Body distribution and ecotoxicological effect of nanoplastics in freshwater fish, Zacco platypus.

The increased consumption of plastics worldwide, has led to the emergence of nanoplastics as important environmental pollutants. Despite the presence of nanoplastics in aquatic environments, their effects on ecosystems remain largely unexplored due to the analysis complexity. This study investigated the organ accumulation and toxic effects of 50 nm polystyrene nanoplastics (PS-NPs) in Zacco platypus (Z. platypus; also known as pale chub fish) using pyrolyzer-gas chromatography-mass spectrometry (Pyr-GC/MS). PS-NPs accumulated in Z. platypus' brain, digestive tract, branchia, and liver, causing changes at cellular level. Over a 14-day exposure, the accumulated PS-NPs led to observable changes in fish behavior (e.g., Total traveled distance and maximum velocity). In addition, the oxidative stress in each organ of Z. platypus increased as the exposure concentration of PS-NPs increased. This study shows that accumulation of nanoplastics in fish, resulting in behavioral changes and biochemical toxicity. As the pattern of change magnifies with exposure time and concentration, from a long-term perspective, the influence of nanoplastics on aquatic ecosystems become evident. This underscores the urgency for continuous research into the potential risks of nanoplastics in aquatic ecosystems.

Distribution and transformation of organophosphate esters in moving bed biofilm reactor.

A moving bed biofilm reactor (MBBR) process in wastewater treatment plants (WWTPs) uses plastic carriers, called biofilm carrier, to increase their treatment efficiency. Biofilm carrier is made up of plastic, containing the OPEs as flame retardants or plasticizers, so OPEs in biofilm carrier are possible to release from WWTPs to the river. This study investigated the effect of the MBBR process in WWTP on aquatic environments, focusing on OPEs. OPE eluted from the biofilm carrier by leaching test was tris(2-chloroethyl) phosphate (TCEP), and the concentration of the effluent compared to the influent was increased in the WWTP of the MBBR process. 3609 mg/day of TCEP would be discharged into the water using the second-order model with rate constant [Formula: see text] = 0.000451 (ng L-1)-1 h-1, which is the most suitable for the leaching concentration of TCEP. It was identified that TCEP in biofilm carrier was transformed into oxidative dechlorinated compounds and oxidative compounds by microorganisms in the bioreactor. As a result of the study, it was confirmed that not only TCEP but also transformation products of TCEP emitted into the water from the MBBR process of WWTP.

Organophosphate esters in Great Lakes fish: An improved analysis to assess concentrations and human exposure via consumption.

Organophosphate esters (OPEs) are flame retardant and plasticizer chemicals added to electronics, furniture, textiles, and other building materials and consumer products. In this study, fillets of fish often caught by anglers in the North American Great Lakes, Lake Trout (Salvelinus namaycush) across four Great Lakes and nearshore fish species near the large urban and industrial centers of Toronto and Hamilton, Canada, were analyzed for 22 OPEs. A rapid microextraction of homogenized tissues with methanol dramatically reduced preparation and sample handling time while achieving recoveries of 69-141%, and the optimized liquid chromatographic separation improved isomeric separations, including aryl-OPEs. Twelve of the 22 OPEs were detected, with frequencies of detection ranging from 8.3% to 98%, and five compounds were detected in >50% of the fish. The average ± standard deviation for the sum of 12 OPEs (ΣOPE12) ranged from 9.6 ± 0.9 (L. Erie 2017) to 74 ± 44 (L. Superior 2001) ng/g wet weight in Lake Trout, and 12 ± 2.7 to 35 ± 30 ng/g wet weight in nearshore fish species from the Toronto and Hamilton areas. The aryl-OPEs were dominant in Lake Trout, comprising 32-77% of total ΣOPE12 concentrations. In nearshore fish, the OPE patterns reflected the relative degree of exposure to run-off and wastewater inputs in the sampled receiving environments. The intake of OPEs via human consumption of Great Lakes Lake Trout and nearshore fish was estimated to range 6.5-31 ng/kg body weight/day, which is approximately 1-2 orders of magnitude lower than exposures via indoor air and ingestion/inhalation of dusts, and 3 orders of magnitude lower than estimated reference doses. The inclusion of additional OPE analytes enabled patterns of exposure and accumulation to be distinguished in fish of different species and location, and were related to source and food web influences.

Identification and Toxicity Prediction of Biotransformation Molecules of Organophosphate Flame Retardants by Microbial Reactions in a Wastewater Treatment Plant.

Organophosphate flame retardants (OPFRs) are substances added to plastics, textiles, and furniture, and are used as alternatives to brominated flame retardants. As the use of OPFRs increases in the manufacturing industry, the concentration in the aquatic environment is also increasing. In this study, OPFRs introduced into a wastewater treatment plant (WWTP) were identified, and the toxicity of biotransformation molecules generated by the biological reaction was predicted. Tris(2-butoxyethyl) phosphate, tris(2-butoxyethyl) phosphate, and triphenyl phosphate were selected as research analytes. Chemicals were analyzed using high-resolution mass spectrometry, and toxicity was predicted according to the structure. As a result, tris(1-chloro-2-propyl) phosphate showed the highest concentration, and the removal rate of OPFRs in the WWTP was 0-57%. A total of 15 biotransformation products were produced by microorganisms in the WWTP. Most of the biotransformation products were predicted to be less toxic than the parent compound, but some were highly toxic. These biotransformation products, as well as OPFRs, could flow into the water from the WWTP and affect the aquatic ecosystem.

