Evaluation of GC-EI&CI-TOFMS for Nontarget Analysis of Industrial Wastewater Using Hydrophilic-Lipophilic-Balanced SPME.

The evaluation of nontarget analysis (NTA) techniques for the monitoring of wastewater is important as wastewater is an anthropogenic pollution source for aquatic ecosystems and a threat to human and environmental health. This study presents the proof-of-concept NTA of industrial wastewater samples. A prototype hydrophilic-lipophilic-balanced (HLB) SPME and gas chromatography interfaced with time-of-flight high-resolution mass spectrometry (GC-TOFMS) with electron ionization (EI) and chemical ionization (CI) in parallel are employed. The HLB-SPME consists of a poly(divinylbenzene-co-N-vinylpyrrolidone) structure, allowing the extraction of hydrophilic as well as lipophilic substances. As the combination of parallel CI and EI data provides a comprehensive data set as a unique feature, this study is strongly focused on the compound identification procedure and confidence reporting of exemplary substances. Furthermore, the use of three different CI reagent ions, including [N2H]+/[N4H]+, [H3O]+, and [NH4]+, enables a broad range of analytes to be ionized in terms of selectivity and softness. The complementary information provided by EI and CI data allows a level 3 identification or higher in 69% of cases. The polarity coverage based on the physicochemical properties of the analytes (such as volatility, water solubility, hydrophilicity, and lipophilicity) was visualized by using Henry's law and octanol-water partitioning constants. In conclusion, the presented approach is shown to be valuable for water analysis and allows enhanced and accelerated compound identification compared to utilizing only one type of ionization.

Enhanced efficiency of MS/MS all-ion fragmentation for non-targeted analysis of trace contaminants in surface water using multivariate curve resolution and data fusion.

Data-independent acquisition-all-ion fragmentation (DIA-AIF) mode of mass spectrometry can facilitate wide-scope non-target analysis of contaminants in surface water due to comprehensive spectral identification. However, because of the complexity of the resulting MS2 AIF spectra, identifying unknown pollutants remains a significant challenge, with a significant bottleneck in translating non-targeted chemical signatures into environmental impacts. The present study proposes to process fused MS1 and MS2 data sets obtained from LC-HRMS/MS measurements in non-targeted AIF workflows on surface water samples using multivariate curve resolution-alternating least squares (MCR-ALS). This enables straightforward assignment between precursor ions obtained from resolved MS1 spectra and their corresponding MS2 spectra. The method was evaluated for two sets of tap water and surface water contaminated with 14 target chemicals as a proof of concept. The data set of surface water samples consisting of 3506 MS1 and 2170 MS2 AIF mass spectral features was reduced to 81 components via a fused MS1-MS2 MCR model that describes at least 98.8% of the data. Each component summarizes the distinct chromatographic elution of components together with their corresponding MS1 and MS2 spectra. MS2 spectral similarity of more than 82% was obtained for most target chemicals. This highlights the potential of this method for unraveling the composition of MS/MS complex data in a water environment. Ultimately, the developed approach was applied to the retrospective non-target analysis of an independent set of surface water samples.

Improving greenness and sustainability of standard analytical methods by microextraction techniques: A critical review.

Since environmental awareness has increased in analytical chemistry, the demand for green sample preparation methods continues to grow. Microextractions such as solid-phase microextraction (SPME) and liquid-phase microextraction (LPME) miniaturize the pre-concentration step and are a more sustainable alternative to conventional large-scale extractions. However, the integration of microextractions in standard and routine analysis methods is rare, although these applications are used most frequently and have a role model function. Therefore, it is important to highlight that microextractions are capable to replace large-scale extractions in standard and routine methods. This review discusses the greenness, benefits, and drawbacks of the most common LPME and SPME variants compatible with gas chromatography based on the following key evaluation principles: Automation, solvent consumption, hazards, reusability, energy consumption, time efficiency, and handling. Furthermore, the need to integrate microextractions into standard and routine analytical methods is presented by using method greenness evaluation metrics AGREE, AGREEprep, and GAPI applied to USEPA methods and their replacements.

