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.

Multivariate optimization of a green procedure for determination of emerging polycyclic aromatic nitrogen heterocycles in PM2.5 from sites with different characteristics.

Emerging polycyclic aromatic nitrogen heterocycles (PANHs) contributes significantly to the health risk associated with inhaling polluted air. However, there is a lack of analytical methods with the needed performance to their determination. This study presents the optimization and validation for the first time of a green microscale extraction procedure for the determination of twenty-one PANHs, including carbazole, indole, and quinolone classes, in particulate matter (PM2.5) samples by gas chromatography-mass spectrometry. A simplex-centroid mixture design and full factorial design (23) were employed to optimize the following extraction parameters: type and volume of solvent, sample size, extraction time, and necessity of a cleanup step. Low limits of detection and quantification (LOD < 0.97 pg m-3 and LOQ < 3.24 pg m-3, respectively) were obtained in terms of matrix-matched calibration. The accuracy and precision of the method were adequate, with recoveries in three levels between 73 to 120% and intraday and interday relative standard deviations from 2.0 to 12.9% and 7.3 to 18.9%, respectively. The green character of the method was evaluated using the Analytical Greenness (AGREE) tool, where a score of 0.69 was obtained, indicating a great green procedure. The method was applied to PM2.5 samples collected from sites with different characteristics; the concentrations ranged from 69.3 pg m-3 (2-methylcarbazole) to 11,874 pg m-3 (carbazole) for individual PANHs and from 2306 to 24,530 pg m-3 for ∑21PANHs. Principal component analysis (PCA) and hierarchical clustering enabled discrimination of the sampling sites according to the PANHs concentrations. The score plots formed two distinct groups, one with samples containing higher concentrations of PANHs, corresponding to sites with a major influence from diesel emissions, and another group with minor PANH contents, corresponding to sites impacted by emissions from urban traffic and industrial activities.

Quantification of polycyclic aromatic sulfur heterocycles in fine airborne urban particles (PM2.5) after multivariate optimization of a green procedure.

Polycyclic aromatic sulfur heterocycles (PASHs), such as benzothiophenes (BT), dibenzothiophenes (DBT) and benzonapthothiophenes (BNT), can be emitted from vehicular traffic and deposited in fine particles matter (PM2.5). The presence of these compounds in PM2.5 is an environmental concern due to air pollution and its toxic properties. In this study, a green microscale solid-liquid extraction method was developed to determine twenty-three PASHs in PM2.5. A simplex-centroid mixture design was applied to optimize the extraction solvent. A full factorial design was used for preliminary evaluation of the factors that influence the extraction process (extraction time, sample size, and solvent volume) and then a Doehlert design for the significant parameters. The optimal extraction conditions based on the experimental design were: sample size, 4.15 cm2; 450 µL of toluene:dichloromethane (80:20,v/v); and extraction duration, 24 min. High sensitivity (LOD < 0.66pg m-3 and LOQ < 2.21 pg m-3) and acceptable recovery (82.8-120 %), and precision (RSD 3.6-14.0 %) were obtained. The greenness of the method was demonstrated using the Analytical GREEnness (AGREE) tool. The method was applied for analyzing PASHs in PM2.5 samples collected in three time intervals per day from years with different sulfur contents in the diesel: S-500 (≤500 ppm sulfur) and S-50 (≤50 ppm sulfur). Fourteen PASHs were quantified with the highest concentrations observed for 2,8-DMDBT and 4,6-DMDBT, which are recalcitrant compounds. The ANOVA test indicated significant differences between sampling periods during the day. The reduction of diesel S-500 to S-50 corresponded to a 28 % decrease in the total sum of PASHs (∑PASHs) evaluated. Spearman's rank correlations allowed for verifying that BTs and DBTs were highly correlated, suggesting that they were derived from similar sources. A weak correlation of 2,1-BNT and 2,3-BNT with BTs and DBTs indicates that these compounds are a chemical proxy for the emission of diesel engines during the combustion process.

Plastic pellets make Excirolana armata more aggressive: Intraspecific interactions and mortality in field and laboratory ecotoxicological assays.

Microplastics, including plastic pellets, get stranded on sandy beaches. They persist in the oceans for long periods and frequently carry contaminants. Acute and chronic toxicity has been observed when marine organisms are exposed to high densities of plastic pellets in laboratory assays. We investigated the toxicity of beach-stranded plastic pellets on macrobenthic populations (Excirolana armata; Crustacea; Isopoda) under natural conditions (in situ). We simulated different pellets densities on a beach not contaminated by pellets, exposing isopods for 6 h and testing possible behavioral responses (i.e., vertical displacement) and mortality effects. No effect was observed on vertical displacement, but higher mortality was reported for organisms exposed to plastic pellets. The lowest pellet density tested commonly found in coastal areas was sufficient to trigger mortality. We also observed that lethargic individuals (near-death) were preyed on by the healthy individuals remaining in the test chambers.

Occurrence, sources, and risk assessment of unconventional polycyclic aromatic compounds in marine sediments from sandy beach intertidal zones.

