Contribution of liquid water content (LWC) to the levels of the carcinogenic particulate nitro(so) compounds and the chemistry affecting LWC were investigated based on the observation of seven nitrosamines and two nitramines in rural (Seosan) and urban (Seoul) area in South Korea during October 2019 and a model simulation. The concentrations of both the total nitrosamines and nitramines were higher in Seosan (12.48 ± 16.12 ng/m³ and 0.65 ± 0.71 ng/m³, respectively) than Seoul (7.41 ± 13.59 ng/m³ and 0.24 ± 0.15 ng/m³, respectively). The estimated LWC using a thermodynamic model in Seosan (12.92 ± 9.77 μg/m³) was higher than that in Seoul (6.20 ± 5.35 μg/m³) mainly due to higher relative humidity (75 ± 9% (Seosan); 62 ± 10% (Seoul)) and higher concentrations of free ammonia (0.13 ± 0.09 μmol/m³ (Seosan); 0.08 ± 0.01 μmol/m³ (Seoul)) and total nitric acid (0.09 ± 0.07 μmol/m³ (Seosan); 0.04 ± 0.02 μmol/m³ (Seoul)) in Seosan while neither fog nor rain occurred during the sampling period. The relatively high concentrations of the particulate nitrosamines (>30 ng/m³) only observed probably due to the higher LWC (>10 μg/m³) in Seosan. It implies that aqueous phase reactions involving NO₂ and/or uptake from the gas phase enhanced by LWC could be promoted in Seosan. Strong correlation between the concentrations of nitrosodi-methylamine (NDMA), an example of nitrosamines, simulated by a kinetic box model including the aqueous phase reactions and the measured concentration of NDMA in Seosan (R = 0.77; 0.37 (Seoul)) indicates that the aqueous phase reactions dominantly enhanced the NDMA concentrations in Seosan. On the other hand, it is estimated that the formation of nitrosamines by aqueous phase reaction was not significant due to the relatively lower LWC in Seoul compared to that in Seosan. Furthermore, it is presumed that nitramines are mostly emitted from the primary emission sources. This study implies that the concentration of the particulate nitrosamines can be promoted by aqueous phase reaction enhanced by LWC.

Hydrochar (HC) serves as a promising adsorbent to remove the cadmium from aqueous solution due to porous structure. The chemical aging method is an efficient and easy-operated approach to improve the adsorption capacity of HC. In this study, four chemical aging hydrochars (CAHCs) were obtained by using nitric acid (HNO₃) with mass fractions of 5% (N5-HC), 10% (N10-HC), and 15% (N15-HC) to age the pristine HC (N0-HC) and remove the Cd²⁺ from the aqueous solution. The results displayed that the N15-HC adsorption capacity was 19.99 mg g⁻¹ (initial Cd²⁺ concentration was 50 mg L⁻¹), which increased by 7.4 folds compared to N0-HC. After chemical aging, the specific surface area and oxygen-containing functional groups of CAHCs were increased, which contributed to combination with Cd²⁺ by physical adsorption and surface complexation. Moreover, ion exchange also occurred during the adsorption process of Cd²⁺. These findings have important implications for wastewater treatment to transform the forestry waste into a valuable adsorbent for Cd²⁺ removal from water.

The performance of the cathode significantly affects the ability of the electro-Fenton (EF) process to degrade chemicals. In this study, a simple method to modify the graphite felt (GF) cathode was proposed, i.e. oxidizing GF by hydrothermal treatment in nitric acid. The surface physical and electrochemical properties of modified graphite felt were characterized by several techniques: scanning electron microscope (SEM), water contact angle, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and linear scanning voltammetry (LSV). Compared with an unmodified GF (GF-0), the oxygen reduction reaction (ORR) activity of a modified GF was significantly improved due to the introduction of more oxygen-containing functional groups (OGs). Furthermore, the results showed that GF was optimally modified after 9 h (GF-9) of treatment. As an example, the H₂O₂ generation by GF-9 was 2.26 times higher than that of GF-0. After optimizing the process parameters, which include the initial Fe²⁺ concentration and current density, the apparent degradation rate constant of levofloxacin (LEV) could reach as high as 0.40 min⁻¹. Moreover, the total organic carbon (TOC) removal rate and mineralization current efficiency (MCE) of the modified cathode were much higher than that of the GF-0. Conclusively, GF-9 is a promising cathode for the future development in organic pollutant removal via EF.

