Search Results (11)

In this work, PM_2.5 was sampled at Dunkerque, a medium-sized city located in northern France. The mean concentration of PM_2.5 during the sampling period was 12.6 ± 9.5 μg·m⁻³. Samples were analyzed for elemental and organic carbon (EC/OC), water-soluble organic carbon (WSOC), humic-like substances (HULIS-C), water-soluble inorganic ions, and major and trace elements. The origin and the variations of species concentrations were examined using elemental enrichment factors, bivariate polar plot representations, and diagnostic concentration ratios. Secondary inorganic ions were the most abundant species (36% of PM_2.5), followed by OC (12.5% of PM_2.5). Secondary organic carbon (SOC) concentrations were estimated to account for 52% of OC. A good correlation between SOC and WSOC indicated that secondary formation processes significantly contribute to the WSOC concentrations. HULIS-C also represents almost 50% of WSOC. The determination of diagnostic ratios revealed the influence of anthropogenic emission sources such as integrated steelworks and fuel oil combustion. The clustering of 72 h air masses backward trajectories data evidenced that higher concentrations of PM_2.5, OC, and secondary inorganic aerosols were recorded when air masses came from north-eastern Europe and the French continental sector, showing the considerable impact of long-range transport on the air quality in northern France. Full article

Throughout the cold and the warm periods of 2020, chemical and toxicological characterization of the water-soluble fraction of size segregated particulate matter (PM) (<0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2 and >7.2 μm) was conducted in the urban agglomeration of Thessaloniki, northern Greece. Chemical analysis of the water-soluble PM fraction included water-soluble organic carbon (WSOC), humic-like substances (HULIS), and trace elements (V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd and Pb). The bulk (sum of all size fractions) concentrations of HULIS were 2.5 ± 0.5 and 1.2 ± 0.3 μg m⁻³, for the cold and warm sampling periods, respectively with highest values in the <0.49 μm particle size fraction. The total HULIS-C/WSOC ratio ranged from 17 to 26% for all sampling periods, confirming that HULIS are a significant part of WSOC. The most abundant water-soluble metals were Fe, Zn, Cu, and Mn. The oxidative PM activity was measured abiotically using the dithiothreitol (DTT) assay. In vitro cytotoxic responses were investigated using mitochondrial dehydrogenase (MTT). A significant positive correlation was found between OP_m^DTT, WSOC, HULIS and the MTT cytotoxicity of PM. Multiple Linear Regression (MLR) showed a good relationship between OP_M^DTT, HULIS and Cu. Full article

Atmospheric particulate matter (PM) contains various chemicals, some of which generate in vivo reactive oxygen species (ROS). Owing to their high reactivity and oxidation ability, ROS can cause various diseases. To understand how atmospheric PM affects human health, we must clarify the PM components having oxidative potential (OP) leading to ROS production. According to previous studies, OP is exhibited by humic-like substances (HULIS) in atmospheric PM. However, the OP-dependence of the chemical structures of HULIS has not been clarified. Therefore, in this study, humic acid (HA, a model HULIS material) was exposed to ozone and ultraviolet (UV) irradiation, and its OP and structures were evaluated before and after the reactions using dithiothreitol (DTT) assay and Fourier transform infrared (FT-IR), respectively. The OP of HA was more significantly increased by UV irradiation than by ozone exposure. FT-IR analysis showed an increased intensity of the C=O peak in the HA structure after UV irradiation, suggesting that the OP of HA was increased by a chemical change to a more quinone-like structure after irradiation. Full article

The incidence and mortality rate of lung cancer is the highest in Xuanwei County, Yunnan Province, China. The mechanisms of the high lung incidence remain unclear, necessitating further study. However, the particle size distribution characteristics of HULIS emitted from residential coal combustion (RCC) have not been studied in Xuanwei. In this study, six kinds of residential coal were collected. Size-resolved particles emitted from the coal were sampled by using a burning system, which was simulated according to RCC made in our laboratory. Organic carbon (OC), elemental carbon (EC), water-soluble inorganic ion, water-soluble potentially toxic metals (WSPTMs), water-soluble organic carbon (WSOC), and HULIS-C (referred to as HULIS containing carbon contents) in the different size-segregated particulate matter (PM) samples were determined for health risk assessments by inhalation of PM. In our study, the ratio of HULIS-Cx to WSOCx values in RCC particles were 32.73–63.76% (average 53.85 ± 12.12%) for PM_2.0 and 33.91–82.67% (average 57.06 ± 17.32%) for PM_2.0~7.0, respectively. The carcinogenic risks of WSPTMs for both children and adults exceeded the acceptable level (1 × 10⁻⁶, indicating that we should pay more attention to these WSPTMs). Exploring the HULIS content and particle size distribution of the particulate matter produced by household coal combustion provides a new perspective and evidence for revealing the high incidence of lung cancer in Xuanwei, China. Full article