The Relationship of Latent Toxoplasmosis and Cigarette Smoking: Seroprevalence, Risk Factor, and Case-Control Study in Fars Province, Southern Iran.

Toxoplasmosis is a parasitic disease with worldwide prevalence. Despite the relatively similar effects of toxoplasmosis and smoking on alteration in neurotransmitters, especially dopamine, little is known about the relation of Toxoplasma gondii infection and addiction to cigarette smoking. Therefore, the main objective of this study was to assess the relationship between latent toxoplasmosis and smoking. Through a case-control study, 216 regular cigarette smokers and 324 nonsmoker age- and gender-matched subjects were evaluated for anti-T.gondii IgG antibodies with enzyme-linked immunosorbent assay (ELISA). During the sampling, a structured questionnaire was used to obtain the demographic information of participants and the risk factors of acquired Toxoplasma. The median ages of case and control groups were 51.04 ± 18.1 (22-97 years) and 51.03 ± 16.5 (21-89 years), respectively (p = 0.99). Anti-T.gondii IgG antibodies were detected in 44 (20.37%) cases and in 135 (41.67%) controls. There was a statistically significant difference for the positivity rate between the smokers and the control group (OR = 0.35; 95%CI: 0.19-0.65; and p = 0.001). The overall prevalence was 33.14%. This study indicated the inverse association between seropositivity to Toxoplasma infection and cigarette smoking. This relationship could be due to the changes that latent toxoplasmosis has on the neurotransmitters, especially dopamine, which needs more research.

Prevalence and Predictors of Toxoplasma gondii Infection in Psychiatric Inpatients in Fars Province, Southern Iran.

Background: Psychiatric patients are at increased risk of exposure to Toxoplasma gondii infection, which may be linked to their living facilities and behaviors. Limited knowledge on the prevalence of T. gondii infection and its associated risk factors in psychiatric patients are available to the international medical communities. Thus, the aim of the current study was to assess seroprevalence of T. gondii and its associated risk factors in psychiatric inpatients in Fars Province, southern Iran. Methods: This cross-sectional study was carried out on psychiatric patients hospitalized in Ibn Sina Hospital affiliated to Shiraz University of Medical Sciences, Fars Province, southern Iran, March to July 2021. Blood samples were collected from 318 psychiatric patients and assessed for the detection of IgG against T. gondii using enzyme-linked immunosorbent assay (ELISA). Moreover, structured questionnaires were completed for the participants at the time of sampling. Logistic regression analysis was used to assess possible associations between the latent toxoplasmosis and the variables. Results: The overall seroprevalence of anti-T. gondii IgG in psychiatric inpatients was 22.3% (71/318; 95% CI = 17.9-27.3). Multivariate analyses revealed that age > 30 years [adjusted odds ratio (AOR) = 2.24, 95% CI = 1.10-4.60, p = 0.03], contact with cats (AOR = 2.52, 95% CI = 1.14-5.58, p = 0.03), raw vegetable consumption (AOR = 3.65, 95% CI = 1.74-7.65, p = 0.001), raw/undercooked meat consumption (AOR = 4.30, 95% CI = 1.47-12.63, p = 0.008), suicide attempt (AOR = 3.77, 95% CI = 1.58-8.97, p = 0.003) and cigarette smoking history (AOR = 0.38, 95% CI = 0.17-0.83, p = 0.02) were independent risk factors for T. gondii infection. Conclusion: The current results demonstrated that contact with cats, raw vegetable consumption and raw/undercooked meat consumption were independent risk factors for T. gondii seropositivity. Moreover, the current study showed significant associations between seropositivity of T. gondii and suicide attempts as well as negative associations between seropositivity of T. gondii and cigarette smoking in psychiatric inpatients using multivariate logistic regression.

Indirect immunofluorescence assay using embryonated eggs of Toxocara in human toxocariasis diagnosis is unreliable due to autofluorescence nature.

