Physicochemical and biological changes on naturally aged microplastic surfaces in real environments over 10 months.

Microplastics (MPs) undergo aging over time, which can influence their behavior in the environment. While laboratory-simulated studies have investigated MP aging, research on natural aging in various real environments remains limited. This study aims to investigate the physical, chemical and biological changes that occur in five types of MPs after more than 10 months of natural aging in three different real environments: seawater, air and soil. Results are compared with previous laboratory experiments. The surface roughness of all types of aged MPs was found to be higher in seawater than in air and soil, which differed from previous simulated studies that showed the highest roughness in air. All aged MPs exhibited the occurrence of hydroxyl and carbonyl groups due to the oxidation processes. Interestingly, the MPs aged in soil showed the lowest level of these functional groups, while in seawater or air, some MPs demonstrated the highest. This contrasts with previous studies indicating the highest level of oxygen-containing functional groups in aged MPs in air. Bacterial analysis identified fourteen bacterial phyla on the surface of aged MPs in all three real environments, with varying abundance in specific environments. Notably, the composition of bacterial communities in the microplastisphere was determined by the surrounding environments, independent of MP types. Natural aging is more complex than laboratory simulations, and the degree of MP aging increases with the complexity of environmental factors. These findings enhance our understanding of the natural aging of MPs in different real environments.

Hairpin DNA-enabled ratiometric electrochemical aptasensor for detection of malathion.

A hairpin DNA-enabled ratiometric electrochemical aptasensor is reported for sensitive and reliable detection of malathion (MAL). The approach employs hairpin DNA (ferrocene-labeled, Fc-hDNA) as a carrier to hybridize MAL aptamers (methylene blue-labeled, MB-Apt) to form double-stranded DNA structures on an electrode. The presence of MAL induces the removal of aptamers, and hDNA re-forms hairpin structures, causing a decrease in the oxidation current of MB (IMB) and an increase in the oxidation current of Fc (IFc). The ratiometric signal of IFc/IMB responds quantitatively to MAL concentrations. To compare analytical performances, a linear single-stranded DNA (ssDNA) is also used to construct the ssDNA-based aptasensor. We demonstrate that hairpin DNA possessing a rigid two-dimensional structure can improve the assembly efficiency of aptamers and the stability of redox probes. The approach combines the advantages of the ratiometric electrochemical method with hairpin DNA-based conformational switching probes, enabling hDNA-based aptasensor with enhanced sensitivity and reliability, offering a linear range of 0.001 to 1.0 ng mL-1. The platform was applied to detect MAL in lettuce, and the statistical analysis indicated that no significant differences were found between the developed platform and HPLC-MS.

Polyethylene terephthalate and di-(2-ethylhexyl) phthalate in surface and core sediments of Bohai Bay, China: Occurrence and ecological risk.

Bohai Bay, a typical semi-enclosed bay, is close to the Beijing-Tianjin-Hebei Region, the economic center of north China. The release of emerging contaminants was considerably increasing with the fast urbanization and industrialization along the coastline. However, such data, e.g. plastic polymers, are still limited. Here, polyethylene terephthalate (PET) and di-(2-ethylhexyl) phthalate (DEHP) in surface sediments and sediment cores from the coastal area of Bohai Bay were investigated. The ranges of PET and DEHP concentrations in surface sediments are 1.49-13.90 mg/kg and 0.23-19.26 mg/kg, respectively. The relatively high contents of PET and DEHP were found near the Haihe River estuary, indicating the importance of riverine input. The PET and DEHP profiles in the cores dated by the 210Pb method showed increasing trends with time. The PET in Bohai Bay was low risk evaluated by the potential ecological risk assessment. Low ecological risks of DEHP to the benthic organisms were found in the sediments, using the environmental risk limits, risk quotient, threshold effect level and probable effect level methods. The pollution levels of PET and DEHP in Bohai Bay obtained in this study may provide important data for making pollution control strategies.

Distributions, temporal trends and ecological risks of polyethylene terephthalate (PET) and di-(2-ethylhexyl) phthalate (DEHP) in sediments of Jiaozhou Bay, China.

