A modified QuEChERS method for determination of organophosphate esters in milk by GC-MS.

Organophosphate esters (OPEs) are substances that have been detected in several matrices due to their use as flame retardants and plasticizers. Human exposure to OPEs can cause endocrine disruption, neurotoxicity, and reproductive disturbance. Ingestion of contaminated food can be a significant route of exposure to OPEs. Food can be contaminated by OPEs in the food chain, during cultivation, and by contact with plasticizers during the production chain of processed foods. In this study, a method for the determination of 10 OPEs in commercial bovine milk was developed. The procedure was based on QuEChERS extraction and gas chromatography coupled to mass spectrometry (GC-MS) analysis. QuEChERS modification included a freezing-out step after the extraction followed by the concentration of the entire acetonitrile phase before the clean-up step. Calibration linearity, matrix effects, recovery, and precision were evaluated. Significant matrix effects were observed, which were compensated by matrix-matched calibration curves. Recoveries ranged from 75 to 105%, with a relative standard deviation ranging from 3 to 38%. The method detection limits (MDLs) were in the range of 0.43-4.5 ng mL-1, while the method quantification limits (MQLs) were within the range from 0.98 to 15 ng mL-1. The proposed method was successfully validated and applied to determine the concentrations of OPEs in bovine milk. The 2-ethylhexyl diphenyl phosphate (EHDPHP) was detected in the analyzed milk samples but at levels below the MQL.

Multilayered solid phase extraction and ultra performance liquid chromatographic method for suspect screening of halogenated pharmaceuticals and photo-transformation products in freshwater - comparison between data-dependent and data-independent acquisition mass spectrometry.

Since conventional biological wastewater treatments are not admittedly effective to convert pharmaceutical active compounds (PhACs) into nontoxic products, natural abiotic mechanisms such as solar photolysis arises as an important degradation process, especially for halogenated molecules. In the present work, photolysis simulation was carried out in-lab for precursors and their respective photo-transformation products (photo-TPs), which were analyzed through reversed-phase ultra-high performance liquid chromatography coupled to high resolution mass spectrometry (RP-UHPLCHRMS). An in-house library was created in order to provide reference information for target (precursors) and suspect screening (photo-TPs) analysis of freshwater samples from impacted aquatic environments. Strategies in the use of data-dependent acquisition (DDA) and data-independent acquisition (DIA), as well as the data processing software are discussed here for the identification of 6 PhACs and photo-TPs. Because no standards of photo-TPs were available, only the target compounds, i.e. sitagliptin (398 ± 2 ng L-1), iohexol (209 ± 5 ng L-1), lamotrigine (103 ± 10 ng L-1), losartan (43 ± 10 ng L-1), ofloxacin (28 ± 7 ng L-1), and sertraline (25 ± 7 ng L-1) could be quantified through multiple standard additions.

Ferroin in dyes degradation by Fenton-like process: a chemical waste recycling perspective.

Published literature describes the formation of the Fe (II)-phenanthroline complex (ferroin) as a stop way for Fenton processes, reducing radical yield. By contrast, this study presents evidence that ferroin can be activated by UVA in mildly acidic media in a photo-Fenton-like process. Because ferroin is the main waste from total iron determination in environmental samples, a recycling approach is suggested. Based on the best practices of waste management planning, an application of the proposed method for treating another chemical waste is presented. Titrimetric ammonia determination waste containing 2.67 mg L-1 methyl red azo dye and 1.33 mg L-1 methylene blue was degraded using the optimized experimental conditions: pH = 5.2-5.4; [H2O2] = 310 mg L-1; [ferroin] = 1.4 mg L-1; temperature = 36 ± 1 °C; reaction time = 165 min under UVA irradiation. Attenuation of most intense spectroscopic bands for the dyes achieved 94% (510 nm) and 96% (665 nm) reduction for methyl red and methylene blue, respectively, with degradation of ferroin itself. The present work brings empirical evidence that is possible to recycle ferroin as photo-Fenton-like process catalyst, as well as determine the best conditions for providing less acidic treated effluents with negligible suspended solid concentration, better than that obtained from classical photo-Fenton processes.

Removal of diclofenac by a local bacterial consortium: UHPLC-ESI-MS/MS analysis of metabolites and ecotoxicity assessment.

Diclofenac (DCF) belongs to the class of nonsteroidal anti-inflammatory drugs, which is one of the most consumed by population and detected in raw sewage. Several studies have reported variable removal rates by biodegradation of diclofenac in wastewater treatment plants (WWTPs). This study deals with the evaluation of the biodegradation of DCF by a bacterial consortium (obtained from pure cultures of Enterobacter hormaechei D15 and Enterobacter cloacea D16), which were isolated from household compost and Algerian WWTP, respectively, as sole carbon source and by co-metabolism, using glucose as carbon source. A 98% removal rate of DCF was observed when it is used as the sole carbon source, whilst only 44% of DCF was removed in co-metabolic conditions. Two metabolites were identified using ultra-high-performance liquid chromatography coupled to electrospray injection tandem mass spectrometry analysis (UHPLC-ESI-MS/MS); one of them was identified as 4'-hydroxy-DCF, and the second metabolite was suspected to be a nitro derivative of DCF, according to comparison with the literature. Biodegradation of DCF by this bacterial consortium generates relatively safe final by-products.