Toxocariasis is caused by infection with the nematode species Toxocara canis and Toxocara cati. Serological methods using eggs, larvae and adult worms of Toxocara spp. as antigen have been used for the diagnosis of human toxocariasis. The current study aimed to evaluate indirect immunofluorescence assay (IFA) using embryonated eggs of Toxocara for diagnosis of human toxocariasis. A total of 58 sera including twenty sera from patients with toxocariasis, 20 from healthy persons and 18 from patients with other parasitic infections were collected and used for the study. The embryonated eggs of Toxocara were prepared as antigen. Indirect immunofluorescence assay was performed using the frozen section of uterus containing embryonated T. canis eggs and unembryonated T. cati eggs. All serum samples had a positive reaction using IFA. The eggs of Toxocara as antigen exposed to the serum samples of toxocariasis, other parasitic infections and healthy persons, followed by IFA gave a bright greenish-yellow fluorescence. A number of samples such as eggs of Toxocara, Toxascaris, Trichuris and strongyloides larvae, and adult worm of Ancylostoma exhibited the bright greenish-yellow autofluorescence under fluorescent microscope. IFA using cryocut of embryonated eggs of Toxocara cannot be used for the diagnosis of human toxocariasis due to the existence of autofluorescence of the unembryonated and embryonated eggs, the second stage larva and adult worms of Toxocara spp.

Dermal microfilariae of dogs, jackals and cats in different regions of Iran.

BACKGROUND: Due to the complexity of retrieving skin-dwelling microfilariae, filarioids of dogs presenting dermal microfilariae (e.g. Cercopithifilaria spp., Onchocerca lupi) are relatively unknown compared to Dirofilaria spp. and Acanthocheilonema spp. whose microfilariae circulate in the blood. Although Cercopithifilaria spp. and O. lupi filarioids are distributed worldwide, there is a paucity of information on their occurrence in Iran. The aim of this study was to investigate these filarioids in a large population of dogs from different regions of Iran. METHODS: From October 2018 to September 2020, skin biopsies were obtained from dogs housed in shelters (n = 557) and privately owned dogs (n = 26) in seven provinces of Iran (Hamedan, Kermanshah, Yazd, Mazandaran, Khuzestan, Lorestan, Esfahan), as well as from three road-killed jackals (Canis aureus) and three cats (Felis catus) in Hamedan province. The skin biopsies were first soaked in saline solution at room temperature overnight, and examined for dermal microfilariae under the microscope. Positive skin specimens and sediments were tested by PCR for a 304-bp region of the mitochondrial cytochrome c oxidase subunit 1 (cox1) gene and amplicons were sequenced. RESULTS: Microfilariae of Cercopithifilaria spp. were found in skin biopsies of 32 of the 583 (5.5%) dogs tested, with infection rates of up to 25% in Kermanshah. No microfilariae were recovered from skin biopsy samples collected from dogs in Khorramabad and Ahvaz, nor from the examined jackals and cats. None of the privately owned dogs were found to be infected. Morphologic and morphometric characteristics of the microfilariae were consistent with C. bainae. Eighteen skin samples were positive for the cox1 gene, of which 15 sequences showed a nucleotide identity of 100% and three of 93.4% with the reference sequence of C. bainae available in GenBank (haplotype I; GenBank accession number: JF461457). CONCLUSIONS: The data from this study broadens current knowledge on the geographical distribution of C. bainae in dogs in Middle Eastern countries. Further studies on different wild canine species in the country (e.g. jackal, fox, wolf) could provide further information on the epidemiology of these filarioids. A particular focus should be put on zoonotic O. lupi given the reports of its presence in human patients from this country.

Introduction of protocols for mass production of Toxoplasma gondii tachyzoites of the genotype II PRU strain.