Identification of biotransformation products of organophosphate ester from various aquatic species by suspect and non-target screening approach.

Organic pollutants that are introduced into the aquatic ecosystem can transform by various mechanisms. Biotransformation is an important process for predicting the remaining structures of pollutants in the ecosystem, and their toxicity. This study focused on triphenyl phosphate (TPHP), which is a commonly used organophosphate flame retardant and plasticizer. Since TPHP is particularly toxic to aquatic organisms, it is essential to understand its biotransformation in the aquatic environment. In the aquatic ecosystem, based on consideration of the producer-consumer-decomposer relationship, the biotransformation products of TPHP were identified, and their toxicity was predicted. Liquid chromatography-high resolution mass spectrometry was used for target, suspect, and non-target analysis. The obtained biotransformation products were estimated for toxicity based on the prediction model. As a result, 29 kinds of TPHP biotransformation products were identified in the aquatic ecosystem. Diphenyl phosphate was detected as a common biotransformation product through a hydrolysis reaction. In addition, products were identified by the biotransformation mechanisms of green algae, daphnid, fish, and microorganism. Most of the biotransformation products were observed to be less toxic than the parent compound due to detoxification except some products (hydroquinone, beta-lyase products, palmitoyl/stearyl conjugated products). Since various species exist in a close relationship with each other in an ecosystem, an integrated approach for not only single species but also various connected species is essential.

Characterizing biotransformation products and pathways of the flame retardant triphenyl phosphate in Daphnia magna using non-target screening.

Triphenyl phosphate (TPHP), one of the organophosphate flame retardants, has been widely used in manufacturing, thereby causing a gradual increase in TPHP concentrations in aquatic environments. However, the information on the biotransformation mechanism of TPHP in invertebrates is lacking. The study identified the biotransformation products of TPHP in Daphnia magna, which showed particularly high toxicity in aquatic organisms, and determined the rates of depuration. Daphnia magna, a standard species for toxicity studies, was exposed to triphenyl phosphate and transferred to the pure medium. The biotransformation products of TPHP and its depuration rates were determined by liquid chromatography-high resolution mass spectrometry. Nine biotransformation products (five in the positive mode and four in the negative mode) of triphenyl phosphate were identified in D. magna. Based on the depuration ratio, the major biotransformation mechanism is estimated to be cysteine conjugation and sulfation. Certain biotransformation products (diphenyl phosphate, hydroxylated triphenyl phosphate, and thiol triphenyl phosphate) might induce toxicity in biota. The results could be used to predict main biotransformation processes and toxic products of organophosphate flame retardants in aquatic invertebrates.

Profiling the decomposition products of perfluorooctane sulfonate (PFOS) irradiated using an electron beam.

Perfluorooctane sulfonate (PFOS) has been found in wastewater treatment plants (WWTPs) and in surface water as a result of domestic uses of textiles, electronics, and surfactants. The detection of PFOS in the aqueous environment has been linked to hazardous biological effects including estrogenicity and genotoxicity. To provide an alternative to conventional processes, one of the radical-based advanced oxidation and reduction processes being tested for treatment of refractory compounds in water, involves the use of an electron beam. Therefore, the aims of this study were to investigate the degradation efficiency of PFOS (100mg/L) by electron beam, to evaluate the predicted toxicity of the radiolysis products using the ECOSAR model, and to identify the radiolytic products of PFOS. As a result of using the ECOSAR model, the toxicity levels of by-products after electron beam treatment were reduced by decreasing the carbon-chain number of PFOS. The molecular structures of the radiolytic products were elucidated using authentic standards via liquid chromatography and tandem mass spectrometry, and by the interpretation of MS2 fragmentation patterns of each product using liquid chromatography with quadrupole time of-flight mass spectrometry (LC-QTOF-MS). In total, ten radiolytic products were confirmed by LC-MS/MS, HPLC, and IC data matching with commercial standards. The two radiolytic substances produced during irradiation with an electron beam were predicted by LC-QTOF-MS. This study led to an understanding of the role of electron beams in the transformation of parent compounds and to the decomposition products created when an electron beam is applied to treat perfluorinated compounds.

Combined toxic effect of airborne heavy metals on human lung cell line A549.

Many studies have demonstrated that heavy metals existing as a mixture in the atmospheric environment cause adverse effects on human health and are important key factors of cytotoxicity; however, little investigation has been conducted on a toxicological study of a metal mixture from atmospheric fine particulate matter. The objective of this study was to predict the combined effects of heavy metals in aerosol by using in vitro human cells and obtain a suitable mixture toxicity model. Arsenic, nickel, and lead were selected for mixtures exposed to A549 human lung cancer cells. Cell proliferation (WST-1), glutathione (GSH), and interleukin (IL)-8 inhibition were observed and applied to the prediction models of mixture toxicity, concentration addition (CA) and independent action (IA). The total mixture concentrations were set by an IC10-fixed ratio of individual toxicity to be more realistic for mortality and enzyme inhibition tests. The results showed that the IA model was statistically closer to the observed results than the CA model in mortality, indicating dissimilar modes of action. For the GSH inhibition, the results predicted by the IA and CA models were highly overestimated relative to mortality. Meanwhile, the IL-8 results were stable with no significant change in immune reaction related to inflammation. In conclusion, the IA model is a rapid prediction model in heavy metals mixtures; mortality, as a total outcome of cell response, is a good tool for demonstrating the combined toxicity rather than other biochemical responses.