Development and performance of an analytical method for polychlorinated naphthalenes and other persistent organic pollutants in dried blood spots.

BACKGROUND: Dried blood spots (DBSs) collected and archived in newborn screening programs (NSP) represent a potentially valuable resource for assessing exposure to a range of organic and inorganic chemicals in newborns. This study develops and optimizes a method to measure polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs) in DBS using the isotope dilution technique, ultrasonic-assisted liquid-liquid extraction, simple cleanup, triple quadrupole GC-MS/MS analysis, and background correction. RESULTS: We minimize the number of extraction repetitions and the volume of solvent, which helps increase throughput while minimizing the potential for contamination. We obtained high recovery and precision for most compounds, and method detection limits (MDLs) were sufficiently low to detect the more prevalent compounds based on representative sample of the US population. MDLs averaged 0.020 ng/mL (recovery: 107 %, precision: 4 %) for PCNs, 0.021 ng/mL (recovery: 97 %, precision: 4 %) for PCBs, 0.021 ng/mL (recovery: 117 %, precision: 2 %) for OCPs, and 0.021 ng/mL (recovery: 96 %, precision: 3 %) for PBDEs. SIGNIFICANCE AND NOVELTY: To our knowledge, this is the first study presenting an analytical method and for PCNs in DBS, and one of the few studies providing an assessment of method performance for persistent organic pollutants in DBS. The optimized method can be applied to a wide range of applications, including exposure assessment, environmental epidemiology, forensics, environmental surveillance, and ecological monitoring.

Stepping-up accurate quantification of chlorinated paraffins: Successful certification of the first matrix reference material.

BACKGROUND: Chlorinated paraffins (CPs) are industrial chemicals categorised as persistent organic pollutants because of their toxicity, persistency and tendency to long-range transport, bioaccumulation and biomagnification. Despite having been the subject of environmental attention for decades, analytical methods for CPs still struggle reaching a sufficient degree of accuracy. Among the issues negatively impacting the quantification of CPs, the unavailability of well-characterised standards, both as pure substances and as matrix (certified) reference materials (CRMs), has played a major role. The focus of this study was to provide a matrix CRM as quality control tool to improve the comparability of CPs measurement results. RESULTS: We present the process of certification of ERM®-CE100, the first fish reference material assigned with certified values for the mass fraction of short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively). The certification was performed in accordance with ISO 17034:2016 and ISO Guide 35:2017, with the value assignment step carried out via an intercomparison of laboratories of demonstrated competence in CPs analysis and applying procedures based on different analytical principles. After confirmation of the homogeneity and stability of the CRM, two certified values were assigned for SCCPs, depending on the calibrants used: 31 ± 9 µg kg-1 and 23 ± 7 µg kg-1. The MCCPs certified value was established as 44 ± 17 µg kg-1. All assigned values are relative to wet weight in the CRM that was produced as a fish paste to enhance similarity to routine biota samples. SIGNIFICANCE AND NOVELTY: The fish tissue ERM-CE100 is the first matrix CRM commercially available for the analysis of CPs, enabling analytical laboratories to improve the accuracy and the metrological traceability of their measurements. The certified CPs values are based on results obtained by both gas and liquid chromatography coupled with various mass spectrometric techniques, offering thus a broad validity to laboratories employing different analytical methods and equipment.

Environmental contaminants in Arctic human populations: Trends over 30 years.

INTRODUCTION: Arctic Monitoring and Assessment Programme (AMAP) monitors persistent organic pollutant (POP) levels in the Arctic populations and assesses health effects related to exposure to them. Many internationally regulated POPs persist in humans and biota, while new Emerging Contaminants of Arctic Concern (ECAC), many of which are unregulated, present additional challenges. Biomonitoring offers valuable insights into temporal trends within human matrices, revealing critical information not only about the efficacy of international regulations but also serving as an early warning system for exposure and risks for human health. METHODS: Data analyzed in this study is aggregated data presented in the AMAP Human Health in the Arctic assessments, which provide data on contaminant concentrations measured in human matrices from adults, and children across various population studies conducted in the Arctic since the 1980 s. Linear regression analyses were used to assess trends of various POPs including organochlorine (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and per- and polyfluoroalkyl substances (PFAS), measured over time from the Arctic populations in Finland, Norway, Sweden, Denmark, Iceland, Canada and Alaska (USA). RESULTS: Overall, decreasing trends were observed for PCBs and OCPs. Regulated PFAS showed decreasing trends, but increasing trends were observed for unregulated PFAS in certain populations. PBDEs showed decreasing or inconsistent trends in certain Arctic populations. CONCLUSIONS: Decreasing trends are observed for legacy POPs, but the trends for new emerging contaminants are inconsistent. More focus is needed on biomonitoring the new emerging contaminants of concern in the Arctic and their implications on human health.

