Simultaneous Determination of Steroids and NSAIDs, Using DLLME-SFO Extraction and HPLC Analysis, in Milk and Eggs Collected from Rural Roma Communities in Transylvania, Romania.

This research aims to determine five steroids and four non-steroidal anti-inflammatory drugs in milk and egg samples collected from rural Roma communities in Transylvania, Romania. Target compounds were extracted from selected matrices by protein precipitation, followed by extract purification by dispersive liquid-liquid microextraction based on solidification of floating organic droplets. The extraction procedure was optimized using a 24 full factorial experimental design. Good enrichment factors (87.64-122.07 milk; 26.97-38.72 eggs), extraction recovery (74.49-103.76% milk; 75.64-108.60% eggs), and clean-up of the sample were obtained. The method detection limits were 0.74-1.77 µg/L for milk and 2.39-6.02 µg/kg for eggs, while the method quantification limits were 2.29-5.46 µg/L for milk and 7.38-18.65 µg/kg for eggs. The steroid concentration in milk samples was

Determination of four acidic nonsteroidal anti-inflammatory drugs in wastewater samples by dispersive liquid-liquid microextraction based on solidification of floating organic droplet and high-performance liquid chromatography.

A simple, environmentally friendly, and sensitive dispersive liquid-liquid microextraction based on solidification of floating organic droplet for the extraction of four acidic nonsteroidal anti-inflammatory drugs (ketoprofen, naproxen, ibuprofen, and diclofenac) from wastewater samples subsequent by high-performance liquid chromatography analysis was developed. The influence of extraction parameters such as pH, the effect of solution ionic strength, type of extraction solvent, disperser solvent, and extraction solvent volume were studied. High enrichment factors (283-302) were obtained through the developed method. The method provides good linearity (r > 0.999) in a concentration range of 1-100 µg/L, good intra- and inter-day precision (relative standard deviation < 7%) and low limits of quantification. The relative recoveries of the selected compounds were situated over 80% both in synthetic and real water samples. The developed method has been successfully applied for the analysis of the selected compounds in wastewater samples.

Simultaneous determination of nitrophenols and poly-aromatic hydrocarbons in aquatic samples by solid phase extraction and HPLC analysis.

A method for the simultaneous extraction and HPLC analysis of nitrophenols and poly-aromatic hydrocarbons (PAHs) in aquatic samples is presented. The efficiency of the solvent extraction and the solid phase extraction (SPE) is compared. The results showed that the polymeric SPE sorbent is the best compromise for the simultaneous extraction of the tested compounds taking into consideration the lipophilicity of PAHs and the polarity of nitrophenols. The best results were obtained on polymeric Strata X sorbent, elution with dichloromethane followed by elution with methanol. Silica gel C18 sorbent is improper for nitrophenols due to the strong interactions with the residual hydroxyl groups of silica gel. The developed SPE-HPLC method was successfully applied for the analysis of these pollutants in different water samples.

Determination of persistent organic pollutants in urban and peri-urban wastewater sludge: environmental and carcinogenic human risk assessment in the case of land application.

The management of digested sludge derived from treatment water plants is a problem worldwide due to the possible transfer of contamination from sludge to amended soil and, in turn, to humans. Within this work, through a chemometric experimental design, a robust GC-MS method for the simultaneous determination of two classes of micropollutants of concern (polycyclic aromatic hydrocarbons-PAHs-and polychlorinated biphenyls-PCBs-including dioxin-like compounds) was developed using microwave-assisted extraction (MAE). The method, which showed interesting greenness features in compliance with the 12 principles of Green Chemistry, allowed PCB and PAH extraction with recoveries higher than 75% (RSD < 14%) with method detection limits between 4.6 and 11.5 µg kg-1 (PAHs) and between 6.9 and 13.7 µg kg-1 (PCBs), without preconcentration. The matrix effect was below 20%. The validated protocol allowed the characterization of two digested sludges sampled in an urban and a peri-urban district, representative models of two scenarios of different anthropic impacts. This study highlighted higher contamination for the sludge derived from the urban area, accounted for by the 4-ring PAHs. In addition, since carcinogenic PAHs were detected, the environmental risk (by mean of the comparison of predicted vs predicted no-effect concentrations) and the carcinogenic human risk from dermal contact (through the calculation of the adsorbed lifetime average daily dose) were assessed in the case of soils amended with the sludges considered, pointing out that the measured concentrations do not pose a risk.

Unveiling Health Inequalities: Exploring Metabolic Dysfunction in Rural Roma Communities.

