The influence of titanium dioxide nanoparticles (nTiO₂) on the transport and deposition of polystyrene microplastics (MPs) in saturated quartz sand was investigated in NaCl solutions with ionic strengths from 0.1 to 10 mM at two pH conditions (pH 5 and 7). Three different-sized polystyrene (PS) MPs (diameter of 0.2, 1, and 2 μm) were concerned in present study. We found that for all three different-sized MPs in NaCl solutions (0.1, 1 and 10 mM) at both pH 5 and 7, lower breakthrough curves and higher retained profiles of MPs with nTiO₂ copresent in suspensions relative to those without nTiO₂ were obtained, demonstrating that the copresence of nTiO₂ in MPs suspensions decreased MPs transport and increased their deposition in quartz sand under all examined conditions. The mechanisms contributing to the increased MPs deposition with nTiO₂ in suspensions at two pH conditions were different. The formation of MPs-nTiO₂ heteroaggregates and additional deposition sites provided by previously deposited nTiO₂ were found to drive to the increased MPs deposition with nTiO₂ in suspensions at pH 5, while the formation of MPs-nTiO₂ aggregates, additional deposition sites and increased surface roughness induced by the pre-deposited nTiO₂ on quartz sand surfaces were responsible for the enhanced MPs deposition at pH 7. The results give insights to predict the fate and transport of different-sized MPs in porous media in the copresence of engineered nanoparticles.

In recent years, the concentration of fine particulate matter has decreased gradually in the Pearl River Delta (PRD) region, but the ozone (O₃) concentration remains high and has become the primary air pollutant. In this study, using a three-dimensional numerical model [nested air quality prediction modeling system (NAQPMS)] coupled with an on-line source apportionment module, the contribution of different source regions and source categories to the O₃ concentration in the PRD region was quantified. A comparison with observation data confirmed that the NAQPMS adequately reproduced surface O₃ concentrations in different seasons. Compared with biogenic emissions, anthropogenic precursors play a dominant role in O₃ production. In Guangzhou city, among different source categories, mobile emission is the largest contributor (accounting for approximately 40%), followed by industry emissions (20%–24%). Regional control measures for solvent use and mobile emissions are effective for reducing O₃ concentration. In the PRD region, self-contribution is more significant in daytime (∼40%) than in nighttime (∼10%) on average. Among the source regions outside PRD, the northern part of Guangdong province, Jiangxi province, and Fujian province are important contributors. Within the PRD region, the self-contribution of each city increases by 12%–32% during O₃ episodes (>80 ppbv) compared with the annual mean contribution. The contribution of the entire PRD region and the entire Guangdong province is 46%–63% and 63%–74% in PRD cities during O₃ episodes. These results indicate that regional collaboration on emission control within PRD or Guangdong province is effective for reducing O₃ episodes in the PRD region. In addition, because long-range transport from regions outside Guangdong province played an important role in the O₃ concentration in the PRD region, long-term emission control measures throughout China in subsequent years should be propitious to further reduce the annual O₃ level and improve air quality in the PRD region.

Microplastics (<5 mm) are distributed ubiquitously in natural environments. The majority of microplastics in aquatic environments are shown to have rough surfaces due to various weathering processes (secondary microplastics; SMP), while laboratory studies predominantly utilise pristine microplastics (primary microplastics; PMP). Here we present the results from a study comparing the chronic effects of pristine PMP and artificially weathered SMP to three different Cladoceran species (Daphnia magna, Daphnia pulex, Ceriodaphnia dubia). We assessed the impact of PMP and SMP on reproductive output using various measured parameters, including time of first brood, size of first brood, size of first three broods, cumulative number of neonates, total number of broods and terminal length of test animals. Our results show that reproductive output of all species declined in a dose-dependent manner. The No Observed Effect Concentration (NOEC) was less than the lowest tested concentration (102 p/mL) for at least one measured endpoint for all species and both PMP and SMP. Further, it was inferred that species sensitivity varied inversely with body size for most endpoints, resulting in C. dubia being the most sensitive species; and D. magna being the least sensitive species under study. In addition, PMP appeared to have greater toxic potential as compared to SMP. This study is the first to directly compare the chronic toxicity of both pristine and weathered microplastic particles on three freshwater toxicological model organisms. Our results indicate that sensitivity in reproduction and growth to microplastics may differ between species and type of microplastic exposed; highlighting the importance of using multiple species and structural types of particles.

