Are volatile methylsiloxanes in downcycled tire microplastics? Levels and human exposure estimation in synthetic turf football fields.

Downcycled rubber, derived from end-of-life tires (ELTs), is frequently applied as crumb rubber (CR) as infill of synthetic turf in sports facilities. This practice has been questioned in recent years as numerous studies have reported the presence of potentially hazardous chemicals in this material. CR particles fall into the category of microplastics (MPs), making them possible vectors for emerging micropollutants. A preliminary study where volatile methylsiloxanes (VMSs) were found in CR originated the hypothesis that VMSs are present in this material worldwide. Consequently, the present work evaluates for the first time the levels and trends of seven VMSs in CR from synthetic turf football fields, while attempting to identify the main sources and impacts of these chemicals. A total of 135 CR samples and 12 other of alternative materials were analyzed, employing an ultrasound-assisted dispersive solid-phase extraction followed by gas chromatography-mass spectrometry (GC-MS), and the presence of VMSs was confirmed in all samples, in total concentrations ranging from 1.60 to 5089 ng.g-1. The levels were higher in commercial CR (before field application), a reflection of the use of VMS-containing additives in tire production and/or the degradation of silicone polymers employed in vehicles. The VMSs generally decreased over time on the turf, as expected given their volatile nature and the wearing of the material. Finally, the human exposure doses to VMSs in CR (by dermal absorption and ingestion) for people in contact with synthetic turf in football fields were negligible (maximum total exposure of 20.5 ng.kgBW-1.year-1) in comparison with the European Chemicals Agency (ECHA) reference doses: 1.35 × 109 ng.kgBW-1.year-1 for D4 and 1.83 × 109 ng.kgBW-1.year-1 for D5. Nevertheless, more knowledge on exposure through inhalation and the combined effects of all substances is necessary to provide further corroboration. This work proved the presence of VMSs in CR from ELTs, another family of chemical of concern to take into account when studying MPs as vectors of other contaminants.

Cupressus macrocarpa leaves for biomonitoring the environmental impact of an industrial complex: The case of Puchuncaví-Ventanas in Chile.

The Punchuncaví Valley is one of the most polluted areas in central Chile affected by anthropogenic emissions from the Ventanas Industrial Complex (IC) where the most important industry is the copper smelter and refinery. In this context, this research aims were to assess the usefulness of the Cupressus macrocarpa as a biomonitor. The leaf samples were taken from five selected sites, located between 0.8 and 15 km away from the source. A total of 34 elements were analyzed in leaf samples by ICP-MS and examined by enrichment factor (EF), hierarchical cluster analysis (HCA), and principal component analysis (PCA). Leaf concentration of As, Ca, Cd, Cu, Dy, Er, Gd, K, Li, Mg, Mn, Mo, Na, Nd, P, Pb, Pr, S, Sb, Sr, Ti, Yb and Zn showed statistically significant differences between sampling sites (p-value < 0.05). A clear trend to increase the concentration of Cu, Sb, S, As, Cd and Pb with the proximity to the IC. Besides, high values of Cu (93.4-369 mg kg-1) and As (7.6-12.7 mg kg-1) were observed near to industrial area exceed the phytotoxic levels reported in plants with EF > 3000% for Cu and >1300% for As. The application of PCA and HCA identified 6 factors related to the industrial complex, traffic and geogenic sources, providing the greatest variance the component related to industrial activity mainly with copper smelter and refinery. According to the results, the C. macrocarpa leaves are a good biomonitor to evaluate the high pollution load for anthropogenic elements in industrial areas.

Tradescantia as a biomonitor for genotoxicity evaluation of diesel and biodiesel exhaust emissions.

Biodiesel, an alternative energy source, is promoted as cleaner and safer than other fuel options due to its reported reduction of particulate and gaseous emissions (CO2, CO, and total hydrocarbons). However, its volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbon (PAHs) emissions are key to understanding its toxic, mutagenic and carcinogenic risk factors. This research was developed to assess the genotoxic impact of exhaust emissions using biodiesel from animal fat, palm oil and soybean oil blended with diesel (B80). Diluted exhaust gases were analyzed simultaneously for pollutant emissions and for toxicity using an exposure chamber called the BioToxMonitor, where Tradescantia pallida and a KU-20 clone were exposed to exhaust following Trad-MCN and Trad-SH bioassays. The results show differences in the emission compositions and considerable mutagenic potential among the three biodiesels tested, with palm oil biodiesel emissions being the least harmful, based on its low pollutant concentrations and the negative response in the TradSH bioassay. In contrast, the animal fat biodiesel and soybean oil biodiesel emissions were as toxic as the diesel emissions, being positive in both Trad bioassays. This could be related to the PAH and carbonyl concentrations found in the vehicular exhaust. The genotoxicity of diesel emissions was related to PM1 and the concentrations of both gas and particle PAHs concentrations, which were two times higher compared to the highest concentrations observed for biodiesel. The data suggest that micronucleus assays in Tradescantia pallida are more sensitive for gaseous pollutant exposure. This is the first reported study of biodiesel exhaust biomonitoring in situ and under controlled conditions inside an exposure chamber.