BACKGROUND: Europe's largest ethnic minority, the Roma, are often confronted with substantial obstacles that result in health disparities. Research indicates that there are elevated rates of both communicable and non-communicable diseases, such as metabolic syndrome (MetS), among Roma communities, often linked to living conditions, limited education, or poverty. This study centers on remote rural Roma settlements in Romania, evaluating the prevalence of metabolic dysfunction, obesity, and liver steatosis while considering socio-economic and lifestyle factors. METHODS: Over a period of 36 months, local visits to a total of 25 rural Roma communities were conducted, where a medical team gathered information through a standardized questionnaire and conducted a physical exam on every participant. Liver steatosis was also recorded with the help of a portable wireless ultrasound device. RESULTS: Our study included 343 participants, with a predominance of female subjects, representing 72.5% (n = 249) of the patients. The prevalence of obesity, defined by a body mass index (BMI) above 30 kg/m2, was 32.2% (n = 111). Arterial hypertension was found to have a prevalence of 54.1% (n = 185), with de novo hypertension being observed in 19.2% patients (n = 66). Type 2 diabetes mellitus was found in 28.9% patients (n = 99), with 19.5% being de novo cases. The prevalence of hepatic steatosis was 57.2% (n = 111/194). A positive association between metabolic features and at-risk behaviors was found. CONCLUSIONS: This study underscores the transition from infectious to metabolic diseases in vulnerable communities and highlights the urgency of targeted public health strategies tailored to the unique needs of rural Roma populations, aiming to mitigate health disparities and promote equitable healthcare access.

Water Quality and Associated Human Health Risk Assessment Related to Some Ions and Trace Elements in a Series of Rural Roma Communities in Transylvania, Romania.

This research aims to assess the content of some ions and trace elements in water sources in 24 rural Roma communities in Transylvania in order to assess the human health risk associated with exposure to such elements and ions. To this end, eight ions (F-, Cl-, Br-, NO2-, NO3-, SO42-, PO43-, NH4+) and ten trace elements (Cr, Ni, As, Pb, Cd, Mn, Cu, Zn, Fe, and Hg) were determined in 71 water samples by ion chromatography coupled with a conductivity detector for ions and atomic absorption spectrophotometry for all trace elements. General parameters were also determined. Non-conformity (as number of samples), according to the EU Drinking Water Directive, was observed as follows: pH (7), EC (7), hardness (1), oxidizability (15), Cl- (4), NO3- (30), SO42- (6), Fe (16), Mn (14), As (3), and Ni (1 sample). The incidence of ions was Cl- (71), SO42- (70), F- (67), NO3- (65), NH4+ (21), Br- (10), PO43-, and NO2- (1 sample) and for trace elements, Mn (59), Fe (50), As (38), Ni (32), Cu (29), Zn (28), Cd (12), Cr (11), and Pb (3 samples). Hg was not detected. Non-carcinogenic (HI) values exceeded one for As in 13 Roma communities, with higher values for children than for adults. For NO3-, the HI values were >1 in 12 for adults and 14 communities for children. The carcinogenic risk (CR) for As through ingestion ranged from 0.795 to 3.50 × 10-4 for adults and from 1.215 to 5.30 × 10-4 for children. CR by dermal contact was in the range of ×10-6 both for adults and children.

New psychoactive substances in several European populations assessed by wastewater-based epidemiology.

Wastewater-based epidemiology (WBE) can be a useful tool to face some of the existing challenges in monitoring the use of new psychoactive substances (NPS), as it can provide objective and updated information. This Europe-wide study aimed to verify the suitability of WBE for investigating the use of NPS. Selected NPS were monitored in urban wastewater by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The main classical illicit drugs were monitored in the same samples to compare their levels with those of NPS. Raw composite wastewater samples were collected in 2016 and 2017 in 14 European countries (22 cities) following best practice sampling protocols. Methcathinone was most frequent (>65% of the cities), followed by mephedrone (>25% of the cities), and only mephedrone, methcathinone and methylone were found in both years. This study depicts the use of NPS in Europe, confirming that it is much lower than the use of classical drugs. WBE proved able to assess the qualitative and quantitative spatial and temporal profiles of NPS use. The results show the changeable nature of the NPS market and the importance of large WBE monitoring campaigns for selected priority NPS. WBE is valuable for complementing epidemiological studies to follow rapidly changing profiles of use of drugs.

Simultaneous Determination of Four Nonsteroidal Anti-Inflammatory Drugs and Three Estrogen Steroid Hormones in Wastewater Samples by Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Droplet and HPLC.

BACKGROUND: Nonsteroidal anti-inflammatory drugs (NSAIDs) and estrogen steroid hormones (estrogens) are pharmaceuticals intensively studied in environmental analysis due to their toxic effect on animal and human beings. OBJECTIVE: Development of a simple, fast, and sensitive extraction method for the simultaneously analysis of four NSAIDs (ketoprofen, naproxen, ibuprofen, and diclofenac) and three estrogens (17ß-estradiol, 17α-ethynylestradiol, and estriol) from wastewater samples. METHOD: Dispersive liquid-liquid microextraction based on solidification of floating organic droplet followed by HPLC analysis with UV detection was developed. The influence of the main extraction parameters, e.g., the volume of extraction solvent and of disperser, the pH, and the ionic strength of sample were evaluated. RESULTS: Good resolutions between the selected drugs were obtained using a reverse-phase column and a mobile phase of acetonitrile and water. This method provides good linearity (r > 0.999) in a concentration range of 1-100 µg/mL, good intra- and inter-day precision (RSD <7%) and low LOQs. The obtained enrichment factors were ranged between 162 and 180 for NSAIDs and between 118 and 185 for estrogens. The relative recoveries were situated >80% for all analysed drugs, except estriol (59%) both in synthetic and real wastewater samples. CONCLUSIONS: The developed method has been successfully applied for the analysis of the selected drugs in wastewater samples collected from the influent of a wastewater treatment plant. HIGHLIGHTS: Four NSAIDs and three estrogens from wastewater samples were simultaneously extracted and analysed using only 10 mL of sample and 50 µL of extraction solvent.

