Aminobenzenesulfonamide functionalized SBA-15 nanoporous molecular sieve: A new and promising adsorbent for preconcentration of lead and copper ions

A rapid method for the extraction and monitoring of nanogram level of Pb²⁺ and Cu²⁺ ions using uniform silanized mesopor (SBA-15) functionalized with aminobenzenesulfonamide groups and flame atomic absorption spectrometry (FAAS) is presented. Aminobenzenesulfonamide functionalized SBA-15 was synthesized according to procedure in the literature and the presence of organic groups in the silica framework was demonstrated by FT-IR spectra. The functionalized product showed the BET surface area 110 m²/g and pore diameter 5.1 nm, based on adsorption-desorption of N₂ at 77 K. The effect of several variables such as (amount of adsorbent, stirring time, pH and presence of other ions in the medium) has been studied. Lead and copper were completely extracted at pH greater than 3 after stirring for 10 min. The maximum capacity of the adsorbent was found to be 191.3 ± 1.4 and 155.0 ± 1.0 μg of lead and copper ions/mg functionalized SBA-15, respectively. The preconcentration factor of the method was found to be 200. The detection limit of the technique was 3.4 and 0.4 ng/mL for Pb²⁺ and Cu²⁺, respectively. The applications of this methodology for real samples were examined by various water type, black tea and pepper samples.     

Cause of PM2.5 pollution during the 2016-2017 heating season in Beijing, Tianjin, and Langfang, China

To investigate the cause of fine particulate matter (particles with an aerodynamic diameter less than 2.5 µm, PM_2.5) pollution in the heating season in the North China Plain (specifically Beijing, Tianjin, and Langfang), water-soluble ions and carbonaceous components in PM_2.5 were simultaneously measured by online instruments with 1-hr resolution, from November 15, 2016 to March 15, 2017. The results showed extreme severity of PM_2.5 pollution on a regional scale. Secondary inorganic ions (SNA, i.e., NO₃^?+SO₄²+ NH₄⁺) dominated the water-soluble ions, accounting for 30%-40% of PM_2.5, while the total carbon (TC, i.e., OC + EC) contributed to 26.5%-30.1% of PM_2.5 in the three cities. SNA were mainly responsible for the increasing PM_2.5 pollution compared with organic matter (OM). NO₃^? was the most abundant species among water-soluble ions, but SO₄^2- played a much more important role in driving the elevated PM_2.5 concentrations. The relative humidity (RH) and its precursor SO₂ were the key factors affecting the formation of sulfate. Homogeneous reactions dominated the formation of nitrate which was mainly limited by HNO₃ in ammonia-rich conditions. Secondary formation and regional transport from the heavily polluted region promoted the growth of PM_2.5 concentrations in the formation stage of PM_2.5 pollution in Beijing and Langfang. Regional transport or local emissions, along with secondary formation, made great contributions to the PM_2.5 pollution in the evolution stage of PM_2.5 pollution in Beijing and Langfang. The favourable meteorological conditions and regional transport from a relatively clean region both favored the diffusion of pollutants in all three cities.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.     

Hydrogeochemical and mineralogical characteristics related to heavy metal attenuation in a stream polluted by acid mine drainage: A case study in Dabaoshan Mine, China

Dabaoshan Mine, the largest mine in south China, has been developed since the 1970s. Acid mine drainage (AMD) discharged from the mine has caused severe environmental pollution and human health problems. In this article, chemical characteristics, mineralogy of ocher precipitations and heavy metal attenuation in the AMD are discussed based on physicochemical analysis, mineral analysis, sequential extraction experiments and hydrogeochemistry. The AMD chemical characteristics were determined from the initial water composition, water-rock interactions and dissolved sulfide minerals in the mine tailings. The waters, affected and unaffected by AMD, were Ca-SO₄ and Ca-HCO₃ types, respectively. The affected water had a low pH, high SO₄^2- and high heavy metal content and oxidation as determined by the Fe²⁺/Fe³⁺ couple. Heavy metal and SO₄^2- contents of Hengshi River water decreased, while pH increased, downstream. Schwertmannite was the major mineral at the waste dump, while goethite and quartz were dominant at the tailings dam and streambed. Schwertmannite was transformed into goethite at the tailings dam and streambed. The sulfate ions of the secondary minerals changed from bidentate- to monodentate-complexes downstream. Fe-Mn oxide phases of Zn, Cd and Pb in sediments increased downstream. However, organic matter complexes of Cu in sediments increased further away from the tailings. Fe³⁺ mineral precipitates and transformations controlled the AMD water chemistry.     

