acid, NH4ReO4, were 0.8, 0.96, 0.02, 0.003 and 0.006. The optimal time and temperature were 20 h and 40°C, respectively. The Langmuir and pseudo-second-order models were fit these adsorption characteristics well. Practical implications Rhenium (Re) is mainly used to chemical petroleum and make superalloys for jet engine parts. This study was representing a technology in separate and purify of Re, which provided a method for the development of the petroleum and aviation industry. Originality/value This contribution provided a novel method to separate ReO4− from MnO4−. The maximum adsorption capacity was 0.1163 mmol/g at 35°C and the adsorption equilibrium time was within 2 h. Meanwhile, the adsorption selectivity rate ReO4−/MnO4− was 19.3 and the desorption rate was 78.3%. Controlling the adsorption experiment at 35°C and desorption experiment at 25°C in aqueous solution, it could remain 61.3% of the initial adsorption capacity with the adsorption selectivity rate of 13.3 by 10 adsorption/desorption cycles, a slight decrease, varied from 78.3% to 65.3%, in desorption rate was observed.

Synthesis of “(aminomethyl)phosphonic acid-functionalized graphene oxide”, and comparison of its adsorption properties for thorium(IV) ion, with plain graphene oxide

The current study presents a simple and scalable method for the synthesis of (aminomethyl)phosphonic acid-functionalized graphene oxide (AMPA-GO) adsorbent. The chemical structure of the new material was disclosed by different instrumental analyses (e.g. FTIR, Raman, XPS, AFM, TEM, XRD, CHN, and UV), and two pertinent mechanisms namely nucleophilic substitution and condensation were suggested for its formation. Adsorption experiments revealed that both AMPA-GO and plain GO have a high affinity toward Th(IV) ions, but the AMPA-GO is superior in terms of adsorption capacity, rate of adsorption, selectivity, pH effect, etc. Indeed, the AMPA-GO can uptake Th(IV) nearly instantaneously, and coexisting Na+ ions have no effect on its adsorption. Thanks to Langmuir isotherm, the maximum adsorption capacities of the GO and AMPA-GO were obtained 151.06 and 178.67 mg g−1, respectively. Interestingly, GO and AMPA-GO both showed a higher preference for thorium over uranium so that the average “K d (Th)/K d (U)” for them was 52 and 44, respectively. This data suggests that chromatographic separation of thorium and uranium is feasible by these adsorbents.

Separation of Rare-Earth Ions from Mine Wastewater Using B12S Nanoflakes as a Capacitive Deionization Electrode Material

In this study, nanoflakes of B12S were fabricated by plasma-assisted reaction of sulfur dichloride in an ionic liquid at room temperature using europium boride as a hard template. The nanoflakes had an average width and thickness of about 3 1urn and 9.6 nm, respectively, and a large specific surface area of 1197.2 m2 g 1. They behaved like typical electric double-layer capacitors with a capacitance of 201.2 F g 1 at 0.2 mA cm 2 During capacitive deionization to recover rare-earth ions, the nanoflakes had higher adsorption selectivity for Sm3+ than for other competing ions present in real mine waste water. This is due to the strong interaction of the electron-concentered S-groups (S’’’) of the nanoflakes with S m3+. This provides an alternative to construct efficient systems to specifically remove Sm3+ from aqueous solution using B12S nanoflakes. This process demonstrates that other boron sulfide compounds can be used to recover valuable ions by capacitive deionization.

Fabrication of Lignin-based Magnetic Adsorbent via Thiol-ene Click Reaction for the Effective Removal of Pb(II)

The effective and selective removal of heavy metal ions from sewage is a major challenge, and of great significance to the treatment and recovery of metal waste. Herein, a novel magnetic lignin-based adsorbent L@MNP was synthesized by thiol-ene click reaction under UV light irradiation. Multiple characterization techniques containing FT-IR, XRD, elemental analysis, VSM, SEM and TEM confirmed the formed nano-morphology and structure of L@MNP. Effects of pH, contact time, initial metal concentration and temperature on the batch adsorption of Pb(II) by L@MNP were investigated. Due to the existence of sulfur and oxygen containing sites, the maximum adsorption capacity of L@MNP for Pb(II) could reach 97.38 mg/g, while the adsorption equilibrium was achieved within 30 min. Adsorption kinetics and isotherms were well described by the pseudo-second-order model and Langmuir model, respectively, suggesting a chemical and monolayer adsorption process. In addition, L@MNP showed a high adsorption selectivity (kPb = 0.903) toward Pb(II) in the presence of other co-existing metal ions. Experimental results also revealed that L@MNP displayed structural stability, easy recovery under external magnetic field, and acceptable recyclability after the fifth cycle. Considering its facile preparation, low cost and high adsorption efficiency, the developed L@MNP adsorbent demonstrated great potential in removing heavy metal ions from wastewater.