Background: Few investigations of genotype II of Toxoplasma gondii, the most prevalent form of the Toxoplasma parasite in humans, have been carried out on due to the rapid conversion of tachyzoites to bradyzoites in its life cycle. The current study aimed to create animal and in vitro models for production of the tachyzoites of the Prugniaud (PRU) genotype II strain. Methods: To develop an immunocompromised model and obtain tachyzoites of the PRU strain, BALB/c mice were orally treated with dexamethasone (10 mg/kg), cyclophosphamide (36 mg/kg), and cyclosporine (18 mg/kg) from 5 days prior to inoculation. Then, 10-15 tissue cysts of PRU strain were inoculated intraperitoneally into the mice. The tachyzoites obtained from mice were then cultivated in a HeLa cell culture. The resulting yield of tachyzoites was cryopreserved in 92% fetal calf serum, 8% dimethyl sulfoxide. The infectivity of these tachyzoites was evaluated using in vivo and in vitro examinations. Results: Numerous tachyzoites were observed in the peritoneal fluid of the immunosuppressed mice within 10-15 days after inoculation, and many tachyzoites were harvested from the HeLa cell culture. Trypan Blue staining showed 80% viability of the tachyzoites recovered from cryopreservation and this was confirmed by HeLa cell culture. In addition, mice infected intraperitoneally with the recovered tachyzoites presented with cysts in the brain after 2 months. Conclusion: We have developed an animal model for mass production of T. gondii tachyzoites of the PRU strain. This method can provide fresh viable tachyzoites of Toxoplasma gondii for use as and when required in future investigations.

Global prevalence and associated risk factors of diarrheagenic Giardia duodenalis in HIV/AIDS patients: A systematic review and meta-analysis.

Giardia duodenalis is one of the leading causes of diarrhea, mostly in underdeveloped nations of Africa and Asia. The present review provides insights into the prevalence, odds ratios (ORs) and associated risk factors of giardiasis in HIV/AIDS patients. Four major English databases (Web of Science, PubMed, Scopus, and Google Scholar) were excavated for relevant literature without time limitation until 20 November 2020. Next, meta-analysis was performed using a random-effects model and 95% confidence intervals (CIs). As well, heterogeneity among studies was evaluated using Cochran's Q and the I2-statistic. Totally, 19,218 HIV/AIDS patients in 130 studies were examined, showing a 5% (95% CI: 4.2%-6%) pooled prevalence. Also, the weighted random-effects OR of G. duodenalis infection among HIV/AIDS patients in comparison with their controls in 48 case-control studies was estimated as 1.71% (95% CI: 1.1%-2.66%, p = 0.016). Based on sensitivity analysis, there was no remarkable variation in the pooled OR upon omitting individual studies. Diarrhea was a potent risk factor, since HIV/AIDS patients with diarrhea were 3.8-times (95% CI: 1.6-8.9, p = 0.002) more prone to G. duodenalis infection than those without diarrhea. Moreover, the prevalence of the parasitic infection was 1.2-times higher in patients without antiretroviral therapy (ART) than those with ART (p = 0.312). Meta-regression was employed to evaluate the possible association between G. duodenalis frequency in HIV/AIDS patients and some variables such as sample size, publication year, and HDI. Additionally, the pooled prevalence of G. duodenalis infection was estimated based on several subgroups, including publication years, WHO regions, countries, continents, country incomes, and CD4+ T-cell levels. Altogether, the epidemiology of giardiasis in HIV/AIDS patients and its association with various risk factors is still open to question and requires more detailed and comprehensive investigations.

Photocatalytic Perfomance of ZnO-Graphene Oxide Composites towards the Degradation of Vanillic Acid under Solar Radiation and Visible-LED.

Graphene oxide (GO) is used to enhance the photocatalytic activity of ZnO nanoparticles for the degradation of vanillic acid (VA) under simulated solar light and visible-LED (λ > 430 nm). ZnO-GO composites are prepared by a mixing and sonication process with different GO loadings (i.e., from 1.8 to 6.5 wt.%). The materials are extensively characterized by thermogravimetric analysis (TGA), physisorption of N2, X-ray diffraction (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM), point of zero charge (pHPZC), and UV-Vis diffuse reflectance spectroscopy (DRUV). The presence of GO increases the photocatalytic activity of all the prepared composites in comparison with the pristine ZnO. The highest photocatalytic activity is found for the composite containing 5.5 wt.% of GO (i.e., ZnO-GO5.5), reaching a VA degradation of 99% and 35% under solar light and visible-LED, respectively. Higher TOC removal/VA degradation ratios are obtained from the experiments carried out under visible-LED, indicating a more effective process for the mineralization of VA than those observed under simulated solar light. The influence of hole, radical, and non-radical scavengers is studied in order to assess the occurrence of the reactive oxygen species (ROS) involved in the photocatalytic mechanism. The study of the photo-stability during three reuse experiments indicates that the presence of GO in the composites reduces the photocorrosion in comparison with pristine ZnO.