Recent classification of metformin as an emerging contaminant warrants assessment of its fate and behaviour in the natural environment especially with land-based application of potentially contaminated wastewaters and biosolids. The present study provided further insight into the sorption mechanisms of metformin and its transformation product guanylurea in soil and upon biosolid fortification. Decreased metformin sorption (12.4%) as measured by the effective distribution coefficient (Kdᵉᶠᶠ) was observed with biosolids amendment while significant increase (2500%) in guanylurea sorption was calculated. Analysis of co-solute effects confirmed their contrasting sorption mechanisms with the absence of competitive effects in unamended soil. Results of the column tests were in good agreement with the batch sorption studies as the fitted values of retardation factors decreased and increased for metformin and guanylurea, respectively, upon addition of biosolids. The shapes of the breakthrough curves suggest slower desorption rates for both compounds in unamended soil resulting to non-equilibrium conditions and back-end tailings. However, in biosolid-amended soil columns, these tailings were less pronounced resembling equilibrium transport. Results also demonstrated enhanced mobility of both compounds upon biosolids fortification. The non-equilibrium chemical transport model fitted the measured data well (0.975 > r² > 0.988) especially for unamended soils which suggests the existence of non-equilibrium conditions and rate-limited sorption sites.

Manufactured nanoparticles (MNPs) undergo transformation immediately after they enter wastewater treatment streams and during their partitioning to sewage sludge, which is applied to agricultural soils in form of biosolids. We examined toxicogenomic responses of the model nematode Caenorhabditis elegans to pristine and transformed ZnO-MNPs (phosphatized pZnO- and sulfidized sZnO-MNPs). To account for the toxicity due to dissolved Zn, a ZnSO₄ treatment was included. Transformation of ZnO-MNPs reduced their toxicity by nearly ten-fold, while there was almost no difference in the toxicity of pristine ZnO-MNPs and ZnSO₄. This combined with the fact that far more dissolved Zn was released from ZnO- compared to pZnO- or sZnO-MNPs, suggests that dissolution of pristine ZnO-MNPs is one of the main drivers of their toxicity. Transcriptomic responses at the EC₃₀ for reproduction resulted in a total of 1161 differentially expressed genes. Fifty percent of the genes differentially expressed in the ZnSO₄ treatment, including the three metal responsive genes (mtl-1, mtl-2 and numr-1), were shared among all treatments, suggesting that responses to all forms of Zn could be partially attributed to dissolved Zn. However, the toxicity and transcriptomic responses in all MNP treatments cannot be fully explained by dissolved Zn. Two of the biological pathways identified, one essential for protein biosynthesis (Aminoacyl-tRNA biosynthesis) and another associated with detoxification (ABC transporters), were shared among pristine and one or both transformed ZnO-MNPs, but not ZnSO₄. When comparing pristine and transformed ZnO-MNPs, 66% and 40% of genes were shared between ZnO-MNPs and sZnO-MNPs or pZnO-MNPs, respectively. This suggests greater similarity in transcriptomic responses between ZnO-MNPs and sZnO-MNPs, while toxicity mechanisms are more distinct for pZnO-MNPs, where 13 unique biological pathways were identified. Based on these pathways, the toxicity of pZnO-MNPs is likely to be associated with their adverse effect on digestion and metabolism.