Photocatalytic performance and dispersion stability of nanodispersed TiO2 hydrosol in electrolyte solutions with different cations

The existence of electrolytes in aquatic environment on the photocatalytic performance and coagulation of nanodispersed TiO₂ hydrosol and the corresponding photocatalytic alteration were investigated by studying cations (Na⁺, K⁺, Ca ²⁺, Mg²⁺, and Al³⁺). The photocatalysis reactions of nano TiO₂ with different dosages of electrolytes were measured by monitoring the degradation of Rhodamine B (RhB) under ultraviolet A (UV-A) irradiation over time. The results showed that the photocatalytic performance of TiO₂ was improved by the presence of Al³⁺, while the performance was impaired by the other tested cations. The negative influences of divalent ions on the photocatalytic performance of TiO₂ were more significant than monovalent ions. The TiO₂ sol dispersed stable at nano scale at low concentration of electrolyte (< 0.01?mol/L) with slight change of pH, and coagulated into micro sizes at high concentration of electrolytes (> 0.1?mol/L) with larger increase or decrease of pH. The positive effects of Al³⁺ on the photodegradation rate of RhB might relate to the strong hydrolytic action of Al³⁺ in aquatic solutions. The photocatalytic processes of TiO₂ in the presence of all ions followed the Langmuir-Hinshelwood model, and the reaction kinetic constant was increased with the decrease of pH caused by different cations. These work suggested a new perspective about the relationship between coagulation and photocatalytic performance of TiO₂ hydrosols in electrolyte with hydrolysable cations, which demonstrated that TiO₂ hydrosols may be suitable as photocatalysts in aquatic environments.     

Photoproducts of tetracycline and oxytetracycline involving self-sensitized oxidation in aqueous solutions: Effects of Ca2+ and Mg2+

Tetracyclines constitute one of the most important antibiotic families and represent a classic example of phototoxicity. The photoproducts of tetracyclines and their parent compounds have potentially adverse effects on natural ecosystem. In this study, the self-sensitized oxidation products of tetracycline (TC) and oxytetracycline (OTC) were determined and the effects of Ca²⁺ and Mg²⁺on self-sensitized degradation were investigated. The Ca²⁺ and Mg²⁺ in the natural water sample accounted for enhancement (pH 7.3) and inhibition (pH 9.0) of photodegradation of TC and OTC due to the formation of metal-ions complexes. The formation of Mg²⁺ complexes was unfavorable for the photodegradation of the tetracyclines at both pH values. In contrast, the Ca²⁺ complexes facilitated the attack of singlet oxygen (¹O₂) arising from self-sensitization at pH 7.3 and enhanced TC photodegradation. For the first time, self-sensitized oxidation products of TC and OTC were verified by quenching experiments and detected by LC/ESI-DAD-MS. The products had a nominal mass 14 Da higher than the parent drugs (designated M+14), which resulted from the ¹O₂ attack of the dimethylamino group on the C-4 atom of the tetracyclines. The presence of Ca²⁺ and Mg²⁺ also affected the generation of M+14 due to the formation of metal-ions complexes with TC and OTC. The findings suggest that the metal-ion complexation has significant impact on the self-sensitized oxidation processes and the photoproducts of tetracyclines.     

Adsorption of chloroacetanilide herbicides on soil and its components Ⅲ. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca²⁺-, Mg²⁺ -. Al³⁺ -and Fe³⁺ -saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor ＞ acetolachlor ＞ alachlor ＞ propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg²⁺ ＜ Ca²⁺ ＜ Al³⁺ ≤ Fe³⁺ which coincided with the iucreasing aciditv of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.     