Analysis of multiclass organic pollutant in municipal landfill leachate by dispersive liquid-liquid microextraction and comprehensive two-dimensional gas chromatography coupled with mass spectrometry.

We propose a simple, fast, and inexpensive method for the analyses of 72 organic compounds in municipal landfill leachate, based on dispersive liquid-liquid microextraction and comprehensive two-dimensional gas chromatography coupled with mass spectrometry. Forty-one organic compounds belonging to several classes including hydrocarbons, mono- and polyaromatic hydrocarbons, carbonyl compounds, terpenes, terpenoids, phenols, amines, and phthalates, covering a wide range of physicochemical properties and linked to municipal landfill leachate, were quantitatively determined. Another 31 organic compounds such as indoles, pyrroles, glycols, organophosphate flame retardants, aromatic amines and amides, pharmaceuticals, and bisphenol A have been identified based on their mass spectra. The developed method provides good performances in terms of extraction recovery (63.8-127%), intra-day and inter-day precisions (< 7.7 and < 13.9 respectively), linearity (R2 between 0.9669 and 0.9999), detection limit (1.01-69.30 µg L-1), quantification limit (1.87-138.6 µg L-1), and enrichment factor (69.6-138.5). Detailed information on the organic pollutants contained in municipal landfill leachate could be obtained with this method during a 40-min analysis of a 4-mL leachate sample, using only 75 µL of extraction solvent.

Occurrence, distribution and ecological risk of trace metals and organic pollutants in surface sediments from a Southeastern European river (Somesu Mic River, Romania).

The increasing contamination of fresh water resources by trace metals and persistent organic pollutants is a major environmental concern. In the present study, we investigated, for the first time, the distribution, sources and ecological risk of trace metals and organic pollutants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), in surface sediments from a Southeastern European river (Somesu Mic River, Romania). Concentrations of Cd, Cr, Cu, Pb, Ni and Zn ranged from 0.04 to 0.4, 9.4 to 43.15, 7.2 to 65.6, 12.3 to 131.4, 14.7 to 47.7 and 42.1 to 236.8 mg kg-1 dw, respectively. Concentrations of total PAHs, PCBs and OCPs ranged from 24.8 to 575.6, 2.7 to 252.7 and 2.1 to 44.3 ng g-1 dw, respectively. Some sediment parameters, i.e., pH, total organic carbon (TOC) and total organic matter (OM) contents, played a significant role in the spatial distribution of contaminants. A combined analysis based on diagnostic ratios and multivariate analyses revealed PAHs originating mainly from pyrolytic sources. PCB compositions showed distinct contamination signatures for tri- to tetra-chlorinated PCBs, characteristic of contamination by Aroclor-1016 and -1254 technical mixtures. The dominant OCP congeners were α-HCH and p,p'-DDD, reflecting past use of technical HCHs and DDTs in agricultural practices. Metal source and pollution status was assessed using geoaccumulation index and enrichment factor, which indicate widespread pollution by Pb, Cd, Zn, Ni and Cu. The use of Sediments Quality Guidelines (SQGs), mean effect range-median quotient (m-ERM-Q) and toxic equivalent factor (TEF) indicated that the highest ecological risks occurred for PCBs and DDTs. This work presents not only initial baseline information on the extent of organic and inorganic contaminations in a river of ecological and economical interest, but also provides a diagnostic ratio/statistical combined approach that can be used to evaluate sediment quality in similar environments.

Comprehensive two-dimensional GC of supercritical fluid and pressurized liquid extracts of tobaccos.

The developments of an analytical strategy based on rapid extraction techniques coupled to comprehensive bi-dimensional gas chromatography (GCxGC) for the characterization of the volatile fraction of tobaccos are presented. The high-peak capacity of GCxGC allows considering global extraction techniques that do not focus on restricted chemical families of products. Thus, potential of pressurized fluid extraction and supercritical fluid extraction (SFE) to provide informative extracts is evaluated and compared. As expected, both techniques enable rapid extraction of compounds of interest. However, because of the easy removal of the extracting fluid, SFE provides more concentrated extracts, allowing a GCxGC direct injection without any concentration step. Moreover, the use of pure carbon dioxide with tuneable extraction power favors the extraction of the compounds of interest while reducing the extraction of interfering heavy compounds. GCxGC conditions, especially concerning the set of columns used, are selected thanks to the comparison of separations obtained on model compounds. The developed methodology is applied not only to compare the three main types of tobaccos but also to discriminate between different tobaccos of the same type.