Di(2-ethylhexyl) phthalate (DEHP), as a widely used plasticizer, is reported to have widespread environmental and global health hazards. Trace amounts of phthalates in the environment are sufficient to disrupt ecological balance and affect human health. However, DEHP-induced splenic toxicity remains in an unknown state. Therefore, to explore the mechanism of DEHP-induced splenic toxicity, male quail were employed with 0, 250, 500 and 750 mg/kg body weight DEHP by daily gastric perfusion for 45 days. Notably, splenic corpuscular border and cell gap enlargement were observed in the spleen tissue of DEHP-exposed quail under the histopathological analysis. Furthermore, DEHP induced dysregulation of oxidative stress markers by increasing malondialdehyde (MDA) content and decreasing superoxide dismutase (SOD), glutathione peroxidase (GPx), and catalase (CAT) activities. Low concentration of DEHP (≤250 mg/kg) exposure suppressed nuclear factor-E2-related factor 2 (Nrf2) signaling pathway, while high concentration of DEHP (≥500 mg/kg) exposure activated Nrf2-mediated defense response. DEHP induced splenic oxidative stress via interfering Nrf2 signal pathway and altering the transcription of its downstream genes. In conclusion, this study suggested that DEHP induced splenic toxicity.

Carbon nanotubes (CNTs) inevitably enter domestic sewage and industrial wastewater with the continuous increase of their production and application field. The potential effect of CNTs on biological wastewater treatment processes has raised wide concerns due to their biotoxicity. In the present study, the performance, microbial community and enzymatic activity of sequencing batch reactors (SBRs) were evaluated under 148-day exposure of amino-functionalized multi-walled CNTs (MWCNTs-NH₂) at 10 and 30 mg/L. The COD removal efficiency at 10 and 30 mg/L MWCNTs-NH₂ gradually reduced from 91.03% and 90.43% on day to 89.11% and 86.70% on day 148, respectively. The NH₄⁺-N removal efficiency at 10 and 30 mg/L MWCNTs-NH₂ gradually reduced from 98.98% and 98.46% on day 1 to 96.65% and 63.39% on day 148, respectively. Compared to 0 mg/L MWCNTs-NH₂, the oxygen-utilizing rate, ammonia-oxidizing rate, nitrite-oxidizing rate, nitrite-reducing rate and nitrate-reducing rate at 30 mg/L MWCNTs-NH₂ were decreased by 52.35%, 60.58%, 55.12%, 56.56% and 57.42% on day 148, respectively. The microbial reactive oxygen species and lactate dehydrogenase release on day 148 was increased by 59.71% and 55.28% at 30 mg/L MWCNTs-NH₂, respectively. The key microbial enzymatic activity related to nitrogen removal decreased with the increase of operation time under MWCNTs-NH₂ stress. The relative abundances of Nitrosomonas, Nitrosospira, Nitrospira and some denitrifying bacteria at 10 mg/L MWCNTs-NH₂ gradually reduced with an increment in operation time. The changes of nitrogen removal rate, microbial community and enzymatic activity of SBR were related to the time-cumulative nonlinear inhibition effect under long-term exposure.

The Bohai Sea, one of the largest marginal seas in China, is extensively influenced by human and industrial activities. The pollutant loads from anthropogenic activities have induced severe ecological problems. The study investigates the physicochemical characteristics of seawater and sediments in Bohai Bay and Laizhou Bay of the Bohai Sea. The diversity and composition of microbial community in sediments are analyzed by 16S rRNA gene amplicon sequencing. The sequencing results present 16 phyla and 31 classes from the samples. Proteobacteria constituted a dominant phylum, of which the classes of Gamma-, Delta-, and Epsilon-are predominant sub-divisions. Nitrogen, phosphorus, and sulfur cycling related microbes present high abundance in both bays. The metabolism of organic matters is the main factor that influences the distribution of microbial communities in Bohai Bay, while the inflow of Yellow River is the dominant factor that influences the distribution of microbial communities in Laizhou Bay. Sulfur oxidizing process is expected to be positively influenced by heavy metals, while ammonia (NH4+) oxidizing process is prone to be negatively affected by heavy metals in both bays. Microbial communities in the offshore sediments of Laizhou Bay and the majority microbial communities in Bohai Bay sediments are subject to similar predominant controlling factors. This phenomenon is likely ascribed to ocean circulation. The results of this study can provide constructive guidelines on ecosystem management of marginal seas in Bohai and elsewhere.