Investigation of simultaneous multiple UV filters degradation efficiency of plasmonic Ag@AgCl photocatalyst in the aquatic environment under sunlight irradiation.

UV filters as an important class of emerging organic pollutants are continuously released into and transported between the aquatic environments. So, the removal of these compounds from aquatic environments is of great importance. This study was conducted to evaluate the simultaneous photodegradation of three widely used UV filter compounds (4-methylbenzylidene camphor, 2-ethylhexyl 4-(dimethylamino) benzoate, ethylhexyl methoxycinnamate), in an aqueous environment under sunlight and Ag@AgCl photocatalyst integrated with plasmonic effect. The plasmonic Ag@AgCl nanocomposite was constructed via photochemical conversion and photoreduction. The enhanced photocatalytic performance can be attributed to the surface plasmon resonance effect of the silver nanoparticles and the hybrid effect caused by AgCl. For the monitoring of the target compounds' degradation before and after photodegradation, an optimized method based on membrane-protected micro-solid-phase extraction coupled with gas chromatography-mass spectrometry (GC-MS) was employed. The simultaneous degradation of selected UV filters was also further investigated in contaminated real samples (river water) and the results showed that the matrix constituents could diminish the photocatalytic degradation efficiency.

Seroprevalence of Toxocara Infection among Asthmatic Children in Shiraz City, Southern Iran.

BACKGROUND: Human toxocariasis is caused by Toxocara canis and T. cati, the nematodes in the intestine of dogs and cats, respectively. Since the association between asthma and toxocariasis is controversial, the aim of the present study was to investigate the seroprevalence of Toxocara infection among asthmatic children in comparison with healthy children. METHODS: This case-control study was conducted on 92 asthmatic and 91 healthy children aged 1-16 years old in Shiraz City, Southern Iran in 2019-2020. The serum samples were tested for IgG anti-Toxocara antibodies by ELISA method using the T. canis larval excretory-secretory (E/S) antigens. The collected data were analyzed using SPSS software. RESULTS: The seroprevalence of toxocariasis in asthmatic patients was higher than the healthy children with no significant difference in Toxocara seropositivity between two groups (9.8% vs 8.8%, P = 0.817). The association between Toxocara infection and variables such as gender and age were not statistically significant. CONCLUSION: There was no significant association between toxocariasis and childhood asthma. Further study on different regions such as urban and rural areas with a large sample size and using questionnaire for considering risk factors of asthma and toxocariasis is recommended.

Optimization and validation of automated solid-phase microextraction arrow technique for determination of phosphorus flame retardants in water.

In the present work, a very sensitive and fully automated direct immersion PAL SPME Arrow procedure, coupled with GC-MS, has been developed and validated for determination of nine phosphorus flame retardants in different types of water samples (river, drinking and rainwater). PDMS/DVB was selected among three commercially available SPME Arrows (PDMS/DVB, DVB/PDMS/CWR and PDMS/CWR), since it resulted in the best sensitivity. The important experimental parameters were optimized via a central composite design response surface methodology and as result, extraction time of 65 min, extraction temperature of 80 °C and added salt concentration of 19% (w/v), were selected as the optimum values. The optimized method showed linear response over the calibration range (2 - 500 ng L-1), with R2-values higher than 0.9937. The precision (RSD%) measured by replicate analyses (n = 7) was estimated at 2 and 100 ng L-1 and was less than 29% and 21%, respectively. The LOQ of PAL SPME Arrow, calculated as S/N = 10, was between 0.2 and 1.2 ng L-1 (for triphenyl phosphate and tris-(1­chloro­2-propyl) phosphate, respectively) with extraction efficiencies between 5.9 and 31% (for tris-(1,3-dichloro-2-propyl) phosphate and tri-n­butyl phosphate, respectively). To assess the performance of the developed technique for real samples, two river water samples, tap water from two regions and a rainwater sample were analyzed. Most of the target analytes were observed in the river samples with concentrations of 1.0 - 250 ng L-1 and the obtained recoveries at 50 ng L-1 ranged between 60 and 107%. Considering the figures of merit of the optimized method, PAL SPME Arrow-GC-MS showed to be the most sensitive analytical approach for determination of phosphorus flame retardants in water, with satisfying precision and accuracy, compared with conventional SPME-NPD, LLE-GC-MS and SPE-LC-MS/MS.