This study investigated the concentrations of polycyclic aromatic compounds (PACs), including parent polyaromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives, in 48 sediment samples from the intertidal region of sandy beaches in Baía de Todos os Santos (BTS), Salvador, State of Bahia, Brazil. The total PAH (∑PAH) concentration, total nitro-PAH (∑nitro-PAH) concentration, and total oxy-PAH (∑oxy-PAH) concentration ranged from 2.11 µg g-1 dry weight (dw) to 28.0 µg g-1 dw, 2.58 µg g-1 dw to 30.2 µg g-1 dw, and 0.34 µg g-1 dw to 3.65 µg g-1 dw, respectively. Elevated concentrations of parent PAHs and nitro-PAHs were found in samples from two sites in BTS, which were also characterized by high percentages of fine-medium sand and low organic matter contents. Potent mutagenic 3-nitrobenzanthrone (3-NBA) was found in 86% of the samples at concentrations ranging from 0.200 µg g-1 dw to 0.690 µg g-1 dw. Furthermore, calculations of the benzo[a]pyrene toxicity equivalency (BaPTEQ) indicated that three carcinogenic high-molecular-weight PAHs accounted for 98.7% of the total maximum PAH concentration. Finally, we assessed the possible environmental risks posed to benthic species living in the sediments of BTS. The results showed that the risk quotient for PAHs (RQPAHs) was ≥1. In turn, the summed RQ for all PACs (∑RQmixture) ranged from 1 to 30, but did not exceed the maximum allowable threshold; thus, the risks posed to benthic species were moderate for all sediment samples.

Customized dispersive micro-solid-phase extraction device combined with micro-desorption for the simultaneous determination of 39 multiclass pesticides in environmental water samples.

A dispersive micro-solid phase extraction (d-µ-SPE) procedure was developed for the simultaneous extraction of 39 multiclass pesticides, containing a variety of chemical groups (organophosphate, organochlorine, pyrethroid, strobilurin, thiocarbamate, triazole, imidazole, and triazine), from water samples. A customized d-µ-SPE glass device was combined with a multi-tube platform vortex and a micro-desorption unit (Whatman Mini-UniPrep G2 syringeless filter), which allowed the unique simultaneous desorption, extract filtration, and injection. A simplex-centroid mixture design and Doehlert design were employed to optimize the extraction conditions. The optimized extraction conditions consisted of an extraction time of 30 min, an addition of 6.74 % of NaCl into 100 mL of water sample, and a desorption time of 24 min with 500 µL of EtAc. The procedure provided a low limit of detection (LOD), ranging from 0.51 ng L-1 (4,4-DDE) to 22.4 ng L-1 (dimethoate), and an enrichment factor ranging from 72.5 (dimethoate) to 200 (tebuconazole). The relative recoveries of the pesticides from spiked freshwater and seawater ranged from 74.2 % (endrin) to 123 % (molinate). The proposed procedure was applied to detect the presence of multiclass pesticides in environmental water samples. Three pesticides commonly applied in Brazil, namely, malathion, dimethoate, and lambda-cyhalothrin, were detected in concentrations ranging from

Sequential determination and chemical speciation analysis of inorganic As and Sb in airborne particulate matter collected in outdoor and indoor environments using slurry sampling and detection by HG AAS.

In this work, fast sequential determination and chemical speciation analysis of inorganic arsenic and antimony in airborne particulate matter collected in outdoor and indoor environments using slurry sampling and detection by hydride generation atomic absorption spectrometry (HG-AAS) is proposed. A Doehlert design was applied to optimise the hydride generation conditions of As and Sb for fast sequential determination in the same aliquot of particulate matter samples after preparation of the slurry. The limits of quantification (LoQ) obtained for As and Sb were 0.3 and 0.9 ng m-3, respectively. The accuracy of the analytical method was confirmed by analysis of the certified reference material of urban particulate matter (SRM NIST 1648a), presenting concordance with certified values of 92.7±7.7% for As and 91.2±9.5% for Sb. Precision was expressed as relative standard deviation (% RSD, n=3), with our results presenting values better than 3.4% and 4.2% for total inorganic As and Sb, respectively. For all analysed samples, total As concentrations and its inorganic species were below the LoQ of the analytical method (<0.3 ng m-3). However, the averages of total inorganic Sb concentrations in airborne particulate matter, collected as total suspended outdoor particles (TSPoutdoor), inhalable particulate matter (PM10), and total suspended indoor particles (TSPindoor), were 3.1±0.5, 2.4±0.6, and 2.6±0.4 ng m-3, respectively. Trivalent Sb (Sb3+) was the predominant inorganic species in all samples investigated, with mean percentages of 76%, 72%, and 73% in TSPoutdoor, PM10, and TSPindoor, respectively. The presence of Sb and its predominant inorganic form (Sb3+) can be attributed to vehicular traffic close to the sampled urban areas. Therefore, fast sequential determination of As and Sb and their inorganic species in particulate matter samples prepared as slurry by FS-HG-AAS is an efficient, accurate, and precise method and can be successfully applied to routine analysis.