Secondary inorganic aerosols, including sulfate, nitrate, and ammonium contribute to a large extent to the severe haze pollution events in China. Understanding their formation mechanisms is critical for designing effective mitigation strategies to control haze pollution, especially as the role of nitrate seemed to become more important recently, especially in some megacities. In the present study, simultaneous observations were conducted in two megacities (Chengdu and Chongqing) in Sichuan Basin of southwest China, one of the regions suffering from severe aerosol pollution. One typical long-lasting pollution event in Chengdu and Chongqing was captured during wintertime from December 25, 2016 to January 5, 2017. The campaign-average of hourly concentrations of PM2.5, sulfate, and nitrate, measured by an Aerosol Analyzer (ZSF) were 101 ± 73.8 μg/m3, 15.9 ± 11.8 μg/m3, and 24.9 ± 20.6 μg/m3, respectively, in Chengdu, and were 87.7 ± 53.8 μg/m3, 19.7 ± 13.5 μg/m3, and 15.1 ± 10.1 μg/m3, respectively, in Chongqing. Nitrate contributed substantially to PM2.5 pollution when PM2.5 was lower than 150 μg/m3, largely due to the strong secondary transformation of NOX to nitrate during the occurrence of the pollution episode. Heterogeneous hydrolysis of N2O5 dominated nitrate formation during nighttime, while photochemical reactions and high-RH enhanced gas- to aqueous-phase dissolution of NH3 and HNO3 or cloud processes likely played important roles for nitrate formation during daytime. RH-dependent heterogeneous reactions contributed greatly to the formation of sulfate. NOX is confirmed to play an important role as an oxidant in accelerating the secondary transformation of SO2 to sulfate at high RH and low O3 levels under neutralization condition during heavy PM2.5 pollution episode. Results from this study identified the formation mechanism of nitrate, especially during the daytime, and addressed the importance of heterogeneous inorganic reactions in the formation of heavy aerosol pollution events.

To identify the sources and heterogeneous reactions of sulfate and nitrate with dust in the atmosphere, airborne particles in Xi'an, inland China during the spring of 2017 were collected and measured for chemical compositions, along with a laboratory simulation of the heterogeneous formation of ammonium nitrate on the dust surface. Our results showed that concentrations of Ca²⁺, Na⁺ and Cl⁻ in the TSP samples were enhanced in the dust events, with the values of 41.8, 5.4 and 4.0 μg m⁻³, respectively, while NO₃⁻ (7.1 μg m⁻³) and NH₄⁺ (2.4 μg m⁻³) remarkably decreased, compared to those in the non-dust periods. During the dust events, NH₄⁺ correlated only with NO₃⁻ (R² = 0.52) and abundantly occurred in the coarse mode (>2.1 μm), in contrast to that in the non-dust periods, which well correlated with sulfate and nitrate and enriched in the fine mode (<2.1 μm). SO₄²⁻ in Xi'an during the dust events existed mostly as gypsum (CaSO₄·2H₂O) and mirabilite (Na₂SO₄·10H₂O) and dominated in the coarse mode, suggesting that they were directly transported from the upwind Gobi Desert region. Our laboratory simulation results showed that during the long-range transport hygroscopic salts in the Gobi dust such as mirabilite can absorb water vapor and form a liquid phase on the particle surface, then gaseous NH₃ and HNO₃ partition into the aqueous phase and form NH₄NO₃, resulting in the strong correlation of NH₄⁺ with NO₃⁻ and their accumulation on dust particles. The dry deposition flux of total inorganic nitrogen (NH₄⁺ + NO₃⁻) in Xi'an during the dust events was 0.97 mg-N m⁻² d⁻¹ and 37% higher than that in the non-dust periods. Such a significant enhanced N-deposition is ascribed to the heterogeneous formation of NH₄NO₃ on the dust particle surface, which has been ignored and should be included in future model simulations.