CO2/N2 Gas Separation Using Pebax/ZIF-7—PSf Composite Membranes

In this study, we mixed the zeolitic imidazolate framework-7 (ZIF-7) with poly(ether-b-amide)® 2533 (Pebax-2533) and used it as a selective layer for a composite membrane. We prepared the composite membrane’s substrate using polysulfone (PSf), adjusted its pore size using polyethylene glycol (PEG), and applied polydimethylsiloxane (PDMS) to the gutter layer and the coating layer. Then, we investigated the membrane’s properties of gases by penetrating a single gas (N2, CO2) into the membrane. We identified the peaks and geometry of ZIF-7 to determine if it had been successfully synthesized. We confirmed that ZIF-7 had a BET surface area of 303 m2/g, a significantly high Langmuir surface area of 511 m2/g, and a high CO2/N2 adsorption selectivity of approximately 50. Considering the gas permeation, with ZIF-7 mixed into Pebax-2533, N2 permeation decreased from 2.68 GPU in a pure membrane to 0.43 GPU in the membrane with ZIF-7 25 wt%. CO2 permeation increased from 18.43 GPU in the pure membrane to 26.22 GPU in the ZIF-7 35 wt%. The CO2/N2 ideal selectivity increased from 6.88 in the pure membrane to 50.43 in the ZIF-7 25 wt%. Among the membranes, Pebax-2533/ZIF-7 25 wt% showed the highest permeation properties and the characteristics of CO2-friendly ZIF-7.

Magnetic single atom catalyst in C2N to induce adsorption selectivity toward oxidizing gases

Density functional theory (DFT) method is used to study the effect of single-atom catalyst (SAC) of Mn embedded in C2N nanoribbon (C2N-NR) on the adsorption properties as an attempt to achieve selectivity. Many gases (e.g., CO, CO2, H2, H2O, H2S, N2 and O2) of interest to energy and environmental applications were tested. The results show that SAC-Mn alters chemisorption processes with all gas molecules except N2. Clear adsorption selectivity is obtained towards oxidizing CO, CO2 and O2 molecules as evidenced by the enhancements in binding energy and charge transfer and the reduction in magnetization. While the SAC-Mn contributes predominantly to Fermi-energy region with spin-down states, the strong binding to oxidizing molecules introduces there more spin-up states to compromise and reduce the magnetization. Hence, C2N-NR:Mn is proposed to be used as platform for gas sensor (if combined with magnetic sensor) to yield high selectivity toward these latter gases.

Confined La 2 O 3 particles in mesoporous carbon material for enhanced phosphate adsorption

Novel phosphate adsorbents with confined La 2 O 3 inside mesoporous carbon were fabricated by the solid-state grinding method using pristine mesoporous carbon material CMK-3 (PCMK-3) and oxidized CMK-3 (OCMK-3) as the matrixes (denoted as La 2 O 3 @PCMK-3 and La 2 O 3 @OCMK-3). Compared with pure La 2 O 3 , La 2 O 3 @PCMK-3 and La 2 O 3 @OCMK-3 exhibited higher normalized phosphate adsorption capacity, indicative of efficient loading of La 2 O 3 inside the mesopores of the carbon materials. Furthermore, La 2 O 3 loading led to substantially enhanced phosphate adsorption. The adsorption capacities of La 2 O 3 @OCMK-3 samples were higher than those of La 2 O 3 @PCMK-3 samples, possibly owing to the oxygen-containing groups forming in OCMK-3 during HNO 3 oxidation, which enhanced the dispersion of La 2 O 3 in the mesopores of OCMK-3. The adsorption capacities of La 2 O 3 @PCMK-3 and La 2 O 3 @OCMK-3 increased with the La 2 O 3 loading amount. Phosphate adsorption onto La 2 O 3 (14.7)@PCMK-3 followed the pseudo-second-order kinetics with respect to correlation coefficient values (larger than 0.99). As pH increased from 3.4 to 12.0, the phosphate adsorption amounts of La 2 O 3 (14.7)@PCMK-3 and La 2 O 3 (15.7)@OCMK-3 decreased from 37.64 mg g −1 and 37.08 mg g −1 to 21.92 mg g −1 and 14.18 mg g −1 , respectively. Additionally, La 2 O 3 @PCMK-3 showed higher adsorption selectivity towards phosphate than coexisting Cl − , NO 3 − and SO 4 2 − . The adsorbent La 2 O 3 (14.7)@PCMK-3 remained stable after five regeneration cycles.