Polycyclic aromatic hydrocarbons (PAHs), some of the most widespread organic contaminants, are highly toxic to soil microorganisms. Whether long-term polluted soils can still respond to the fresh input of pollutants is unknown. In this study, the soil enzyme activity, soil microbial community structure and function and microbial metabolism pathways were examined to systematically investigate the responses of soil microorganisms to fresh PAH stress. Microbial activity as determined by soil dehydrogenase and urease activity was inhibited upon microbe exposure to PAH stress. In addition, the soil microbial community and function were obviously shifted under PAH stress. Both microbial diversity and richness were decreased by PAH stress. Rhizobacter, Sphingobium, Mycobacterium, Massilia, Bacillus and Pseudarthrobacter were significantly affected by PAH stress and can be considered important indicators of PAH contamination in agricultural soils. Moreover, the majority of microbial metabolic function predicted to respond to PAH stress were affected adversely. Finally, soil metabolomics further revealed specific inhibition of soil metabolism pathways associated with fatty acids, carbohydrates and amino acids. Therefore, the soil metabolic composition distinctively changed, reflecting a change in the soil metabolism. In summary, fresh contaminant introduction into long-term polluted soils inhibited microbial activity and metabolism, which might profoundly affect the whole soil quality.

Ecotoxicological studies show the association between pesticide pollution and transgenerational toxicity in aquatic organisms. However, a less considered risk is that many pesticides can be metabolized and transferred to offspring as new toxicants. In this study, we used zebrafish to evaluate the maternal transfer risk of fipronil (FIP), which is a great threat to aquatic organisms with toxic metabolite formation. After 28-day exposure to environmentally relevant concentrations (1.0, 5.0 and 10.0 μg/L) of FIP in adult female zebrafish (F0), the toxicants off-loading and transgenerational toxicity in offspring were studied. High burdens of FIP and its sulfone metabolite were found in both F0 and the embryos (F1), resulting in increased CYP450 activity. The residual levels of the metabolite were higher than those of the parent compound. Chiral analysis further showed a preferential accumulation of S-enantiomer of FIP in both F0 and F1. Maternal exposure to FIP increased the malformation rate and decreased the swim speed in larvae. Additionally, after exposure, the levels of thyroid hormones (THs), including triiodothyronine (T3) and thyroxine (T4), decreased in both generations, particularly in the F1. Gene transcription expression along the hypothalamic-pituitary-thyroid (HPT) axis was also significantly affected. Maternal exposure to FIP increased sulfone metabolite enrichment and cause multiple toxic effects in F1. Findings from this study highlight the key role of biologically active product formation in the maternal transfer of pollutants and associated risk assessment.

Aromatic halogenated chemicals are an unregulated class of byproducts (DBPs) generated from disinfection processes in the water environment. Information on the toxicological interactions, such as antagonism and synergism, present in DBP mixtures remains limited. This study aimed to determine the toxicological effects of aromatic halogenated DBP mixtures on the freshwater bacterium Vibrio qinghaiensis sp.-Q67. The acute toxicities of seven DBPs and their binary mixtures toward V. qinghaiensis sp.-Q67 were determined through microplate toxicity analysis. The toxicities of single DBPs were ranked as follows: 2,5-dibromohydroquinone > 2,4-dibromophenol > 4-bromo-2-chlorophenol ≈ 2,6-dibromo-4-nitrophenol > 2,6-dichloro-4-nitrophenol > 2-bromo-4-chlorophenol > 4-bromophenol. The percentages of synergism (experimental values higher than the predicted concentration addition) on the levels of 50%, 20%, and 10% effective concentrations reached 61%, 41%, and 31%, respectively. These results indicated that the probability of synergism decreased as concentration levels decreased. The synergetic effects of the compounds were dependent on concentration levels and concentration ratios. The proposed quantitative structure–activity relationship model can be used to predict the interactive toxicities exerted by 105 binary DBP mixture rays of 21 DBP mixture systems.

The fast-growing production and application of carbon nanotube (CNT) materials in a variety of industrial products inevitably lead to their release to wastewater and surface water. CNT would experience oxidization in wastewater treatment plant due to the presence of large amount of disinfectants, such as H₂O₂ and O₃, which in turn affects the environmental fates and risks of CNT. In this study, oxidized CNT materials (O-CNTs) were prepared by treating CNT with H₂O₂/UV and O₃ (denoting as H₂O₂-CNT and O₃-CNT, respectively). A variety of characterizations indicated that oxygen containing groups were generated on CNT surface upon the oxidation, and the O/C ratio increased in the order of pristine CNT < H₂O₂-CNT < O₃-CNT. In the presence of Na⁺, K⁺ and Mg²⁺, the O-CNTs displayed better colloidal stability than the pristine CNT, and the stability increased with the oxidation degree (indicated by O/C ratio). This could be explained by the more negative surface charge and stronger hydrophilicity of the O-CNTs. Unexpectedly, in the presence of Ca²⁺, the most oxidized O₃-CNT exhibited the poorest colloidal stability. The abundant carboxyl groups in O₃-CNT provided effective binding sites for cation bridging effect through Ca²⁺ and led to stronger aggregation. Increasing pH was more favorable to disperse CNTs (both O-CNT and pristine CNT) in the presence of Na⁺, but much less effective in inhibiting the aggregation of O₃-CNT in presence of Ca²⁺. This could be explained by the stronger cation bridging effect due to enhanced deprotonation the –COOH groups at higher pH conditions. The calculated Hamaker constants of the CNTs decreased with the oxidation degree, implying that there was lower van der Waals force between the O-CNTs. The Derjaguin–Landau–Verwey–Overbeek (DLVO) calculation confirmed that O-CNTs had to overcome higher energy barrier and thus showed better colloidal stability than the pristine CNT in the presence of Na⁺.