Cadmium is one of the most serious metal pollutants in the Bohai Sea. Previous studies revealed that mitochondrion might be the target organelle of Cd toxicity. However, there is a lack of a global view on the mitochondrial responses in marine animals to Cd. In this work, the mitochondrial responses were characterized in clams Ruditapes philippinarum treated with two concentrations (5 and 50 μg/L) of Cd for 5 weeks using tetraethylbenzimidazolylcarbocyanine iodide (JC-1) staining, ultrastructural observation and quantitative proteomic analysis. Basically, a significant decrease of mitochondrial membrane potential (△Ψm) was observed in clams treated with the high concentration (50 μg/L) of Cd. Cd treatments also induced specific morphological changes indicated by elongated mitochondria. Furthermore, iTRAQ-based mitochondrial proteomics showed that a total of 97 proteins were significantly altered in response to Cd treatment. These proteins were closely associated with multiple biological processes in mitochondria, including tricarboxylic acid (TCA) cycle, oxidative phosphorylation, fatty acid β-oxidation, stress resistance and apoptosis, and mitochondrial fission. These findings confirmed that mitochondrion was one of the key targets of Cd toxicity. Moreover, dynamical regulations, such as reconstruction of energy homeostasis, induction of stress resistance and apoptosis, and morphological alterations, in mitochondria might play essential roles in Cd tolerance. Overall, this work provided a deep insight into the mitochondrial toxicity of Cd in clams based on a global mitochondrial proteomic analysis.

Polycyclic aromatic hydrocarbons containing at least 24 carbon atoms (≥C₂₄-PAH) are often associated with pyrogenic processes such as combustion of fuel, wood or coal, and occur in the environment in diesel particulate matter, black carbon and coal tar. Some of the ≥C₂₄-PAH, particularly the group of dibenzopyrenes (five isomers, six aromatic rings) are known to show high mutagenic and carcinogenic activita.Gas chromatography – mass spectrometry is a well-established method for the analysis of lower molecular weight PAH but is not optimally suited for the analysis of ≥C₂₄-PAH due to their low vapor pressures. Also, hundreds of ≥C₂₄-PAH isomers are possible but only a few compounds are commercially available as reference standards. Therefore, in this study, a combination of multidimensional liquid chromatography, UV–Vis diode array detection, PAH selective and highly sensitive atmospheric pressure laser ionization – mass spectrometry is used to detect and unequivocally identify PAH. For identification of PAH in two bituminous coals and one petrol coke sample, unique and compound specific UV–Vis spectra were acquired. It was possible to identify ten compounds (naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[e,ghi]perylene, dibenzo[cd,lm]perylene, benzo[a]coronene, phenanthrol[5,4,3,2-abcde]perylene, benzo[ghi]naphtho[8,1,2-bcd]perylene, benzo[pqr]naphtho[8,1,2-bcd]perylene, naphtho[8,1,2-abc]coronene and tribenzo[e,ghi,k]perylene) by comparison of acquired spectra with spectra from literature. Additionally, it was possible to detect similar distribution patterns in different samples and signals related to alkylated naphthopyrenes, naphthofluoranthenes or dibenzopyrenes. Subsequent effect-directed analysis of a bituminous coal sample using the microEROD (ethoxyresorufin-O-deethylase) bioassay showed high suitability and revealed lower EROD induction for the ≥C₂₄-PAH (TEQ range 0.67–10.07 ng/g) than for the allover < C₂₄-PAH containing fraction (TEQ 84.00 ng/g). Nevertheless, the toxicity of ≥C₂₄-PAH has a significant impact compared with <C₂₄-PAH and must be considered for risk assessment. The LC-DAD-APLI-MS method, presented in this study, is a powerful tool for the unequivocal identification of these ≥ C₂₄-PAH.