Spatiotemporal distribution and ecological risk of the polyethylene terephthalate (PET) plastic polymer and plasticizer di-(2-ethylhexyl) phthalate (DEHP) were investigated using both surface and core sediments in Jiaozhou Bay, China. The concentrations of PET and DEHP ranged 210.6-1929.7 µg/kg and 0-591.2 µg/kg, respectively. The depth profiles of PET and DEHP in the sediment cores indicated that PET and DEHP pollution increased since the 1970s, which is in accord with the regional PET and DEHP consumption history. The levels of PET in Jiaozhou Bay was found to represent low ecological risk based on the assessment models for Potential Ecological Risk factor and Potential Ecological Risk. The amounts of DEHP also posed a low risk to the aquatic organisms in the sediment phase as indicated by the Risk Quotient method.

Tunable Electrochemical C-N versus N-N Bond Formation of Nitrogen-Centered Radicals Enabled by Dehydrogenative Dearomatization: Biological Applications.

Herein, an environmentally friendly electrochemical approach is reported that takes advantage of the captodative effect and delocalization effect to generate nitrogen-centered radicals (NCRs). By changing the reaction parameters of the electrode material and feedstock solubility, dearomatization enabled a selective dehydrogenative C-N versus N-N bond formation reaction. Hence, pyrido[1,2-a]benzimidazole and tetraarylhydrazine frameworks were prepared through a sustainable transition-metal- and exogenous oxidant-free strategy with broad generality. Bioactivity assays demonstrated that pyrido[1,2-a]benzimidazoles displayed antimicrobial activity and cytotoxicity against human cancer cells. Compound 21 exhibited good photochemical properties with a large Stokes shift (approximately 130 nm) and was successfully applied to subcellular imaging. A preliminary mechanism investigation and density functional theory (DFT) calculations revealed the possible reaction pathway.

Organophosphate di- and tri-esters in indoor and outdoor dust from China and its implications for human exposure.

Organophosphate (OP) esters are emerging environmental contaminants, but little is known about their occurrence in dust. In this study, 19 OP triesters and their 11 diester degradation products were measured in indoor dust and outdoor dust collected from China. ∑OP triester concentrations in indoor dust (median: 2380 ng/g dry weight [dw]) were an order of magnitude higher than those in outdoor dust (446 ng/g dw). The median concentrations of ∑OP diesters in indoor and outdoor dust were 260 and 96.8 ng/g dw, respectively. Dust samples collected from eastern and southern China contained higher concentrations of ∑OP di- and tri-esters than those from the other regions. Dust from the most urbanized areas in China including Beijing, Shanghai, and Guangzhou exhibited the highest concentrations of ∑OP di- (>1000 ng/g dw) and triesters (>4000 ng/g dw). We also found notable concentrations of emerging aryl-OP triesters in dust (3.85-10.6 ng/g dw). Significant correlations existed between the concentrations of bis(2-ethylhexyl) phosphate (BEHP) and tris(2-ethylhexyl) phosphate (TEHP) (rho = 0.672-0.691, p < 0.01), as well as DPHP and triphenyl phosphate (TPHP) (rho = 0.537-0.766, p < 0.01) in dust samples, indicating that OP diesters originated from the degradation of triesters. High molar concentration ratios of DEP to triethyl phosphate (TEP) and DPHP to TPHP/ethylhexyl diphenyl phosphate (EHDPP) suggested that these OP triesters degrade readily. Significant correlations were found between the concentrations of ∑OP di- (R2 = 0.390, p < 0.05) and tri-esters (R2 = 0.475, p < 0.01) in paired indoor-outdoor dust samples, which suggested that indoor dust was the source of OP esters to the outdoor environment. The estimated daily intake (EDI) of ∑OP diesters through dust ingestion was 0.21 ng/kg bw/d for adults and 2.59 ng/kg bw/d for children. The exposure levels of OP diesters, DEP and DPHP, were comparable to those of their parent triester compounds.

An optimized density-based approach for extracting microplastics from soil and sediment samples.

Microplastic pollution in the environment has received growing attention worldwide. A major impediment for accurate measurements of microplastics in environmental matrixes is to extract the particles. The most commonly-used method for separation from soil or sediment is flotation in dense liquid based on the relatively low density of plastic particles. This study provides an improved and optimized process for extraction of microplastic particles by modifying the floatation technique and floatation solution. Microplastics in soils and sediments are extracted by adding 200 g dry soil or sediment sample to 1.3 L mix of the saturated NaCl and NaI solutions in a volume ratio of 1:1 and aerating for 40 s then filtering the supernatant. The accuracy and precision of the new approach is validated by recovery experiments using soil and sediment samples spiked with six common microplastic compounds: polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS) and expanded polystyrene (EPS), and comparison with the previous method. The optimized approach is further compared with the previous approach using the real soil and sediment samples.