Linking water to research on coupled human and natural systems (CHANS) has attracted wide interest as a means of supporting human-natural sustainability. However, most current research does not focus on water environmental properties; instead, it is at the stage of holistic status assessment and measures adjustment from the point of view of the whole study region without revealing the dynamic interaction between human activities and natural processes. This paper establishes an integrated model that combines a System Dynamics model, a Cell Automaton model and a Multiagent Systems model and exploits the potential of the combined model to reveal regions' human-water interaction status during the process of urban evolution, identify the main pollution sources and spatial units, and provide the explicit space-time measurements needed to enhance local human-natural sustainability. The successful application of the integrated model in the case study of Changzhou City, China reveals the following. (1) As the city's development has progressed, the water environment status in some spatial units is still unsatisfactory and may even become more serious, especially in the urban areas of the Urban District and Liyang County. The concentration of Chemical Oxygen Demand (COD) in monitoring section 157 of the Urban District has increased from 36.90 mg/l to 40.84 mg/l. The main source of this increase is the increase in secondary industry. (2) With the application of the spatially explicit measures of the sewage treatment ratio improvement and new sewage plant construction, the water quality in the urban area has significantly improved and now satisfies the water quality standards. The measure of livestock manure utilization enhancement is adopted to improve the spatial units in which livestock is the main pollution source and achieve the goal of water quality improvement. The model can be used to support the sustainable status assessment of human-water interaction and to identify effective measures that can be used to realize human-water sustainability along with social-economic development.

Antifouling booster biocides are chemicals used in protective paints to tackle the adhesion of fouling organisms to maritime artificial structures. However, they are also known to exert toxic effects on non-target organisms. Recent research developments have highlighted the potential use of engineered micro/nanomaterials (EMNMs) as carriers of antifouling booster biocides in order to control their release and to reduce the harmful effects on living biota. In the present study, we sought to assess the toxicity of two commercially-available booster biocides: (zinc pyrithione (ZnPT) and copper pyrithione (CuPT)); three unloaded engineered micro/nanomaterials (EMNMs); layered double hydroxides (LDH), silica nanocapsules (SiNC), polyurea microcapsules (PU); , and six novel EMNMs (loaded with each of the two biocides). The exposure tests were conducted on the larval stage (nauplii) of the brine shrimp Artemia salina and on two embryonic developmental stages of the European purple sea urchin Paracentrotus lividus. The findings indicate that the unloaded LDH and PU (i.e. both biocide-free EMNMs) have non/low toxic effects on both species. The unloaded SiNC, in contrast, exerted a mild toxic effect on the A. salina nauplii and P. lividus embryos. The free biocides presented different toxicity values, with ZnPT being more toxic than CuPT in the P. lividus assays. LDH-based pyrithiones demonstrated lower toxicity compared to the free forms of the state-of-the-art compounds, and constitute good candidates in terms of their antifouling efficacy.

The transport and retention of nanoplastics (NP, 200 nm nanopolystyrene) functionalized with surface carboxyl (NPC), sulfonic (NPS), low-density amino (negatively charged, NPA−), and high-density amino (positively charged, NPA+) groups in seawater-saturated sand with/without humic acid were examined to explore the role of NP surface functionalities. The mass percentages of NP recovered from the effluent (Meff) with a salinity of 35 practical salinity units (PSU) were ranked as follows: NPC (19.69%) > NPS (16.37%) > NPA+ (13.33%) > NPA− (9.78%). The homoaggregation of NPS and NPA− was observed in seawater. The transport of NPA− exhibited a ripening phenomenon (i.e., a decrease in the transport rate with time) due to the high attraction of NP with previously deposited NP, whereas monodispersed NPA+ presented a low Meff value because of the electrostatic attraction between NPA+ and negatively charged sand. Retention experiments showed that the majority of NPC, NPS and NPA+ accumulated in a monolayer on the sand surface, whereas NPA− accumulated in multiple layers. Suwannee River humic acid (SRHA) could remarkably improve the transportability of NPC, NPS, and NPA− by increasing steric repulsion. The strong attraction between NPA+ and the deposited NPA+ in the presence of SRHA triggered the weak ripening phenomenon. As seawater salinity decreased from 35 PSU to 3.5 PSU, the increase in electrostatic repulsion of NP-NP and NP-sand enhanced the transport of NPC, NPS, and NPA−, and the ripening of NPA− breakthrough curves disappeared. In deionized water, NPC, NPS, and NPA− achieved complete column breakthrough because the electrostatic repulsion between NP and sand intensified. However, the Meff values of NPA+ in 3.5 PSU seawater and deionized water presented limited increments of 15.49% and 23.67%, respectively. These results indicated that the fate of NP in sandy marine environments were strongly affected by NP surface functionalities, seawater salinity, and coexisting SRHA.