The present study investigated the physiological responses, photosynthetic activity, and microbial community structure of leaf-associated biofilms on the microphyte Vallisneria natans during a harmful algal bloom. Results of the physiological and photosynthetic indices (Fᵥ/Fₘ ratios [maximum quantum yield of photosystem II (PSII)]; malondialdehyde content; total chlorophyll; and activities of superoxide dismutase, catalase and peroxidase) indicated that algal blooms could cause inhibition of photosynthesis, oxidative stress and an antioxidant system stress response in Vallisneria natans leaf-associated biofilms. Multifractal analysis suggested that allelochemicals or algal organic matter released by cyanobacteria could reduce the surface roughness of the leaf. Microbial diversity analysis of the biofilms showed that algal blooms slightly altered the microbial community structure while the richness and evenness of the microbial composition remained stable. This study provided useful information to better understand the adverse effects of algal blooms on submerged macrophytes.

China continues to suffer from severe acid deposition, despite the government implying a series of policies to control air pollution. In this study, rainwater samples were collected from 2011 to 2016 in Sichuan province to measure the pH values and the concentrations of nine inorganic ions (SO₄²⁻, NO₃⁻, NH₄⁺, Cl⁻, Na⁺, Ca²⁺, K⁺, Mg²⁺, and F⁻), and then to investigate their spatiotemporal variations. Besides, the dominant sources for the acidic ions in the precipitation were also revealed by statistical model. The results showed that the rainwater continued to be highly acidic, and the Volume-Weighted Mean (VWM) pH value was calculated to be 5.18 during 2011 and 2016. NH₄⁺, Ca²⁺, NO₃⁻, and SO₄²⁻ were the dominant water-soluble inorganic ions, accounting for 79.2% of the total ions on average. The remarkable decrease in NO₃⁻ and SO₄²⁻ concentrations (from 75.9 to 54.3 μeq L⁻¹ and from 285 to 145 μeq L⁻¹, respectively) resulted in an increase in the pH value of rainwater from 5.24 in 2011 to 5.70 in 2016. The concentrations of SO₄²⁻, NO₃⁻, F⁻, Na⁺, and K⁺ showed remarkably seasonal variation, with the highest value observed in winter, followed by spring and autumn, and the lowest value observed in summer. High VWM concentration of these ions in winter were mainly due to adverse meteorological conditions (e.g., rare rainfall, lower planetary boundary height, and stagnant air) and intensive anthropogenic emissions. SO₄²⁻, NO₃⁻, and F⁻ ions peaked in the southeastern Sichuan province, which is a typical industrial region. NH₄⁺ concentrations decreased from 268 μeq L⁻¹ in the east to 10.4 μeq L⁻¹ in the western Sichuan province, which could be related to the development of agriculture in the eastern Sichuan province. Ca²⁺ peaked in southeastern Sichuan province due to intensive construction activities and severe stone desertification. On the basis of Positive Matrix Factorization (PMF) analysis, four sources of inorganic ions in rainwater were identified, including anthropogenic source, crust, biomass burning, and aging sea salt aerosol. Geographically Weighted Regression (GWR) was used to find the spatial correlations between the socio-economic factors and ions in the rainwater. At the regional scale, the influence of fertilizer consumption and Gross Agricultural Production (GAP) on NH₄⁺ increased from east to west; moreover the influence of Gross Industrial Production (GIP) on SO₄²⁻ and NO₃⁻ also increased.