Whilst numerous studies have explored the spatial patterns and underlying causes of PM₂.₅, little attention has been paid to the spatial heterogeneity of the factors affecting PM₂.₅. In this study, a geographically weighted regression (GWR) model was used to explore the strength and direction of nexus between various factors and PM₂.₅ in Chinese cities. A comprehensive interpretive framework was established, composed of 18 determinants spanning the three categories of natural conditions, socioeconomic factors, and city features. Our results indicate that PM₂.₅ concentration levels were spatially heterogeneous and markedly higher in cities in eastern China than in cities in the west of the country. Based on the results of GWR, significant spatial heterogeneity was identified in both the direction and strength of the determinants at the local scale. Among all of the natural variables, elevation was found to be statistically significant with its effects on PM₂.₅ in 95.60% of the cities and it correlated negatively with PM₂.₅ in 99.63% cities, with its effect gradually weakening from the eastern to the western parts of China. The variable of built-up areas emerged as the strongest variable amongst the socioeconomic variables studied; it maintained a positive significant relationship in cities located in the Pearl River Delta and surrounding areas, while in other cities it exhibited a negative relationship to PM₂.₅. The highest coefficients were located in cities in northeast China. As the strongest variable amongst the six landscape factors, patch density maintained a positive relationship in part of cities. While in cities in the northeast regions, patch density exhibited a negative relationship with PM₂.₅, revealing that increasing urban fragmentation was conducive to PM₂.₅ reductions in those regions. These empirical results provide a basis for the formulation of targeted and differentiated air quality improvement measures in the task of regional PM₂.₅ governances.

At present, the study of microplastic sources is in a relatively preliminary stage due to the complexity of microplastic features in the environment. Based on a literature review, we developed a source-specific classification system for the quantitative analysis of microplastic sources. The classification system includes ten types of microplastics based on morphology and composition and can identify their main sources and the associated probabilities. To reflect the complexity of types and sources in the regional combination of microplastics, we first propose a microplastic diversity index (D1-D’(MP)). We use the South China Sea as an example to carry out quantitative source analysis and calculate the diversity index. Eight types of microplastics were found, mainly consisting of maritime coatings (type “Gran_coat”) (33.0%) and synthetic fibers (type “Fib_thin”) (29.6%). We also found that the diversity increased with offshore distance. In addition, we partitioned surface microplastics globally according to a two-dimensional microplastic abundance-diversity index. We believe that these indicators can effectively reflect pollution status and ultimately lead to different types of control measures. In the future, additional indicators for the characterization of microplastics must be included in the classification system to establish a one-to-one source analysis system for microplastic characteristics and source apportionment. In general, our study may provide new insights into the establishment of more accurate and quantitative source apportionment techniques and effective pollution control.

Frequently detected residuals of antibiotics in crops has drawn increasing attention from research community and the general public. This study was conducted under the controlled environmental conditions to investigate the uptake, translocation and distribution of three different veterinary antibiotics (VAs) in plants of Zea mays L. (maize, the third largest crop in the world, especially in China) and the associated mechanisms. The distribution color-maps of mixed-VAs showed that the highest RCF (root concentration factors) values of chlortetracycline (CTC) and sulfamethoxazole (SMZ) were found in the 0.5–2.0 mm zone (cell division zone), while the highest RCF value of sulfathiazole (ST) was in the 6.0–8.0 mm zone (elongation zone) of root tips (0.5–10.0 mm) after 120 h of exposure to VAs. The translocation factor (TF) of CTC was greater than 1.0, but the TFs of SMZ and ST were less than 1.0 under addition of single antibiotic. However, the TFs of three VAs were all greater than 1.0 at the end of exposure under addition of mixed-VAs. The dissipation of antibiotics by maize was also demonstrated by harvesting all plant parts in an enclosed system. The possible mechanisms for uptake and translocation of VAs in maize were investigated by adding multiple respiration inhibitors into the culture solution. The RCFs of VAs were suppressed heavily by salicylhydroxamic acid (SHAM) and sodium azide (NaN3), which indicates that the uptake of VAs was an active process. The results of TFs and stem concentration factors (SCFs) of CTC and SMZ in HgCl2 treatments revealed that the translocation of VAs was associated with the aquaporin activity in maize. The findings from this study will have significant implications for the management of crop food contamination by VAs and for the development of phytoremediation technology for antibiotics in the environment.