Mangrove sediments can store high amount of pollutants that can be more or less bioavailable depending on environmental conditions. When in available forms, these elements can be subject to an uptake by mangrove biota, and can thus become a problem for human health. The main objective of this study was to assess the distribution of some trace elements (Fe, Mn, Co, Ni, Cr, As, and Cu) in tissues of different plants and snails in a tropical mangrove (Can Gio mangrove Biosphere Reserve) developing downstream a megacity (Ho Chi Minh City, Vietnam). In addition, we were interested in the relationships between mangrove habitats, sediment quality and bioaccumulation in the different tissues studied. Roots and leaves of main mangrove trees (Avicennia alba and Rhizophora apiculata) were collected, as well as different snail species: Chicoreus capucinus, Littoraria melanostoma, Cerithidea obtusa, Nerita articulata. Trace elements concentrations in the different tissues were determined by ICP-MS after digestion with concentrated HNO₃ and H₂O₂. Concentrations differed between stands and tissues, showing the influence of sediment geochemistry, species specific requirements, and eventually adaptation abilities. Regarding plants tissues, the formation of iron plaque on roots may play a key role in preventing Fe and As translocation to the aerial parts of the mangrove trees. Mn presented higher concentrations in the leaves than in the roots, possibly because of physiological requirements. Non-essential elements (Ni, Cr and Co) showed low bioconcentration factors (BCF) in both roots and leaves, probably resulting from their low bioavailability in sediments. Regarding snails, essential elements (Fe, Mn, and Cu) were the dominant ones in their tissues. Most of snails were “macroconcentrators” for Cu, with BCF values reaching up to 42.8 for Cerithidea obtusa. We suggest that high quantity of As in all snails may result from its high bioavailability and from their ability to metabolize As.

Continual efforts have been made to determine a simple and universal method of estimating heavy metal phytoavailability in terrestrial systems. In the present study, a mechanism-based multi-surface model (MSM) was developed to predict the partition of Ni(II) in soil–solution phases and its bioaccumulation in wheat (Triticum aestivum L.) in 19 Chinese soils with a wide range of soil properties. MSM successfully predicted the Ni(II) dissolution in 0.01 M CaCl2 extracting solution (R2 = 0.875). The two-site model for clay fraction improved the prediction, particularly for alkaline soils, because of the additional consideration of edge sites. More crucially, the calculated dissolved Ni(II) was highly correlated with the metal accumulation in wheat (R2 = 0.820 for roots and 0.817 for shoots). The correlation coefficients for the MSM and various chemical extraction methods have the following order: soil pore water > MSM ≈ diffuse gradient technique (DGT) > soil total Ni > 0.43 M HNO3 > 0.01 M CaCl2. The results suggested that the dissolved Ni(II) calculated using MSM can serve as an effective indicator of the bioavailability of Ni(II) in various soils; hence, MSM can be used as an supplement for metal risk prediction and assessment besides chemical extraction techniques.