Nitrogen can substitute helium as a mobile phase in the analysis of wastewater treatment matrices for persistent organic pollutants by gas chromatography - electron capture detection system.

Municipal wastewater treatment plants are required to monitor persistent organic pollutants (POPs) in their wastewater treatment related discharges and to assess the impact of the discharges on the environment and public health. One tool for monitoring chlorinated organic pollutants particularly is a gas chromatographic (GC) system coupled to a pair of halogen-specific electron capture detectors (ECDs) with helium (He) as the mobile phase. He supplies, however, has become inconsistent and unreliable lately. In its place, N2 gas is evaluated in this study as a potential substitute for He in quantifying organochlorine pesticides, polychlorinated biphenyls, chlordane congeners and toxaphene in wastewater treatment related matrices (influent, effluent, benthic sediment, mussel tissue, and biosolids/sludge). N2 is inert, inexpensive and requires no additional hardware to incorporate into the basic functions of a GC-ECD. Our results show that, with the usual data quality controls (blank, laboratory control, matrix spike/duplicate and proficiency testing samples, and the fact that certified reference materials data met requirements), N2 can replace He for regulatory purposes. And when necessary, the N2-based retention times (tN) can be predicted reliably from He-based retention times (tHe), irrespective of column chemistry or POPs (here: tN = 1.90tHe + 0.04, R2 = 0.996).

The emerging and legacy persistent organic contaminants in corals of the South China Sea.

Seawater warming, ocean acidification and chemical pollution are the main threats to coral growth and even survival. The legacy persistent organic contaminants (POCs), such as polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), and the emerging contaminants, including polybrominated diphenyl ethers (PBDEs), dechlorane plus (DPs) and novel brominated flame retardants (NBFRs) were studied in corals from Luhuitou fringing reef in Sanya Bay and Yongle atoll in Xisha Islands, the South China Sea (SCS). Total average concentrations of ∑16PAHs, ∑23OCPs, ∑34PCBs, ∑8PBDEs, ∑2DPs and ∑5NBFRs in 20 coral species (43 samples) from the SCS were 40.7 ± 34.6, 5.20 ± 5.10, 0.197 ± 0.159, 3.30 ± 3.70, 0.041 ± 0.042 and 36.4 ± 112 ng g-1 dw, respectively. PAHs and NBFRs were the most abundant compounds and they are likely to be dangerous pollutants for future coral growth. Compared to those found in other coral reef regions, these pollutants concentrations in corals were at low to median levels. Except for PBDEs, POCs in massive Porites were significantly higher than those in branch Acropora and Pocillopora (p < 0.01), as large, closely packed corals may be beneficial for retaining more pollutant. The current study contributes valuable data on POCs, particularly for halogenated flame retardants (HFRs, including PBDEs, DPs and NBFRs), in corals from the SCS, and will improve our knowledge of the occurrence and fate of these pollutants in coral reef ecosystems.

Organochlorine pesticide contamination of soils and dust from an urban environment in the Niger Delta of Nigeria.

The concentrations, sources, and risk of twenty organochlorine pesticides (OCPs) in soils and dusts from a typical urban setting in the Niger Delta of Nigeria were examined. The Σ20 OCP concentrations (ng g-1) varied from 4.49 to 150 with an average value of 32.6 for soil, 4.67 to 21.5 with an average of 11.7 for indoor dust, and 1.6 to 96.7 with an average value of 23.5 for outdoor dust. The Σ20 OCP concentrations in these media were in the order: soil > outdoor dust > indoor dust, which was in contrast with the order of the detection frequency, i.e., indoor dust (95 to 100 %) > soil (60 to 90 %) > outdoor dust (30 to 80 %). The concentrations of the different OCP classes in these media followed the order: aldrin + dieldrin + endrin and its isomers (Drins) > chlordanes > dichlorodiphenyltrichloroethane (DDTs) > hexachlorocyclohexane (HCHs) > endosulfans for outdoor dust and soil, while that of the indoor dust followed the order: Drins > chlordanes > endosulfans > DDTs > HCHs. The cancer risk values for human exposure to OCPs in these sites exceeded 10-6 which indicates possible carcinogenic risks. The sources of OCPs in these media reflected both past use and recent inputs.