Occurrence and risk assessment of organophosphate esters in urban rivers from Piracicaba watershed (Brazil).

Organophosphate esters (OPEs) are substances globally used as flame retardants and plasticizers that have been detected in all environmental compartments. This study aimed to evaluate the occurrence and sources of ten OPEs in the Piracicaba River Basin (Brazil). Twelve sampling sites were selected in five rivers with different pollution sources; six sampling campaigns were performed encompassing dry and wet seasons. ΣOPEs ranged from 0.12 to 6.2 µg L-1; the levels in urban areas were higher than in rural and non-urban areas, but no overall tendency concerning the seasonal effect on OPEs concentrations was observed. Tris(2-butoxyethyl) phosphate (TBOEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were the most abundant and frequently detected compounds. Nine OPEs were detected at higher concentrations in a site affected by effluents from textile industries. An acute toxicity test using Daphnia similis was performed for tris(2-ethylhexyl) phosphate (TEHP) for the calculation of a preliminary predicted no effect concentration (PNEC). The risk quotient (RQ) approach was applied and risk to aquatic environment related to TEHP levels was observed in areas adjacent to textile industries, but more toxicity studies are required for the determination of a more reliable PNEC.

Response surface methodology applied to tropical freshwater treatment.

This paper presents the profits and disadvantages of the chemometrics approach instead of the one-factor-at-a-time (OFAT) coagulation diagram approach for tropical water physicochemical treatment. Central composite design associate to response surface methodology (CCD-RSM) is used to find the real best conditions for coagulant dosage and pH aiming at high-turbidity removal. The number of experiments needed to chemometrics model construction (12) is comparatively smaller than that used in the coagulation diagram (84), saving financial and environmental resources. Arguments for Water Treatment Plants (WTP) considering the replacement of coagulation diagram approach by the CCD-RSM approach in drinking water treatment are presented. Chemometrics models are all constructed on a free software platform, providing the best pH within the range 7.7-8.1, and the best coagulant dosage (polyaluminium chloride, PAC) between 2.0 and 3.1 mg Al2O3 L-1 (equivalent in mass). CCD-RSM provides a faster, lower-cost and more reliable alternative tool for WTP decision-making instead of the OFAT model, mainly for waters more affected by seasonal effects as can be seen in tropical and subtropical countries.

Organophosphate esters by GC-MS: An optimized method for aquatic risk assessment.

Organophosphate esters used as flame retardants and plasticizers are ubiquitous contaminants in surface waters. Many studies indicate that these compounds are neurotoxicants, endocrine disruptors, and may affect reproduction and development of aquatic organisms. Thus, analytical methods that allow accurate quantification of these contaminants at environmentally relevant concentrations are desirable for risk assessment studies. In this study, a method based on solid phase extraction and gas chromatography coupled to mass spectrometry was developed for determination of organophosphate esters in river water extracts. Multivariate optimization was used to determine the best conditions for injection of larger volumes of sample in a Programmable Temperature Vaporization inlet. Furthermore, the matrix effect on the instrumental response was evaluated and compensated by association of extraction-blank-matched calibration and isotopically labeled focus standards. The method quantification limits ranged from 0.009 to 0.11 µg/L, staying below the predicted non-effect concentration for the aquatic compartment for all analytes, which is a requisite for using in risk assessment studies. The method was applied to freshwater samples collected in rivers from the Sao Paulo State, Brazil, and eight out of the ten target organophosphate esters were quantified, being tris(2-chloroisopropyl) phosphate and tris(phenyl) phosphate the most frequently detected compounds.

Optimization of UV/H2O2 and ozone wastewater treatment by the experimental design methodology.

The objective of this study was to optimize UV/H2O2 and ozonation systems by means of an experimental design using as a response the efficiency of the operational conditions to remove the methylene blue (MB) dye. Two classes of experimental planning were used: the Doehlert matrix (DM) and the central composite design (CCD). The most important variables for each process were hydrogen peroxide concentration, the ratio of illuminated volume/total volume of the reactor and recirculation flow rate for UV/H2O2, and ozone flow rate, consumed ozone and MB concentration for the ozonation. The DM was more efficient in optimizing the systems, since it used a smaller number of experiments and achieved similar results when compared to the CCD. After optimization, the disinfection efficiency of the systems was tested with secondary effluent evaluating the inactivation of microbiological indicators, Escherichia coli and total coliforms, using the optimized and the worst condition previously obtained with MB removal as response. The inactivation efficiencies in the optimum conditions were about 99%, allowing an efficient disinfection as well as the production of an effluent with quality to be reused according to specific legislations, while at the worse conditions, the inactivation did not reach standards for reuse.