A green method for the determination of illicit drugs in wastewater and surface waters-based on a semi-automated liquid-liquid microextraction device.

Liquid-phase microextraction (LPME) is a simple, low-cost, and eco-friendly technique that enables the detection of trace concentrations of organic contaminants in water samples. In this work, a novel customized microextraction device was developed for the LPME extraction and preconcentration of nine illicit drugs in surface water and influent and effluent wastewater samples, followed by analysis by GC-MS without derivatization. The customized device was semi-automated by coupling it with a peristaltic pump to perform the collection of the upper layer of the organic phase. The extraction parameters affecting the LPME efficiency were optimized. The optimized conditions were: 100 µL of a toluene/DCM/EtAc mixture as extractor solvent; 30min of extraction time under vortex agitation (500rpm) and a solution pH of 11.6. The limits of detection and quantification ranged from 10.5ng L-1 (ethylone) to 22.0ng L-1 (methylone), and from 34.9ng L-1 to 73.3ng L-1 for these same compounds, respectively. The enrichment factors ranged from 39.7 (MDMA) to 117 (cocaethylene) and the relative recoveries ranged from 80.4% (N-ethylpentylone) to 120% (cocaine and cocaine-d3). The method was applied to real surface water, effluent, and influent wastewater samples collected in Salvador City, Bahia, Brazil. Cocaine was the main drug detected and quantified in wastewater samples, and its concentration ranged from 312ng L-1 to 1,847ng L-1. Finally, the AGREE metrics were applied to verify the greenness of the proposed method, and an overall score of 0.56 was achieved, which was considered environmentally friendly.

Spatio-temporal assessment, sources and health risks of water pollutants at trace levels in public supply river using multivariate statistical techniques.

The Joanes River is located in the northeast of Brazil, crosses the Camaçari Petrochemical Complex, the largest integrated industrial complex in the Southern Hemisphere, which has over 90 companies in the chemical and petrochemical industry. The present study aims to evaluate spatial distribution, seasonal variation and identify possible sources of trace metal contamination in surface water samples of the Joanes River. Samples were collected in the dry (December 2018) and rainy (August 2019) seasons. Analysis of trace elements (As, Cd, Cr, Cu, Ni, Mn and Pb) were performed by ICP-MS. A total of 60 water samples were obtained. Samples were analyzed using exploratory techniques such as principal component analysis (PCA) and cluster analysis (CA). It was possible to characterize the samples according to the seasonal variation. The formation of two groups was observed. Among these, samples from the rainy season presented the higher levels of metals in relation to the samples of the dry season. Natural and anthropic sources of metal contamination were identified using CA. Similarity was shown in the relationship between the metals As-Pb and Ni-Cd-Cr-Cu in the dry season, and Cd-Ni and Pb-As-Cr-Cu in the rainy season. Dermal absorption (HQderm) and ingestion hazard quotients (HQing) routes exhibited values of less than one for all the elements analyzed for adults and children, in both rainy and dry seasons. This indicated that the pollutants analyzed posed little or no health risk over a lifetime of exposure. According to international guidelines (US EPA), the values of Cu, Pb and Cr were above the limit established.