Presence of polycyclic aromatic hydrocarbons and persistent organochlorine pollutants in human Milk: Evaluating their levels, association with Total antioxidant capacity, and risk assessment.

Breastfeeding provides numerous health benefits for both infants and mothers, promoting optimal growth and development while offering protection against various illnesses and diseases. This study investigated the levels of polychlorinated biphenyls (PCB), organochlorine pesticides (OCP) and polycyclic aromatic hydrocarbons (PAH) in human milk sampled in Zadar (Croatia). The primary objectives were twofold: firstly, to evaluate the individual impact of each compound on the total antioxidant capacity (TAC) value, and secondly, to assess associated health risks. Notably, this study presents pioneering and preliminary insights into PAH levels in Croatian human milk, contributing to the limited research on PAH in breast milk worldwide. PCB and OCP levels in Croatian human milk were found to be relatively lower compared to worldwide data. Conversely, PAH levels were comparatively higher, albeit with lower detection frequencies. A negative correlation was established between organic contaminant levels and antioxidative capacity, suggesting a potential link between higher antioxidative potential and lower organic contaminant levels. Diagnostic ratio pointed towards traffic emissions as the primary source of the detected PAH. The presence of PAH suggests potential health risk, underscoring the need for further in-depth investigation.

Characterization and health risks of short- and medium-chain chlorinated paraffins in the gas and size-fractionated particulate phases in ambient air.

Short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) have garnered significant attention because they have persistence and potential toxicity, and can undergo long-distance transport. Chlorinated paraffins (CPs) inhaled in the size-fractionated particulate phase and gas phase can carry different risks to human health due to their ability to accumulate in different regions of the respiratory tract and exhibit varying deposition efficiencies. In our study, large-volume ambient air samples in both the size-fractionated particulate phase (Dp < 1.0 µm, 1.0-2.5 µm, 2.5-10 µm, and Dp ≥ 10 µm) and gas phase were collected simultaneously in Beijing using an active sampler. The overall levels of SCCPs and MCCPs were relatively high, the ranges being 57-881 and 30-385 ng/m3, respectively. SCCPs tended to be partitioned in the gas phase (on average 75% of the ΣSCCP concentration), while MCCPs tended to be partitioned in the particulate phase (on average 62% of the ΣMCCP concentration). Significant correlations were discovered between the logarithm-transformed gas-particle partition coefficients (KP) and predicted subcooled vapor pressures (PL0) (p < 0.01 for SCCPs and MCCPs) and between the logarithm-transformed KP values and octanol-air partition coefficients (KOA) (p < 0.01 for SCCPs and MCCPs). Thus, the slopes indicated that organic matter absorption was the dominant process involved in gas-particle partitioning. We used the ICRP model to calculate deposition concentrations for particulate-associated CPs in head airways region (15.6-71.4 ng/m³), tracheobronchial region (0.8-4.8 ng/m³), and alveolar region (5.1-21.9 ng/m³), then combined these concentrations with the CP concentrations in the gas phase to calculate estimated daily intakes (EDIs) for inhalation. The EDIs for SCCPs and MCCPs through inhalation of ambient air for the all-ages group were 67.5-184.2 ng/kg/day and 19.7-53.7 ng/kg/day, respectively. The results indicated that SCCPs and MCCPs in ambient air do not currently pose strong risks to human health in the study area.

Short- and medium-chain chlorinated paraffins in surface sediment from Lake Ontario.