Mercury-antimony (HgSb) mining activities are important anthropogenic sources of Hg and Sb to the local environment. The Xunyang HgSb mine situated in Shaanxi Province is an active Hg mine in China. To understand the emission, transportation, and deposition of Sb through HgSb mining activities, current study systematically monitored the Sb concentration in precipitation in the Xunyang HgSb mining district. Five groups of experimental pots were carefully designed to further investigate the influence of HgSb mining activities on the Sb contamination in the local surface soil. Based on the overtime increasing of the Sb concentrations in soil from experimental pots, for the first trial, we estimated the atmospheric deposition flux/mass of Sb in the Xunyang HgSb mining district. Our results showed that the concentrations of Sb in precipitation in the Xunyang HgSb mining district ranged from 0.71 μg L−1 to 19 μg L−1 (mean = 4.2 ± 4.5 μg L−1), which was orders of magnitude higher than that at the control site. As expected, the concentration of Sb in precipitation was highly elevated near of the HgSb smelter and gradually decreased with distance from the smelter. After 12 months exposure, Sb concentrations in soil of experimental pots were increased by 1.2–8.5 times. The average atmospheric wet and dry deposition flux of Sb in the Xunyang HgSb mining district were 7.2 ± 6.9 μg m−2 day−1 and 2.1 ± 4.7 mg m−2 day−1, respectively; the annual wet and dry deposition mass of Sb through HgSb mining activities were estimated to be 1.6 t y−1 and 158 t y−1, respectively, indicating that dry deposition was the dominant pathway (98 ± 1.2%) for the removal of Sb from the atmosphere. Our results confirmed that the ongoing HgSb mining activities resulted to serious Sb contamination to terrestrial ecosystems, posing a potential threat to local residents in the Xunyang HgSb mining district.

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.

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.

The presence of PM₂.₅ may affect the photodegradation of benzene in the natural atmosphere. On one hand, the photodegradation of benzene may be promoted with the increase in PM₂.₅ concentrations, owing to adsorption and catalysis effect of PM₂.₅ surface; On the other hand, PM₂.₅ can scatter or block ultraviolet light and lead to weakening the photochemical reactions in the atmospheric system. It is very difficult to prove which process is dominant in the real atmosphere due to the complexity of the atmosphere. Based on coupling detrended fluctuation analysis, the goal of this work is to reveal the role of PM₂.₅ in the photodegradation of benzene in real atmosphere over long time scales. The 9 years regular monitoring data from 2007 to 2016 in Puzi of Taiwan are analyzed. A new nonlinear parameter (PDB) is established to characterize the photodegradation degree of atmospheric benzene. Based on sliding window technique, the correlations between the temporal variation of PDB and PM₂.₅ are analyzed. The results show that there is a positive correlation between PDB and PM₂.₅ in daytime and little correlation between them in nighttime. It indicates that PM₂.₅ mainly plays the promoting effect on the photodegradation of atmospheric benzene. This is the first study to directly determine the role of PM₂.₅ in the photochemical behavior of atmospheric benzene based on long term field observation data. Moreover, the results suggest that the regional transport of PM₂.₅ could seriously affect the geochemistry cycle of some VOCs. This research provides a new analysis method to directly quantify the effect of PM₂.₅ on the photodegradation of VOCs in the real atmosphere. It is helpful for evaluating the role of PM₂.₅ in the complex photochemical system.

Perfluorooctanoic acid (PFOA) toxicity is of considerable concern due to its wide application, environmental persistence, and bioaccumulation. In the current study, we used a scaffold-free three-dimensional (3D) spheroid model of mouse liver cells (AML12) to explore the toxicity of PFOA and emerging alternatives (HFPO-DA and PFO4DA). Comparing the short-term (24 and 72 h treatment) toxicity of PFOA between conventional 2D monolayer cells and 3D spheroids, we found that spheroids had higher EC₅₀ values and lower ROS levels after treatment, indicating their greater resistance to PFOA. Cell viability (i.e., adenosine triphosphate (ATP) content and lactate dehydrogenase (LDH) leakage) and liver-specific function (i.e., albumin secretion) were stable in spheroids through 28 day of culture. However, under 100 and 200 μM-PFOA treatment for 28 day, ROS levels, LDH leakage, and caspase3/7 activity all increased significantly. As a sensitive parameter, ROS showed a significant increase at 21 day, even in the 50 μM-PFOA group. Consistent with the elevation of ROS and caspase3/7, the expressions of oxidative stress- and apoptosis-related genes, including Gsta2, Nqo1, Ho-1, caspase3, p53, and p21, were induced in dose- and time-dependent manners after PFOA exposure. The peroxisome proliferator-activated receptor alpha (PPARα) pathway was also activated after treatment, with significant induction of its target genes, Fabp4 and Scd1. Similar to PFOA, both HFPO-DA and PFO4DA activated the PPARα pathway, induced ROS levels, and initiated cell damage, though at a relatively lower extent than that of PFOA. Our results imply that the 3D spheroid model is a valuable tool in chronic toxicological studies.

