Molecular insights into the reactivity of aquatic natural organic matter towards hydroxyl (•OH) and sulfate (SO4•−) radicals using FT-ICR MS

The higher scavenging capacity of natural organic matter (NOM) to hydroxyl radical ((OH)-O-center dot) than sulfate radical (SO4 center dot-) has been long-acknowledged. However, the difference in reactivity and the influence of initial characteristics, especially at the molecular-level, remain unaddressed. In this study, the reactivities of different NOM isolates to (OH)-O-center dot and SO4 center dot- were compared based on the determined second-order rate constants following the depletion of UV254-absorbing moieties. Three NOM isolates with varying characteristics were selected to investigate the influence of initial characteristics on their reactivities. With the identified reactive molecules using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), the distinct reactivity between the radicals and the influence of the initial characteristics were illustrated. The reactivity towards SO4 center dot- was dominated by the electron density of the molecules (i.e., double bond equivalent (DBE)), while that of (OH)-O-center dot was also shaped by molecular size (i.e., m/z) and composition (i.e., N- or S-incorporation). The examination on the exclusively reactive molecules (accounting for 10-20%) reflected a preferred H-abstraction by (OH)-O-center dot and decarboxylation by SO4 center dot-. Moreover, the analysis on the shared reactive molecules (80-90%) based on the UV254 versus electron-donating capacity (EDC) dependency revealed a prevalent (OH)-O-center dot addition while single electron transfer to SO4 center dot-. The different reaction rates associated with the proposed transformation pathways supported the observed higher reactivity of NOM to (OH)-O-center dot than SO4 center dot-

Probing and Comparing the Photobromination and Photoiodination of Dissolved Organic Matter by Using Ultra-High-Resolution Mass Spectrometry

Photochemical halogenation of dissolved organic matter (DOM) may represent an important abiotic process for the formation of natural organobromine compounds (OBCs) and natural organoiodine compounds (OICs) within surface waters. Here we report the enhanced formation of OBCs and OICs by photohalogenating DOM in freshwater and seawater, as well as the noticeable difference in the distribution and composition pattern of newly formed OBCs and OICs. By using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry, various OBCs and OICs were identified during the photohalogenation processes in sunlit waters. The respective number of OBCs and OICs formed in artificial seawater (ASW) under light radiation was higher than that in artificial freshwater (AFW), suggesting a possible role of the mixed reactive halogen species. OBCs were formed mainly via substitution reactions and addition reactions accompanied by other reactions and distributed into three classes: unsaturated hydrocarbons with relatively low oxygen content, unsaturated aliphatic compounds, and saturated fatty acids and carbohydrates with relatively high hydrogen content. Unlike the OBCs, OICs were located primarily in the region of carboxylic-rich alicyclic molecules composed of esterified phenolic, carboxylated, and fused alicyclic structures and were generated mainly through electrophilic substitution of the aromatic proton. Our findings call for further investigation on the exact structure and toxicity of the OBCs and OICs generated in the natural environment

Toxicity of biosynthesized silver nanoparticles to aquatic organisms of different trophic levels

Although biosynthesized nanoparticles are regarded as green products, research on their toxicity to aquatic food chains is scarce. Herein, biosynthesized silver nanoparticles (Alcea rosea-silver nanoparticles, AR-AgNPs) were produced by the reaction of Ag ions with leaf extract of herbal plant Alcea rosea. Then, the toxic effects of AR-AgNPs and their precursors such as Ag+ ions and coating agent (A. rosea leaf extract) on organisms of different trophic levels of a freshwater food chain were investigated. To the three studied aquatic organisms including phytoplankton (Chlorella vulgaris), zooplankton (Daphnia magna) and fish (Danio rerio), the coating agents of AR-AgNPs showed no toxic effects, and Ag+ ions were more toxic in comparison to AR-AgNPs. Further investigations revealed that the release of Ag+ ions from AR-AgNPs to the test media were not considerable due to the high stability of AR-AgNPs, thus the toxicity stemmed mainly from the particles of AR-AgNPs in all the three trophic levels. Based on values of 72-h EC50 for C. vulgaris, 48-h LC50 for D. magna and 96-h LC50 for D. rerio, the most sensitive organism to AR-AgNPs exposure was D. magna (the second trophic level)

Aluminum Dialkyl Phosphinate Flame Retardants and Their Hydrolysates: Analytical Method and Occurrence in Soil and Sediment Samples from a Manufacturing Site