Concentrations of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) were analyzed and investigated in surficial sediment collected in 2018 from ten different nearshore sites in Lake Ontario and the St. Lawrence River influenced by inputs from varying urban and historical land uses. Sites were grouped into two categories of tributary and lake according to their location. Results show that tributary sites had higher concentrations of total chlorinated paraffin (CP) than lake sites. Humber Bay, a lake site, had the highest total CP concentration (55,000 ng/gTOC) followed by Humber River, a tributary site (50,000 ng/gTOC). The lowest concentrations were found in eastern Lake Ontario and Lake St. Francis in the St. Lawrence River (540 ng/gTOC). Higher concentrations of chlorinated paraffins (CPs) were found where runoff and wastewater inputs from urban areas, current industrial activities, and population were the greatest. Levels of MCCPs were higher than SCCPs at all sites but one, Lake St. Francis. Among the SCCPs, C13 and among the MCCPs C14 were the dominant chain length alkanes, with C14 being the highest among both groups. The SCCPs and MCCPs profiles suggest that they can be used to distinguish between sites impacted by local sources vs. sites impacted by short-/long-range transport of these chemicals.

Characteristics and degradation mechanisms of polychlorinated naphthalenes in surface soil in Yangtze River Delta, China.

Both thermal and environmental processes are significant factors influencing the existing characteristics, e.g., congener distributions, and existing levels, of polychlorinated naphthalenes (PCNs) in the environment. Soil plays an important role in the life cycle of PCNs, but degradation of PCNs in soils has never been reported. In this study, we collected surface soil samples from 13 cities in the Yangtze River Delta, which is one of the most crowded areas of China and analyzed the samples for 75 PCNs. The long-range transportation from polluted areas was the major source for PCNs in remote areas, but the PCN profiles in remote areas reported in our previous studies were different from those in human settlement in this study, indicating there is a transformation of PCNs after emissions from anthropogenic activities. Two experiments were then designed to reveal the degradation mechanisms, including influencing factors, products, and pathways, of PCNs in surface soils. Based on the experiments, we found that the major factor driving the losses of PCNs in surface soils was volatilization, followed by photo irradiation and microbial metabolism. Under photo-irradiation, the PCN structures would be destroyed through a process of dechlorination followed by oxidation. In addition, the dechlorination pathways of PCNs have been established and found to be significantly influenced by the structure-related parameters.

A new sustainable filtration membrane extraction method based on nanoconfined liquid phase extraction: Determination of organochlorinated pesticides and pyrethroids in tea samples.

BACKGROUND: Pesticides are used in agricultural production for prevent and control crop diseases and pests, but it is easy to cause excessive pesticides residues in agricultural products, polluting the environment and endangering human health. Due to their unmatched and sustainable capabilities, nanoextraction procedures are becoming every day more important in Analytical Chemistry. In particular, nanoconfined liquid phase extraction has shown extraction capabilities toward polar, medium polar, and/or nonpolar substances, which can be easily modulated depending on the nanoconfined solvent used. Furthermore, this "green" technique showed excellent characteristics in terms of recoveries, extraction time (≤1 min), reliability, and versatility. (97) RESULTS: In this work, the advantages of this technique have been coupled with those of filtration membrane extraction, making use of carbon nanofibers (CnFs) growth on carbon microspheres (CµS). This substrate has been deposited on a filter, which combined with gas chromatographic mass spectrometry (GC-MS) analysis successfully employed for the nanoextraction of 30 pesticides (18 organochlorine and 12 pyrethroids) in tea samples. Under the optimized extraction conditions, the linear range with standard solutions was from 1 to 1000 ng mL-1 (R2 ≥ 0.99), the limit of detections in tea samples were in the range 0.56-17.98 µg kg-1. The accuracy of the developed method was evaluated by measuring the extraction recovery of the spiked tea samples, and recoveries between 74.41 % and 115.46 %. (119) SIGNIFICANCE: Considering the versatility of nanoconfined liquid phase extraction and the functionality of the filtration membrane extraction procedure, this new extraction method can be considered a powerful candidate for automatized high-throughput analyses of real samples. (34).

Assessing the effect of COVID 19 lockdowns on the composition of organic compounds and potential source of PM2.5 in Hanoi, Vietnam.