Tradescantia as a biomonitor for pesticide genotoxicity evaluation of iprodione, carbaryl, dimethoate and 4,4'-DDE.

There is a current tendency to develop and apply environmentally friendly techniques that meet the requirements of green analytical chemistry as an alternative to conventional analytical methods. For toxicity evaluation, these alternatives may be found in bioassays such as Tradescantia. This technique, developed in the 1980s, is highly sensitive to evaluate environmental mutagens, simple and cheap. In this paper, the sensibility of both the Tradescantia micronucleus bioassay (Trad-MCN) and the Tradescantia stamen hair bioassay (Trad-SH) were studied for carbaryl, dimethoate and iprodione, common agricultural and domestic pesticides that are currently used in Chile, which have never been tested with such bioassays. Biomonitor exposures were performed by capillary absorption for each individual pesticide over a wide range of concentrations, from maximum residue limits (trace levels) up to the application dose in agricultural fields. In addition, the organochloride 4,4'-DDE was included but only in the concentration range from 0.01mgL-1 to 1mgL-1, mimicking residue concentrations since it is not a commercial product but, rather, the main breakdown product of the persistent organochloride pesticide 4,4-DDT, whose use was discontinued in Chile in the 1980s. The Trad-MCN bioassay revealed a significant increase in micronucleus frequency at the early tetrads of meiotic pollen mother cells of the biomonitor Tradescantia pallida var. purpurea, induced by 4,4'-DDE (for 1mgL-1), dimethoate (for 40mgL-1, 200mgL-1, 400mg/L-1) and carbaryl (for 889mgL-1). Iprodione did not generate any significant change at the tested concentration. Meanwhile, the Trad-SH bioassay was carried out by analysis of the phenotype variations of the stamen hair cells of the Tradescantia clone KU-20 for the same pesticides and doses. This bioassay was not sufficiently sensitive for toxicity evaluation of most of the pesticides tested, with exception of dimethoate in low doses (2 and 5mg/L-1).

Obtaining polycyclic aromatic hydrocarbon concentration ratios and molecular markers for residential wood combustion: Temuco, a case study.

It is known that residential wood combustion (RWC) is an important source of fine particle emissions. The purpose of this work was to characterize the chemical composition of the particulate matter present in the Temuco urban atmosphere during winter, specifically the polycyclic aromatic hydrocarbon (PAH) profile, because PAHs are considered to be among the key compounds in particulate matter toxicity. During the 2008 winter monitoring campaign, samples of particulate matter with aerodynamic diameters of < or = 10 (PM10) and < or = 2.5 (PM2.5) microm were taken on days with contamination episodes. Sixteen U.S. Environmental Protection Agency (EPA) PAH compounds were extracted with toluene and determined by gas chromatography-mass spectrometry (GC-MS). The results show that phenantrene was the predominant compound associated with particulate matter at a concentration range between 300 and 600 ng m(-3), 18 times higher than the second most abundant PAH compound. High-molecular-mass compounds such as dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3,c,d]pyrene were also found, but they were minorities in the set. It was recognized from the PAH concentration ratios of the Temuco atmospheric aerosol that the main contamination source was in fact residential wood combustion; although not all the concentration ratios evaluated match the reported reference values, probably due to the kind of biomass used, the characteristics of Chilean heating appliances and climate.

Analysis of s-triazine-degrading microbial communities in soils using most-probable-number enumeration and tetrazolium-salt detection.

A simple and sensitive method for the detection and enumeration of microbial s-triazine-degrading microorganisms in soil was designed. The procedure is based on the ability of some microbes to use s-triazines, such as simazine, atrazine, and cyanuric acid, as sole nitrogen source. It employs the respiration indicator 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) to detect metabolic activity and the most-probable-number (MPN) enumeration in microtiter plates. The method was used to identify simazine- and cyanuric acid-degrading activities in agricultural soils treated with the herbicide simazine. The MPN-TTC method showed that the number of simazine- and cyanuric acid-degrading microorganisms increased four weeks after the herbicide simazine had been applied.

Analysis of s-triazine-degrading microbial communities in soils using most-probable-number enumeration and tetrazolium-salt detection

A simple and sensitive method for the detection and enumeration of microbial s-triazine-degrading microorganisms in soil was designed. The procedure is based on the ability of some microbes to use s-triazines, such as simazine, atrazine, and cyanuric acid, as sole nitrogen source. It employs the respiration indicator 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) to detect metabolic activity and the most-probable-number (MPN) enumeration in microtiter plates. The method was used to identify simazine- and cyanuric acid-degrading activities in agricultural soils treated with the herbicide simazine. The MPN-TTC method showed that the number of simazine- and cyanuric acid-degrading microorganisms increased four weeks after the herbicide simazine had been applied (AU)

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