Humic-like substances (HULIS) are of great interest due to their optical and chemical characteristics. In this study, a total of 180 samples of atmospheric particulate matter (PM) of different sizes were collected from summer 2018 to spring 2019, in order to analyze the size distribution, to investigate the seasonal variation and then to identify the key sources of HULIS. The annual mean concentration of HULIS in the total suspended particulates reached 5.12 ± 1.42 μg/m³. The HULIS concentration was extremely higher in winter (8.35 ± 2.06 μg/m³) than in autumn (4.88 ± 0.95 μg/m³), in summer (3.62 ± 1.68 μg/m³) and in spring (3.36 ± 0.99 μg/m³). The average annual ratio of water-soluble organic carbon (WSOC) to OC and the ratio of HULIS to WSOC reached 0.546 ± 0.092 and 0.56 ± 0.06, respectively. Throughout the whole year, the size distributions of WSOC and HULIS-C were relatively smooth. The peaks of WSOC appeared at 1.8~3.2 μm and 0.56~1.0 μm, while the peaks of HULIS-C were located at 3.2~5.6 μm, 1.0~1.8 μm and 0.18~0.32 μm. The distribution of the HULIS particle mode was similar in spring, summer and autumn, while there was a lower proportion of the coarse mode and a higher proportion of the condensation mode in winter. By using the comprehensive analysis of principal component analysis (PCA), air mass backward trajectories (AMBTs) and fire point maps, key sources of WSOC and HULIS in Shanghai were identified as biomass combustion (48.42%), coal combustion (17.49%), secondary formation (16.07%) and vehicle exhaust (5.37%). The remaining part might be contributed by crustal dust sources, marine sources and/or other possible sources. This study provides new insight into the characteristics and size distribution of HULIS in Shanghai, thereby providing a practical base for further modeling. Full article

The chemical and optical properties and sources of atmospheric PM_2.5 humic-like substances (HULIS) were investigated from October to December 2016 in both industrial and suburban areas in Changzhou, China, during polluted and fair days. The average PM_2.5 concentration in the industrial region was 113.06 (±64.3) μg m⁻³, higher than 85.27 (±41.56) μg m⁻³ at the suburban site. The frequency of polluted days was significantly higher in the industrial region. In contrast, the chemical compositions of PM_2.5 at the two sampling sites exhibited no statistically significant differences. Rapidly increased secondary inorganic ions (SNA = NH₄⁺ + SO₄²⁻ + NO₃⁻) concentrations suggested secondary formation played an important role in haze formation. The daily mean concentration of humic-like substance (HULIS) was 1.8–1.9 times that of HULIS-C (the carbon content of HULIS). Our results showed that HULIS accounted for a considerable fraction of PM_2.5 (industrial region: 6.3% vs. suburban region: 9.4%). There were no large differences in the mass ratios of HULIS-C/WSOC at the two sites (46% in the industrial region and 52% in the suburban region). On average, suburban HULIS-C constituted 35.1% of organic carbon (OC), higher than that (21.1%) in the industrial region. Based on different MAE (mass absorption efficiency) values under different pollution levels, we can infer that the optical properties of HULIS varied with PM levels. Moreover, our results showed no distinct difference in E₂/E₃ (the ratio of light absorbance at 250 nm to that at 365 nm) and AAE_300–400 (Absorption Angstrom Exponent at 300–400 nm) for HULIS and WSOC. the MAE₃₆₅ (MAE at 365 nm) value of HULIS-C was different under three PM_2.5 levels (low: PM_2.5 < 75 μg m⁻³, moderate: PM_2.5 = 75–150 μg m⁻³, high: PM_2.5 > 150 μg m⁻³), with the highest MAE₃₆₅ value on polluted days in the industrial region. Strong correlations between HULIS-C and SNA revealed that HULIS might be contributed from secondary formation at both sites. In addition, good correlations between HULIS-C with K⁺ in the industrial region implied the importance of biomass burning to PM_2.5-bound HULIS. Three common sources of HULIS-C (i.e., vehicle emissions, biomass burning, and secondary aerosols) were identified by positive matrix factorization (PMF) for both sites, but the contributions were different, with the largest contribution from biomass burning in the industrial region and secondary sources in the suburban region, respectively. The findings presented here are important in understanding PM_2.5 HULIS chemistry and are valuable for future air pollution control measures. Full article

In this study, the source-based optical properties of polydisperse carbonaceous aerosols were determined from PM_2.5 concentrations measured at a Global Atmospheric Watch station in South Korea. The extinction and absorption coefficients of carbonaceous aerosols were calculated using the Mie theory and assuming a lognormal size distribution. Based on the mass concentration from the EPA’s Positive Matrix Factorization (PMF) receptor model, which considers five source identification and apportionment factors (biogenic source, local biomass burning, secondary organic aerosol, transported biomass burning, and mixed sources), the source-based size-resolved mass extinction and absorption efficiencies were estimated for each source using a multilinear regression model. The results show that the source-based optical properties depend on the aerosol size and physicochemical characteristics of the chemical compounds. The long-range transport of biomass burning (LBB) aerosol, which has a mass concentration of 20%, holds a 12.1–23.1% total extinction efficiency—depending on the size and refractive index—in the range of 0.1–0.5 μm in geometric mean diameter and humic-like substances (HULIS) imaginary refractive index of 0.006–0.3. Biogenic sources of aerosols with small diameters have higher mass absorption efficiencies (MAE) than other sources, depending on the size and refractive index. Full article