In Mediterranean areas, dry deposition is a major component of the total atmospheric N input to natural habitats, particularly to forest ecosystems. An innovative approach, combining the empirical inferential method (EIM) for surface deposition of NO₃⁻ and NH₄⁺ with stomatal uptake of NH₃, HNO₃ and NO₂ derived from the DO₃SE (Deposition of Ozone and Stomatal Exchange) model, was used to estimate total dry deposition of inorganic N air pollutants in four holm oak forests under Mediterranean conditions in Spain. The estimated total deposition varied among the sites and matched the geographical patterns previously found in model estimates: higher deposition was determined at the northern site (28.9 kg N ha⁻¹ year⁻¹) and at the northeastern sites (17.8 and 12.5 kg N ha⁻¹ year⁻¹) than at the central-Spain site (9.4 kg N ha⁻¹ year⁻¹). On average, the estimated dry deposition of atmospheric N represented 77% ± 2% of the total deposition of N, of which surface deposition of gaseous and particulate atmospheric N averaged 10.0 ± 2.9 kg N ha⁻¹ year⁻¹ for the four sites (58% of the total deposition), and stomatal deposition of N gases averaged 3.3 ± 0.8 kg N ha⁻¹ year⁻¹ (19% of the total deposition). Deposition of atmospheric inorganic N was dominated by the surface deposition of oxidized N in all the forests (means of 54% and 42% of the dry and total deposition, respectively). The relative contribution of NO₂ to dry deposition averaged from 19% in the peri-urban forests to 11% in the most natural site. During the monitoring period, the empirical critical loads provisionally proposed for ecosystem protection (10–20 kg N ha⁻¹ year⁻¹) was exceeded in three of the four studied forests.

Correct characterization of metal speciation and reactivity is a prerequisite for the risk assessment and remedial activity management of contaminated soil. To better understand the intrinsic reactivity of Pb and Zn, nine heavily and poorly contaminated soils were investigated using the combined approaches of chemical extractions, multi-element stable isotopic dilution (ID) method, and multi-surface modelling. The ID results show that 0.1–38% of total Pb and 3–45% of total Zn in the studied soils are isotopically exchangeable after a 3-day equilibration. The intercomparison between experimental and modelling results evidences that single extraction with 0.43 M HNO3 solubilizes part of non-isotopically exchangeable fraction of Pb and Zn in the studied soils, and cannot be used as a surrogate for ID to assess labile Pb and Zn pools in soil. Both selective sequential extraction (SSE) and modelling reveal that Mn oxides are the predominant sorption surface for Pb in the studied soils; while Zn is predicted to be mainly associated with soil organic matter in the soil with low pH and Fe/Mn oxides in the soils with high pH. Multi-surface modelling can provide a reasonable prediction of Pb and Zn adsorption onto different soil constituents for the most of the studied soils. The modelling could be a promising tool to decipher the underlying mechanism that controls metal reactivity in soil, but the submodel for Mn oxides should be incorporated and the model parameters, especially for the 2-pK diffuse layer model for Mn oxides, should be updated in the further studies.

Air pollution plays a pivotal role in the deterioration of many materials used in buildings and cultural monuments causing an inestimable damage. This study aims to estimate the impacts of air pollution (SO2, HNO3, O3, PM10) and meteorological conditions (temperature, precipitation, relative humidity) on limestone, copper and bronze based on high resolution air quality data-base produced with AMS-MINNI modelling system over the Italian territory over the time period 2003–2010. A comparison between high resolution data (AMS-MINNI grid, 4 × 4 km) and low resolution data (EMEP grid, 50 × 50 km) has been performed. Our results pointed out that the corrosion levels for limestone, copper and bronze are decreased in Italy from 2003 to 2010 in relation to decrease of pollutant concentrations. However, some problem related to air pollution persists especially in Northern and Southern Italy. In particular, PM10 and HNO3 are considered the main responsible for limestone corrosion. Moreover, the high resolution data (AMS-MINNI) allowed the identification of risk areas that are not visible with the low resolution data (EMEP modelling system) in all considered years and, especially, in the limestone case. Consequently, high resolution air quality simulations are suitable to provide concrete benefits in providing information for national effective policy against corrosion risk for cultural heritage, also in the context of climate changes that are affecting strongly Mediterranean basin.