The ambient air quality during COVID-19 lockdowns has been improved in many cities in the world. This study is to assess the changes in persistent organic pollutants in PM2.5 during the COVID-19 lockdown in Hanoi. Individual organic species in PM2.5 ((e.g., polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs), and organochlorine pesticides (OCPs)) were measured in an urban residential area in Hanoi from before the March 10th to April 22nd, 2020, including before the partial lockdown (BL) and the partial lockdown (PL) phases. During the PL phase, the concentration of Σ14PAHs and Σ28PCBs was reduced by 38 and 52% compared with the BL period, respectively. The diagnostic ratio method implied that the sources of PAHs within the PL phase had a less effect on traffic and industrial activities than in the BL phase. The characteristic ratio method indicated that PCBs were mixed by commercial product and combustion process in both the BL and the PL periods, however, the source of PCBs in the BL phase was influenced by municipal waste incineration more than those in the PL phase. The decreasing concentration of Σ20OCPs during the partial lockdown was attributed to the restriction of human activities during the quarantine period. The results suggested that the source of OCPs was probably derived from the usage of pesticides in current and, historical degradation or the transportation of pesticides from the soil to the atmosphere.

Monitoring of environmental persistent organic pollutants in hair samples of cats and dogs.

This study investigated 32 persistent organic pollutants, including 9 organochlorine pesticides, 15 polychlorinated biphenyls, 6 polycyclic aromatic hydrocarbons, and 2 organophosphate pesticides in the hair samples of domestic cats and dogs living in an urban area in Samsun, Turkiye. Hair samples were collected from 35 cats and 38 dogs, grouped by sex and age (<3 or >3 years old). Samples were extracted using a liquid-liquid extraction method and analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The results revealed the presence of organochlorine pesticides (n = 58, 468.65 ± 92.30 ng/g), polycyclic aromatic hydrocarbons (n = 57, 15.65 ± 3.91 ng/g), polychlorinated biphenyls (n = 55, 54.11 ± 9.47 ng/g), and organophosphate pesticides (n = 25, 568.43 ± 113.17 ng/g) in the samples. PCBs 81, 118, 128, 208, and 2,4-DDE were not detected in any samples. Only one sample did not contain any of the searched compounds. Fluorene was the most frequently detected pollutant (n = 53, 72.6 %), followed by ß-hexachlorocyclohexane (n = 34, 46.6 %). The highest maximum concentration was observed for hexachlorobenzene (2748.03 ng/g), followed by aldrin (2313.45 ng/g) and fenitrothion (2081.13 ng/g). Pollutant concentrations did not differ between cats and dogs, sexes, and ages (p > 0.05). This study highlights the significant threat that urban areas pose to pets, and therefore, POPs should be monitored periodically in hair and other samples. To the best of our knowledge, this is the first report to investigate POP levels in hair samples from cats and dogs in Turkiye.

Safety evaluation of organochlorine pesticides and polybrominated diphenyl ethers in imported canned fish in Nigeria.

Organochlorine pesticide (OCP) and polybrominated diphenyl ether (PBDE) concentrations were measured in thirty popular brands of imported canned fish (mackerel, sardines, and tuna) in Nigeria to ascertain potential threats to humans arising from their consumption. The Σ20 OCP concentrations in mackerel ranged from 0.47 to 7.36 ng g-1, while those of tuna and sardines varied from 1.06 to 2.19 and 0.11 to 12.7 ng g-1, respectively. The Σ39 PBDE concentrations in mackerel varied from 0.06 to 4.21 ng g-1, while those of tuna and sardines ranged from 0.19 to 3.18 and 0.04 to 8.26 ng g-1, respectively. The estimated daily intake (EDI) of OCPs and PBDEs from ingestion of the canned fish by adults and children were in the magnitude of 0.03 to 17.6 ng kg-1 bw day-1 and 9.9 × 10-3 to 11.5 ng kg-1 bw day-1 respectively. The hazard index (HI) and total cancer risk (TCR) values for OCPs and PBDEs from ingestion of the canned fish were less than 1 and 10-6, respectively. The dietary intakes of OCPs and PBDEs from these brands of canned fish by adults and children result in no adverse non-cancer and cancer risks.

Positive association between chlorinated paraffins and the risk of allergic diseases in children and adolescents.