We prepared humo-pectic hydrogels through ionotropic gelation by crosslinking natural pectins of different degree of methyl-esterification with either humic substances (HS) extracted from cow manure compost or humic-like substances (HULIS) from depolymerized lignocellulose biorefinery waste. The hydrogels were characterized by solid-state ¹³C-NMR spectroscopy, scanning electron microscopy, spectroscopic magnetic resonance imaging and rheological analyses. Their ability to work as controlled release systems was tested by following the release kinetics of a previously incorporated model phenolic compound, like phloroglucinol. Our results indicated that the release properties of hydrogels were influenced by the molecular composition of HS and HULIS and by the different degrees of methyl-esterification of pectins. The hydrogel made by the high methoxyl pectin and HS showed the fastest rate of phloroglucinol release, and this was attributed not only to its morphological structure and crosslinking density but also to the least formation of ionic interactions between phloroglucinol and the polysaccharidic chains. Our study suggests that the efficiency of novel humo-pectic hydrogels as sustainable carriers of agroproducts to crops is related to a careful choice of the characteristics of their components. Full article

Lignocellulase production from straw fermentation has been widely investigated but the research has neglected to quantify fermentation-derived residue transformation to the humus-like substance (HULIS). To investigate the conversion efficacy of corn stalk residue to HULIS, the amount of HULIS associated with chemical composition and structural changes of humic acid-like substances (HAL) was investigated in a 30 L solid-state fermentation tank during a short period of eight days. The results show that the highest decomposition rate of corn stalk and the highest activity of cellulase, xylanase, and β-glucosidase appeared at the fourth day. At the end of fermenting process, the amount of humic acid-like substances (HAL) and the percentage of HAL in humus acid (PQ value) increased 17.5% and 8.9%, respectively, indicating Trichoderma reesei facilitates the transformation of corn stalk residue to HAL. Fatty acids decreased while aromatic carbon and carboxyl content significantly increased during the ongoing fermentation, which had a positive impact on the HAL thermal stability. The FTIR spectral and thermal analysis revealed an improvement in HAL degrees of condensation, oxidation, and aromatization. The present study suggests that the residue of corn stalks fermented with T. reesei might be a good fertilizer to improve soil characteristics. Full article

The primary objective of this study was to investigate the molecular compositions of humic-like substances (HULISs) in size-resolved ambient aerosols, which were collected using an Anderson-type air sampler (eight size cuts between 0.43 and 11 μm) during the winter season (i.e., the heating period of 8–12 January 2018) in Songdo, South Korea. The aerosol samples collected during the pre- (preheating, 27 November–1 December 2017) and post-winter (postheating, 12–16 March 2018) periods were used as controls for the winter season samples. According to the concentrations of the chromophoric organics determined at an ultraviolet (UV) wavelength of 305 nm, most of the HULIS compounds were found to be predominantly enriched in particles less than 2.1 μm regardless of the sampling period, which shows that particulate matter (diameter less than 2.5 μm; PM_2.5) aerosols were the dominant carriers of airborne organics. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (UHR FT–ICR MS) analysis of the aerosol-carried organic substances revealed that as the aerosol size increased the proportions of CHO and nitrogen-containing CHO (CHON) compounds decreased, while the proportion of sulfur-containing CHO (CHOS) species increased. In particular, the ambient aerosols during the heating period seemed to present more CHO and CHON and less CHOS molecules compared to aerosols collected during the pre- and postheating periods. The aerosols collected during the heating period also exhibited more aromatic nitrogen-containing compounds, which may have originated from primary combustion processes. Overall, the particle size distribution was likely influenced by source origins; smaller particles are likely from local sources, such as traffic and industries, and larger particles (i.e., aged particles) are likely derived from long-range transport generating secondary organic aerosols (SOAs) in the atmosphere. The results of the size-segregated particles can be utilized to understand particle formation mechanisms and shed light on their toxicity to human health. Full article

In this study, the sensitivity of the optical properties of carbonaceous aerosols, especially humic-like substances (HULIS), are investigated based on a one-year measurement of ambient fine atmospheric particulate matter (PM_2.5) at a Global Atmospheric Watch (GAW) station in South Korea. The extinction, absorption coefficient, and radiative forcing (RF) are calculated from the analysis data of water soluble (WSOC) and insoluble (WISOC) organic aerosols, elemental carbon (EC), and HULIS. The sensitivity of the optical properties on the variations of refractive index, hygroscopicity, and light absorption properties of HULIS as well as the polydispersity of organic aerosols are studied. The results showed that the seasonal absorption coefficient of HULIS varied from 0.09 to 11.64 Mm⁻¹ and EC varied from 0.11 to 3.04 Mm⁻¹ if the geometric mean diameter varied from 0.1 to 1.0 µm and the geometric standard deviation varied from 1.1 to 2.0, with the imaginary refractive index (IRI) of HULIS varying from 0.006 to 0.3. Subsequently, this study shows that the RF of HULIS was larger than other constituents, which suggested that HULIS contributed significantly to radiative forcing. Full article