Environmental chemicals such as phthalate esters may have adverse effects on anogenital distance (AGD), but the evidence in both genders has not been reviewed systematically. The objective of the present study is to conduct a systematic review and meta-analysis of studies that analyzed the relationship between exposure to phthalates and AGD. English papers published up to March 2018 were searched in PubMed, Scopus, Clarivate-Web of Science, and Google scholar. We applied fixed-effects models to calculate pooled beta coefficient [β]. In the case of heterogeneity, random-effects models were used. Using the comprehensive search strategies, 313 papers were identified and after screening, 10 of them were included in this study. In primary analyses, we found that exposure to phthalates was not associated with short AGD (β = −0.11; 95% CI, −0.27, 0.06; I² = 0%). However, results of subgroup analyses indicated that in boys, the sum of di-2-ethylhexyl phthalate (∑DEHP) metabolites had significant association with the risk of shortened anopenile distance (AGDAP) (β = −0.915, 95% CI: 1.629, −0.2) and anoscrotal distance (AGDAS) (β = −0.857, 95% CI: 1.455, −0.26). In addition, urinary monobutyl phthalate (MBP), monoethyl phthalate (MEP), and monoisobutyl phthalate (MiBP) were associated with short AGDAP. We also observed significant association between monobenzylphthalate (MBzP) and anofourchette distance (AGDAF) in girls. Our study provided findings on significant association of exposure to ∑DEHP metabolites, MBP, MEP, and MiBP with shortened AGDAP in boys. The mechanisms of phthalates effect on AGD may involve receptors and enzymes involved in steroidgenesis, negative influence on Leydig cells, cell proliferation, gonocyte cell numbers, and testosterone production.

Microalgae are widely used as representative primary producers in ecotoxicology, while macrophytes are much less studied. Here we compared the bioavailability and cellular toxicity pathways of 2 h-exposure to 10−6 mol L−1 Cu in the macrophyte Elodea nuttallii and the green microalga Chlamydomonas reinhardtii.Uptake rate was similar but faster in the algae than in the macrophyte, while RNA-Sequencing revealed a similar number of regulated genes. Early-regulated genes were congruent with expected adverse outcome pathways for Cu with Gene Ontology terms including gene regulation, energy metabolism, transport, cell processes, stress, antioxidant metabolism and development. However, the gene regulation level was higher in E. nuttallii than in C. reinhardtii and several categories were more represented in the macrophyte than in the microalga. Moreover, several categories including oxidative pentose phosphate pathway (OPP), nitrate metabolism and metal handling were only found for E. nuttallii, whereas categories such as cell motility, polyamine metabolism, mitochondrial electron transport and tricarboxylic acid cycle (TCA) were unique to C. reinhardtii. These differences were attributed to morphological and metabolic differences and highlighted dissimilarities between a sessile and a mobile species. Our results highlight the efficiency of transcriptomics to assess early molecular responses in biota, and the importance of studying more aquatic plants for a better understanding on the impact and fate of environmental contaminants.

We have previously reported on the ubiquitous presence of perchlorate in the deposited and airborne fine dusts of Malta and shown that the source of the chemical in the dusts of this small central Mediterranean island is fireworks. There are no local geologic or anthropogenic sources of perchlorate other than firework manufacture and display. The hypothesis was tested that ground-deposited perchlorate will be mobilized in runoff and would partly migrate to the water table and eventually also affect tap water, one third of which being derived from groundwater. Forty four percent of 36 groundwater samples contained perchlorate above detection limit with mean and median values of 1.09 and 1.1 μg L−1. Sixty-two percent of 16 runoff samples collected during storms contained perchlorate above detection limit with mean and maximum concentrations, respectively, of 50.8 and 129 μg L−1, values which are far too high to be explained by atmospheric inputs given that rainwater perchlorate levels are typically <3 μg L−1. Between 42 and 89% of the tap waters analyzed in three sampling campaigns contained perchlorate above detection limit and had mean concentrations ranging from 0.4 to 1.6 μg L−1 suggesting contamination levels similar to those reported from China but lower than levels reported from the USA. The phenomenon of contamination of the water resources of Malta by perchlorate is probably unique in that it results not from geologic or industrial inputs but from an intense and prolonged pyrotechnic activity that is deeply rooted in the popular culture of the islanders.