Heterogeneous (gas-solid) chemistry of atmospheric Cr: A case study of Astana, Kazakhstan.

Hexavalent chromium (Cr(VI)) is a known carcinogen derived from both anthropogenic and natural sources. This work reports the size-segregated concentrations of total Cr(VI) in particulate matter (PM) in Astana, the capital of Kazakhstan, and provides new insights into the gas-solid reactions of atmospheric Cr. A study of total Cr(VI) in the particulate matter, via a microwave-assisted digestion technique, was conducted using a 5-stage Sioutas Cascade impactor that captures airborne particles in size ranges: >2.5 µm, 1.0-2.5 µm, 0.50-1.0 µm, 0.25-0.50 µm, and <0.25 µm. The total Cr(VI) concentration in the size fraction <0.25 µm was the highest with a maximum value of 9.7 ng/m3. This high concentration may pose a greater risk because smaller airborne particles can penetrate deeper into the lower respiratory tract of the lungs. Total suspended particles Cr(VI) exceeded the 8.0 ng/m3 Reference Concentration (RfC) by 22 times. The overall total Cr(VI) concentration in summer was significantly higher than in fall (p < 0.05), which could be due to factors, including higher temperatures, ozone, and NO2 concentrations in summer and a higher VOC concentration in fall. The results indicate that the interaction between Cr(III) and Cr(VI) through gas-solid reaction can control the speciation of atmospheric Cr.

N,Zn-Doped Fluorescent Sensor Based on Carbon Dots for the Subnanomolar Detection of Soluble Cr(VI) Ions.

The development of a fluorescent sensor has attracted much attention for the detection of various toxic pollutants in the environment. In this work, fluorescent carbon dots (N,Zn-CDs) doped with nitrogen and zinc were synthesized using citric acid monohydrate and 4-pyridinecarboxyaldehyde as carbon and nitrogen sources, respectively. The synthesized N,Zn-CDs served as an "off" fluorescence detector for the rapid and sensitive detection of hexavalent chromium ions (Cr(VI)). The zinc metal integrated into the heteroatomic fluorescent carbon dot played a functional role by creating a coordination site for the hydrogen ions that were displaced after the addition of Cr to the solution matrix. The stepwise addition of Cr(VI) effectively quenched the fluorescence intensity of the N,Zn-CDs, and this phenomenon was attributed to the internal filter effect. A low detection limit of 0.47 nmol/L for Cr(VI) was achieved in the fluorescence experiments. Real water samples were used to evaluate the practical application of N,Zn-CDs for the quantification of Cr(VI). The results show acceptable recoveries and agreement with ion chromatography-ultraviolet spectrometry results. These good recoveries indicate that the fluorescence probe is very well suited for environmental measurements.

Formation of cluster mode particles (1-3 nm) in preschools.

This study is the first study that reports the cluster particle (1-3 nm) formation (CPF) in two modern preschools located in Nur-Sultan city of Kazakhstan from October 28 to November 27, 2019. The average particle number concentration and mode diameter values during major CPF events in Preschool I and Preschool II were found to be 1.90 × 106 (SD 6.43 × 106) particles/cm3 and 1.60 (SD 0.85) nm, and 1.11 × 109 (SD 5.46 × 109) particles/cm3 and 2.16 (SD 1.47) nm, respectively. The ultraviolet PM concentration reached as high as 7 µg/m3 in one of the measurement days. The estimated emission rate in Preschool I for CPF events was 9.57 × 109 (SD 1.92 × 109) particles/min. For Preschool II, the emission rate was 7.25 × 109 (SD 12.4 × 109) particles/min. We identified primary cluster particles (CPs) emitted directly from the sources such as candle burning, and secondary CPs formed as a result of the oxidation of indoor VOCs or smoking VOCs. The secondary CPs are likely to be SOA. Indoor VOCs were mainly emitted during cleaning activities as well as during painting and gluing. Indoor VOCs are the controlling factors in the CPF events. Changes in the training and cleaning programs may result in significant reductions in the exposure of the children to CPs.

Impact of volatile organic compounds on chromium containing atmospheric particulate: insights from molecular dynamics simulations.

The effect of volatile organic compounds (VOCs) on chromium-containing atmospheric particles remains obscured because of difficulties in experimental measurements. Moreover, several ambiguities exist in the literature related to accurate measurements of atmospheric chromium concentration to evaluate its toxicity. We investigated the interaction energies and diffusivity for several VOCs in chromium (III)-containing atmospheric particles using classical molecular dynamics simulations. We analyzed xylene, toluene, ascorbic acid, carbon tetrachloride, styrene, methyl ethyl ketone, naphthalene, and anthracene in Cr(III) solutions, with and without air, to compare their effects on solution chemistry. The interaction energy between Cr(III) and water changed from 48 to 180% for different VOCs, with the highest change with anthracene and the lowest change with naphthalene. The results revealed no direct interactions between Cr(III) particles and the analyzed volatile organic compounds, except ascorbic acid. Interactions of Cr(III) and ascorbic acid differ significantly between the solution phase and the particulate phase. The diffusion of Cr(III) and all the VOCs also were observed in a similar order of magnitude (~ 10-5 cm2/s). The results can further assist in exploring the variation in chromium chemistry and reaction rates in the atmospheric particles in the presence of VOCs.