Contaminants may induce immune response polarization, leading to immune diseases, such as allergic diseases. Evidence concerning the effects of chlorinated paraffins (CPs), an emerging persistent organic pollutant, on immune system is scarce, particularly for epidemiological evidence. This study explores the association between CPs exposure and allergic diseases (allergic rhinitis, atopic eczema, and allergic conjunctivitis) in children and adolescents in the Pearl River Delta (PRD) in China. Herein, 131,304 children and adolescents from primary and secondary schools in the PRD were included and completed the questionnaire survey. The particulate matter (PM) samples were collected in the PRD and the PM2.5-bound CP concentrations were analyzed. In the multivarious adjustment mixed effect model (MEM), an IQR increase in ∑CPs was significantly associated with allergic diseases (rhinitis, eczema, and conjunctivitis) with the estimated odds ratios (ORs) for 1.11 (95% CI: 1.10, 1.13), 1.17 (95% CI: 1.15, 1.19), and 1.82 (95% CI: 1.76, 1.88), respectively. Interaction analysis indicated that overweight and obese individuals might have greater risk. Similar effect estimates were observed in several sensitivity analyses. This study provided epidemiological evidence on the immunotoxicity of CPs. More studies to confirm our findings and investigate mechanisms are needed.

First comprehensive assessment of dietary chlorinated paraffins intake and exposure risk for the rural population of the Tibetan Plateau, China.

Knowledge regarding the occurrence of short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) in foodstuffs and their dietary exposure risks for rural Tibetan residents remains largely unknown. Herein, we collected main foodstuffs (including highland barley, vegetables, Tibetan butter, mutton, and yak beef) across the rural Tibetan Plateau and characterized the CP profiles and concentrations. The highest SCCPs concentrations were detected in Tibetan butter (geometric mean (GM): 240.6 ng/g wet weight (ww)), followed by vegetables (59.4 ng/g ww), mutton (51.4 ng/g ww), highland barley (46.3 ng/g ww), and yak beef (31.7 ng/g ww). For MCCPs, the highest concentrations were also detected in Tibetan butter (319.5 ng/g ww), followed by mutton (181.9 ng/g ww), vegetables (127.0 ng/g ww), yak beef (71.2 ng/g ww), and highland barley (30.3 ng/g ww). The predominant congener profiles of SCCPs were C13Cl7-8 in mutton and yak beef, C10Cl7-8 in Tibetan butter, and C10-11Cl6-7 in highland barley and vegetables. The predominant congener profiles of MCCPs were C14Cl7-9 in all sample types. Combined with our previous results of free-range chicken eggs, the median estimated daily intakes (EDIs) of SCCPs and MCCPs via diet for Tibetan rural adults and children was estimated to be 728.8 and 1853.9 ng/kg bw/day and 2565.6 and 5952.8 ng/kg bw/day, respectively. In the worst scenario, MCCPs might induce potential health risks for rural Tibetan population. To our knowledge, this is the first systematic dietary exposure research of SCCPs and MCCPs in the remote rural areas.

A novel honeycomb-like 3D-printed device for rotating-disk sorptive extraction of organochlorine and organophosphorus pesticides from environmental water samples.

In this study, 3D-printing based on fused-deposition modeling (FDM) was employed as simple and cost-effective strategy to fabricate a novel format of rotating-disk sorptive devices. As proof-of-concept, twenty organochlorine and organophosphorus pesticides were determined in water samples through rotating-disk sorptive extraction (RDSE) using honeycomb-like 3D-printed disks followed by gas chromatography coupled to mass spectrometry (GC-MS). The devices that exhibited the best performance were comprised of polyamide + 15 % carbon fiber (PA + 15 % C) with the morphology being evaluated through X-ray microtomography. The optimized extraction conditions consisted of 120 min of extraction using 20 mL of sample at stirring speed of 1100 rpm. Additionally, liquid desorption using 800 µL of acetonitrile for 25 min at stirring speed of 1100 rpm provided the best response. Importantly, the methodology also exhibited high throughput since an extraction/desorption platform that permitted up to fifteen simultaneous extractions was employed. The method was validated, providing coefficients of determination higher than 0.9706 for all analytes; limits of detection (LODs) and limits of quantification (LOQs) ranged from 0.15 to 3.03 µg L-1 and from 0.5 to 10.0 µg L-1, respectively. Intraday precision ranged from 4.01 to 18.73 %, and interday precision varied from 4.83 to 20.00 %. Accuracy was examined through relative recoveries and ranged from 73.29 to 121.51 %. This method was successfully applied to analyze nine groundwater samples from monitoring wells of gas stations in São Paulo. Moreover, the greenness was assessed through AGREEprep metrics, and an overall score of 0.69 was obtained indicating that the method proposed can be considered sustainable.