Automated determination of picogram-per-liter level of water taste and odor compounds using solid-phase microextraction arrow coupled with gas chromatography-mass spectrometry.

Taste and odor compounds are organic chemicals produced via biochemical processes, and their presence, even at low nanogram-per-liter concentrations, can make water useless for drinking purposes. In this work, a very sensitive and completely automated analytical procedure, based on solid-phase microextraction, has been developed and optimized for determination of seven taste and odor compounds in water media, well below their odor threshold. The selected analytes were isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, geosmin, 2-methylisoborneol, 2,4,6-trichloroanisole, 2,4,6-bromoanisole, and beta-ionone. Compared with a conventional approach, the recently introduced PAL SPME Arrow showed a significant enhancement in sensitivity and also outstanding robustness and stability. Three commercially available fiber coatings, as well as experimental parameters of the headspace extraction procedure, such as extraction temperature, time, and ionic strength of the aqueous sample, were investigated to optimize the method. The linearity of the response was assessed over a three-orders-of-magnitude range, with R2 values higher than 0.9914. The method was satisfactorily precise, with RSDs less than 11% at the second lowest calibration point (10-26 ng L-1). The calculated LODs (S/N = 3) were below odor thresholds of the target analytes and varied between 0.05 and 0.6 ng L-1, for just 10 mL of water sample. An original and spiked river water sample was also analyzed, and relative recoveries of 75-116% were achieved. Based on these analytical performance characteristics, and compared with other published methods, the present method can be considered as the most sensitive wholly automated approach for determination of taste and odor compounds in water.

Determination of ultraviolet filter compounds in environmental water samples using membrane-protected micro-solid-phase extraction.

A method based on membrane-protected micro-solid-phase extraction coupled with gas chromatography and mass spectrometry was developed for the determination of six ultraviolet filter compounds in various aqueous media. Multiwalled carbon nanotubes as the sorbent were encapsulated in a sealed polypropylene membrane packet and immersed in the sample to extract the analytes, and then dichloromethane was used for desorption purpose. The method was sensitive enough for quantitative analysis of the target analytes, with limits of quantification between 0.01 and 0.06 µg/L, and produced a linear response (R2  > 0.991) over the calibration range (0.05-6 µg/L). The obtained reproducibility was practically suitable with relative standard deviation values of less than 14% in pure water (spiked at 0.20/µg L) and less than 15% in real samples. The optimized method was applied for the analysis of real water samples with varying matrix complexity: tap, river, and dam water; geothermal spa; and sewage treatment plant effluent. Various levels and patterns of contamination were observed in the examined samples, while the sample from spa was the most contaminated, regarding the target analytes. Matrix spikes and matrix spike replicates were also analyzed to validate the technique for analysis of real aqueous samples, and satisfactory results were achieved.

Matrix Solid-Phase Dispersion Based on Carbon Nanotube Coupled with Dispersive Liquid-Liquid Microextraction for Determination of Organochlorine Pesticides in Soil.

