Microplastics (MPs) can cause adverse effects and pose potential threats to humans and the environment. In addition, dissolved organic matter leached from MPs (MP-DOM) is also a critical issue due to its ecotoxicity and potential to form disinfection by-products (DBPs) during the disinfection process of water treatment plants. However, limited information is available on the dynamic transformation of MP-DOM during UV irradiation and subsequent disinfection, which may further influence the formation of DBPs in MP-DOM. Herein, PSMPs-DOM were leached in aqueous solutions under UV irradiation and the samples were then chlorinated. PSMPs-DOM before and after chlorination were characterized by multiple spectral technologies and methods. With prolonged irradiation time, the aromaticity, molecular weight, humic-like substances and oxygen-containing functional groups of PSMPs-DOM increased, suggesting the continuous transformation of PSMPs-DOM. After chlorination, the aromaticity, molecular weight and humic-like substances of PSMPs-DOM decreased, among which the changes of C2 and oxygen-containing functional groups were more significant. Besides, the PSMPs-DOM formed under prolonged irradiation exhibited higher chlorine reactivity, owing to the more aromatic structures and unsaturated bonds. TCM, DCBM, DBCM and TBM were detected in all chlorinated PSMPs-DOM samples, while the PSMPs-DOM formed at the later stage of irradiation exhibited lower THMs formation potential. The correlation results showed that the conversion of humic-like substances in PSMPs-DOM affected the THMs formation potential, with photo-induced humic-like substance being a more dominant factor. This study provided more information on the relationship between the compositional transformation of MP-DOM and their potential to form DBPs, which may facilitate the assessment of potential toxicity associated with MPs-containing water, as well as the development of more effective water treatment methods.
In wastewater-based epidemiology (WBE), the selection of appropriate biomarkers presents a significant challenge. Recently, sulfated bisphenols have garnered attention as potential WBE biomarkers due to their increased stability in wastewater compared to glucuronide conjugates. This study aims to comprehensively assess the feasibility of employing sulfated BPA and BPS as WBE biomarkers by analyzing both WBE and human biomonitoring data. To conduct this research, wastewater samples were collected from six domestic wastewater treatment plants in Guangzhou, China, and urinary concentration of BPA and BPS were obtained from peerreviewed literature. The results revealed that mean urinary concentrations of BPA and BPS, calculated using Monte Carlo simulations, significantly exceeded those reported in human biomonitoring studies. Furthermore, the per capita mass load ratio of sulfated BPA and BPS in human urine to the mass load in wastewater was found to be below 10 %. This outcome suggests that the excretion of BPA-S and BPS-S in urine does not make a substantial contribution to wastewater, hinting at the existence of other notable sources. Consequently, our study concludes that sulfated BPA-S and BPS-S are not suitable candidates as WBE biomarkers. This work provides a referenceable analytical framework for evaluating the feasibility of WBE biomarkers and emphasizes the necessity for caution when utilizing WBE to assess human exposure to chemicals.
Bisphenol analogues (BPs) are ubiquitous in the environment and have gained significant attention regarding their associated health risks. However, there is a lack of comprehensive biomonitoring data on BPs and their metabolites in human urine. To address this, we conducted a study evaluate the exposure to BPs in the general population of Guangzhou, China. A total of 1440 urine samples were collected from volunteers and analyzed for the presence of BPs and their metabolites after being pooled into 36 groups based on age and gender. The findings revealed the common detection of ten free-form BPs, as well as the urinary metabolites of BPA and BPS, in the pooled urine samples. BPA was the predominant free-form compound, constituting 50% of the total BPs. The primary urinary metabolites of BPA and BPS are BPA-G and BPS-G, respectively, indicating glucuronidation as their primary metabolic pathway. The composition of urinary metabolites of BPA and BPS varied by age and sex, while the concentration of total BPs in urine was not significantly associated with age and sex. Enzymatic hydrolysis yielded a mean amplification of individual BPs concentrations in urine samples ranging from 1.8 times (BPA) to 4.6 times (BPS). Based on the outcomes, it was estimated that conjugated forms accounted for 96.9%, 96.2%, 94.7%, 94.1%, 92.6%, 89.1%, 87.3%, 87.2%, 87.1% and 85.8% of BPP, BPAF, BPZ, BPE, BPAP, BPF, BPA, BPC, BPS and BPF, respectively, in the pooled urine samples. Preliminary risk assessments indicated that the estimated daily intake of BPA was much higher than the latest proposed tolerable daily intake. Due to the unavailability of health-based guideline values for alternative BPs, some of them exhibit daily intakes comparable to BPA, implying that greater attention should be paid to health risks associated with exposure to BPs.
Metal cations can be adsorbed on the surface of PSMPs which change the surface properties of PSMPs and lead to the aggregation of PSMPs in aqueous solution. However, previous studies have only examined the processes of aggregation and adsorption independently, without investigating the correlation of adsorption and aggregation. In this study, the adsorption and aggregation experiment were carried out simultaneously and monitored simultaneously. The results of this study reveal that, prior to charge reversal of polystyrene microplastic (PSMPs), both adsorption and aggregation increased gradually with increasing metal cations concentration, and were mutually reinforcing. However, following charge reversal, adsorption increased while aggregation decreased, indicating that adsorption inhibited aggregation. The Zeta potentials of PSMPs increase consistently with increasing metal cations concentrations suggested that electrostatic force was one of the primary mechanisms for the adsorption of metal cations by PSMPs. The FTIR analysis reveal that the peak corresponding to C--C stretching shifted from 1630 cm-1 to 1628 cm-1, 1621 cm-1, and 1615 cm-1 when Ag+, Cu2+ or Cr3+ metal cations were existed, and the results indicated that there might be interactions such as cations-pi between PSMPs and metal cations. This information is crucial in determining the environmental fate and impact of PSMPs that have adsorbed metal cations pollutants.
Heavy metal cations are a typical type of inorganic pollutant that has persistent distribution characteristics in aquatic environments and are easily adsorbed on carriers, posing serious threats to ecological safety and human health. Some studies have shown that the coexistence of dissolved organic matter (DOM) and microplastics (MPs) promotes the adsorption of heavy metal cations, but the mechanism of promoting the adsorption process has not been thoroughly studied. In this study, the effect of polystyrene microplastics (PSMPs) on the binding properties of Pb2+ onto humic acid (HA) in aquatic environments was investigated by spectral analysis and two-dimensional correlation (2D-COS) analysis. When PSMPs co-existed with HA, the adsorption capacity of Pb2+ increased. On the one hand, Pb2+ is directly adsorbed on HA through the mechanism of complexation reaction, ion exchange and electrostatic interaction. On the other hand, Pb2+ is first adsorbed on PSMPs by electrostatic action and indirectly adsorbed on HA in the form of PSMPs-Pb2+ owing to the interaction between HA and PSMPs, which increases the adsorption amount of Pb2+ on HA. This study is significant for studying the migration and regression of heavy metal cation contaminants when PSMPs co-exist with DOM in an aqueous environment.