Vortex-assisted dispersive micro-solid-phase extraction using silica-supported Fe2O3-modified khat (Catha edulis) biochar nanocomposite followed by GC-MS for the determination of organochlorine pesticides in juice samples.

In this paper, dispersive micro-solid phase extraction technique was developed for the purpose of extracting and preconcentrating organochlorine pesticide residues in juice samples before their separation and quantitative analysis by gas chromatography-mass spectrometry. A sorbent composed of a silica-supported Fe2O3-modified khat leftover biochar nanocomposite (SiO2-Fe2O3-KLBNC) was implemented in the process. To improve the dispersion of the sorbent in the solution, vortex mixer was employed. Experimental parameters influencing the performance of the method were optimized, and the optimal conditions were established. With these conditions, linear dynamic ranges ranged from 0.003 to 100.0 ng/mL were achieved, with a correlation coefficient (r2) ≥ 0.9981. The limits of detection and quantification, determined by signal-to-noise ratios of 3 and 10, respectively, were found to be in the ranges of 0.001-0.006 ng/mL and 0.003-0.020 ng/mL. Intra- and inter-day precision, values ranging from 0.3-4.8% and 1.7-5.2% were obtained, respectively. The matrix-matched extraction recoveries demonstrated favorable outcomes, falling within the range of 83.4-108.3%. The utilization of khat leftover as an adsorbent in contemporary sample preparation methodologies offers a cost-effective alternative to the currently available, yet expensive, adsorbents. This renders it economically viable, particularly in resource-constrained regions, and is anticipated to witness widespread adoption in the coming future.

Carcinogenic, non-carcinogenic risk, and attributable cases to organochlorine pesticide exposure in women from Northern Mexico.

This study aimed to estimate the carcinogenic and non-carcinogenic risk as well as the attributable cases due to exposure to organochlorine pesticides (OCPs): hexachlorobenzene (HCB), dichlorophenyltrichloroethane (DDT), hexachlorocyclohexane (HCH), heptachlor, and chlordane. From serum concentrations of pesticides of interest in a sample of 908 women from Northern Mexico, the risk for both cancer and non-cancer health effects was evaluated. The population attributable fraction (PAF) was also calculated based on summary association estimates between exposure to OCPs and different health events. Findings revealed that due to their OCP exposure slightly less than half of the women in the sample were at increased risk of developing non-cancerous diseases. Moreover, approximately 25% and 75% of participants were at risk of develop some type of cancer associated with their HCB and DDE concentrations, respectively. In addition, it was estimated that 40.5% of type 2 diabetes, 18.7% of endometriosis, and 23.1% of non-Hodgkin's lymphoma cases could have been prevented if women had not been exposed to these OCPs. Results suggest that the use of OCPs may have contributed to the disease burden in the study area and, based on the time required for these substances to be eliminated from the body, there are probably some women who are still at elevated risk of developing diseases associated to OCPs.

Efficiency of clustering methods and self-organizing maps of Adriatic sardines and anchovies regarding organochlorine and fatty acid burden.

The Adriatic Sea plays a crucial role as both a significant fishing ground and a thriving trading market for small pelagic edible fish. Recognized for their nutritional value, these fish are esteemed for their high protein content and abundance of polyunsaturated omega-3 and omega-6 fatty acids, making them a sought-after and healthful food choice. Nevertheless, pelagic species can also serve as a reservoir for lipophilic organochlorine pollutants, posing potential risks to human health. In this study, we compared traditional classification methods traditional principal component analysis (PCA) and Ward's clustering with an advanced self-organizing map (SOM) algorithm in determining distribution patterns of 24 organochlorines and 19 fatty acids in sardine and anchovy samples taken from the eastern Adriatic. The outcomes reveal the strengths and weaknesses of the three approaches (PCA, Ward's clustering, and SOM). However, it is evident that SOM has proven to be the most effective in offering detailed information and data visualization. Although sardines and anchovies exhibit similar distribution patterns for p,p'-DDE, PCB-28, PCB-138, PCB-153, PCB-118, and PCB-170, they differ in the concentrations of fatty acids such as stearic, palmitic, myristic, oleic, docosapentaenoic, and docosahexaenoic acid. Our findings supply valuable insights for environmental authorities and fish consumers concerning the potential risks associated with organochlorines in these two types of fish.