Chemical characteristics and source apportionment of PM2.5 in a petrochemical city: Implications for primary and secondary carbonaceous component

To study the pollution features and underlying mechanism of PM_2.5 in Luoyang, a typical developing urban site in the central plain of China, 303 PM_2.5 samples were collected from April 16 to December 29, 2015 to analyze the elements, water soluble inorganic ions, organic carbon and elemental carbon. The annual mean concentration of PM_2.5 was 142.3 μg/m³, and 75% of the daily PM_2.5 concentrations exceeded the 75 μg/m³. The secondary inorganic ions, organic matter and mineral dust were the most abundant species, accounting for 39.6%, 19.2% and 9.3% of the total mass concentration, respectively. But the major chemical components showed clear seasonal dependence. SO₄^2? was most abundant specie in spring and summer, which related to intensive photochemical reaction under high O₃ concentration. In contrast, the secondary organic carbon and ammonium while primary organic carbon and ammonium significantly contributed to haze formation in autumn and winter, respectively. This indicated that the collaboration effect of secondary inorganic aerosols and carbonaceous matters result in heavy haze in autumn and winter. Six main sources were identified by positive matrix factorization model: industrial emission, combustion sources, traffic emission, mineral dust, oil combustion and secondary sulfate, with the annual contribution of 24%, 20%, 24%, 4%, 5% and 23%, respectively. The potential source contribution function analysis pointed that the contribution of the local and short-range regional transportation had significant impact. This result highlighted that local primary carbonaceous and precursor of secondary carbonaceous mitigation would be key to reduce PM_2.5 and O₃ during heavy haze episodes in winter and autumn.     

Preparation of floating BiOCl0.6I0.4/ZnO photocatalyst and its inactivation of Microcystis aeruginosa under visible light

Frequent occurrence of harmful algal blooms has already threatened aquatic life and human health. In the present study, floating BiOCl_0.6I_0.4/ZnO photocatalyst was synthesized in situ by water bath method, and and applied in inactivation of Microcystis aeruginosa under visible light. The composition, morphology, chemical states, optical properties of the photocatalyst were also characterized. The results showed that BiOCl_0.6I_0.4 exhibited laminated nanosheet structure with regular shape, and the light response range of the composite BZ/EP-3 (BiOCl_0.6I_0.4/ZnO/EP-3) was tuned from 582 to 638 nm. The results of photocatalytic experiments indicated that BZ/EP-3 composite had stronger photocatalytic activity than a single BiOCl_0.6I_0.4 and ZnO, and the removal rate of chlorophyll a was 89.28% after 6 hr of photocatalytic reaction. The photosynthetic system was destroyed and cell membrane of algae ruptured under photocatalysis, resulting in the decrease of phycobiliprotein components and the release of a large number of ions (K⁺, Ca²⁺ and Mg²⁺). Furthermore, active species trapping experiment determined that holes (h⁺) and superoxide radicals (·O₂⁻) were the main active substance for the inactivation of algae, and the p-n mechanism of photocatalyst was proposed. Overall, BZ/EP-3 showed excellent algal removal ability under visible light, providing fundamental theories for practical algae pollution control.     

Chemical compositions of PM2.5 aerosol during haze periods in the mountainous city of Yong'an, China

Haze phenomena were found to have an increasing tendency in recent years in Yong'an, a mountainous industrial city located in the center part of Fujian Province, China. Atmospheric fine particles (PM_2.5) in the urban area during haze periods in three seasons (spring, autumn and winter) from 2007 to 2008 were collected, and the mass concentrations and chemical compositions (seventeen elements, water soluble inorganic ions (WSIIs) and carbonaceous species) of PM_2.5 were determined. PM_2.5 mass concentrations did not show a distinct difference among the three seasons. The carbonaceous species organic carbon (OC) and elemental carbon (EC) constituted up to 19.2%-30.4% of the PM_2.5 mass during sampling periods, while WSIIs made up 25.3%-52.5% of the PM_2.5 mass. The major ions in PM_2.5 were SO₄^2-, NO₃^- and NH₄⁺, while the major elements were Si, K, Pb, Zn, Ca and Al. The experimental results (from data based on three haze periods with a 10-day sampling length for each period) showed that the crustal element species was the most abundant component of PM_2.5 in spring, and the secondary ions species (SO₄^2-, NO₃^-, NH₄⁺, etc.) was the most abundant component in PM_2.5 in autumn and winter. This indicated that dust was the primary pollution source for PM_2.5 in spring and combustion and traffic emissions could be the main pollution sources for PM_2.5 in autumn and winter. Generally, coal combustion and traffic emissions were considered to be the most prominent pollution sources for this city on haze days.     

Die Bleisulfidhalogenide Pb2SJ2 und Pb2SBr2

The Science of Nature -