Aluminum dialkyl phosphinates (ADPs) are emerging phosphorus flame retardants due to their superior characteristics, but their analytical method, and occurrence and fate in environments have never been reported. For the first time, we developed a method for the analysis of trace ADPs and their hydrolysates (dialkyl phosphinic acids, DPAs), and studied their occurrences and fates in soils and sediments. We found that ADPs are hardly dissolved in water and organic solvents, but are dissolved and hydrolyzed to DPAs in 30 mM NH₃·H₂O, thus both ADPs and DPAs can be determined by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) in the form of DPAs. ADPs and DPAs in soil and sediment samples were determined by (i) extracting both ADPs and DPAs with 75 mM NH₃·H₂O, and selectively extract DPAs only with formic acid–water–methanol (5:5:90, v/v/v); (ii) quantifying the total content of ADPs and DPAs, and DPAs by LC-MS/MS analysis of the DPA contents in the former and the latter extract, respectively; and (iii) calculating ADPs from the content difference between the former and the latter extracts. The limit of quantifications (LOQs) of the proposed method were 0.9–1.0 μg/kg, and the mean recoveries ranged from 69.0% to 112.4% with relative standard deviations ≤21% (<i>n</i> = 6). In soil and sediment samples around a manufacturing plant, ADPs and DPAs were detected in surface soils in the ranges of 3.9–1279.3 and 1.0–448.6 μg/kg, respectively. While ADPs were found in all the samples of the soil and sediment cores from the drain outlet and the waste residue treatment site at levels ranging from 30.8 to 4628.0 μg/kg, DPAs were found in more than 90% of these samples with concentrations in the range of 1.1–374.6 μg/kg. The occurrences of ADPs and DPAs are not in correlation with the total organic carbon, whereas the occurrences of DPAs are highly correlated with the sample pH. Our study also suggests that the DPAs in the samples sourced from the hydrolysis of ADPs. The high hydrolysis degrees of ADPs (up to 49.6%) suggest that once released into the environment, ADPs are likely to coexist with their hydrolysates. Thus, to evaluate the environmental safety of ADPs, the environmental behavior and toxicity of both ADPs and DPAs should be considered

Swelling-Induced Fragmentation and Polymer Leakage of Nanoplastics in Seawater

Nanoplastics (NPs) have been successively detected in different environmental matrixes and have aroused great concern worldwide. However, the fate of NPs in real environments such as seawater remains unclear, impeding their environmental risk assessment. Herein, multiple techniques were employed to monitor the particle number concentration, size, and morphology evolution of polystyrene NPs in seawater under simulated sunlight over a time course of 29 days. Aggregation was found to be a continuous process that occurred constantly and was markedly promoted by light irradiation. Moreover, the occurrence of NP swelling, fragmentation, and polymer leaching was evidenced by both transmission electron microscopy and scanning electron microscopy techniques. The statistical results of different transformation types suggested that swelling induces fragmentation and polymer leakage and that light irradiation plays a positive but not decisive role in this transformation. The observation of fragmentation and polymer leakage of poly(methyl methacrylate) and poly(vinyl chloride) NPs suggests that these transformation processes are general for NPs of different polymer types. Facilitated by the increase of surface functional groups, the ions in seawater could penetrate into NPs and then stretch the polymer structure, leading to the swelling phenomenon and other transformations

Impact of Precursor Concentration on Perovskite Crystallization for Efficient Wide-Bandgap Solar Cells

High-crystalline-quality wide-bandgap metal halide perovskite materials that achieve superior performance in perovskite solar cells (PSCs) have been widely explored. Precursor concentration plays a crucial role in the wide-bandgap perovskite crystallization process. Herein, we investigated the influence of precursor concentration on the morphology, crystallinity, optical property, and defect density of perovskite materials and the photoelectric performance of solar cells. We found that the precursor concentration was the key factor for accurately controlling the nucleation and crystal growth process, which determines the crystallization of perovskite materials. The precursor concentration based on Cs0.05FA0.8MA0.15Pb(I0.84Br0.16)3 perovskite was controlled from 0.8 M to 2.3 M. The perovskite grains grow larger with the increase in concentration, while the grain boundary and bulk defect decrease. After regulation and optimization, the champion PSC with the 2.0 M precursor concentration exhibits a power conversion efficiency (PCE) of 21.13%. The management of precursor concentration provides an effective way for obtaining high-crystalline-quality wide-bandgap perovskite materials and high-performance PSCs