The presented article describes the methodology and results of investigating the capability of multi-walled carbon nanotube as sorbent in an efficient extraction method for determination of organochlorine pesticides, α-BHC, ß-BHC, γ-BHC, heptachlor, endrin, aldrin, 4,4'-DDD, 4,4'-DDE and 4,4'-DDT, in soil media. Matrix solid-phase dispersion was optimized for extraction from small amounts of soil samples and the resulting extracts were pre-concentrated using dispersive liquid-liquid microextraction. The most important experimental parameters of both extraction procedures were studied and the optimum conditions for simultaneous analysis of the target analytes were determined. In the final analysis procedure, a 0.20 g portion of dried soil sample was extracted by dichloromethane after being mixed with 0.020 g of carbon nanotube and 0.400 g of silica gel. Then, dispersive liquid-liquid extraction was used to pre-concentrate the extract before injecting the sample into the gas chromatographic system. The pre-concentration step showed to have up to 32 times of enrichment capability and the total procedure had reasonable sensitivity and reproducibility, with limit of detections <1.6 ng g-1 and relative standard deviation values below 8.1%, respectively. It was also demonstrated that the organic content of the soil can alter the extraction efficiency (70-105%), depending on both the amount of the organic matter and the individual analyte. Therefore, the importance of matrix spike samples, throughout the method validation procedure, was confirmed.

Chemometrics-Assisted Fast-Elution HPLC-DAD for the Quantification of Selected UV Filters and Parabens in Suncare Formulations.

In the present study, a fast LC method coupled with multivariate curve resolution (MCR) alternating least-squares (ALS) and alternating trilinear decomposition (ATLD) was developed for the determination of the resolution of and quantitation of benzophenone-3, 4-methylbenzylidene camphor, octocrylene, ethylhexyl dimethyl para-aminobenzoic acid, butyl methoxydibenzoilmethane, and methyl and propyl parabens in suncare products. Chromatographic separation was optimized using full factorial and Box-Behnken designs. MCR-ALS and ATLD performance in quantitating the analytes in synthetic mixtures (which were randomly prepared in ultra-pure water) and blank sunscreen products was studied, and satisfying results were obtained. Acceptable qualification and quantification results were also achieved in the presence of matrix interferences via a short chromatographic runtime (5 min), and the second-order advantage was fully exploited, with MCR-ALS clearly emerging as the superior model. Average recoveries ranged from 98.0 to 112.5%, and RSD values were lower than 6.5%. LODs between 0.066 and 0.243 µg/g were achieved. In addition to acceptable precision and accuracy, the merits of the proposed method are that the analysis is fast and there is minimal solvent consumption. Moreover, coelution of analytes and interference from components in the sample matrixes were overcome with multivariate analysis.

Direct analysis of six antibiotics in wastewater samples using rapid high-performance liquid chromatography coupled with diode array detector: a chemometric study towards green analytical chemistry.

In this work, a rapid HPLC-DAD method has been developed for the analysis of six antibiotics (amoxicillin, metronidazole, sulfamethoxazole, ofloxacine, sulfadiazine and sulfamerazine) in the sewage treatment plant influent and effluent samples. Decreasing the chromatographic run time to less than 4 min as well as lowering the cost per analysis, were achieved through direct injection of the samples into the HPLC system followed by chemometric analysis. The problem of the complete separation of the analytes from each other and/or from the matrix ingredients was resolved as a posteriori. The performance of MCR/ALS and U-PLS/RBL, as second-order algorithms, was studied and comparable results were obtained from implication of these modeling methods. It was demonstrated that the proposed methods could be used promisingly as green analytical strategies for detection and quantification of the targeted pollutants in wastewater samples while avoiding the more complicated high cost instrumentations.

Multivariate curve resolution-assisted determination of pseudoephedrine and methamphetamine by HPLC-DAD in water samples.

In the present study, a simple strategy based on solid-phase extraction (SPE) with a cation exchange sorbent (Finisterre SCX) followed by fast high-performance liquid chromatography (HPLC) with diode array detection coupled with chemometrics tools has been proposed for the determination of methamphetamine and pseudoephedrine in ground water and river water. At first, the HPLC and SPE conditions were optimized and the analytical performance of the method was determined. In the case of ground water, determination of analytes was successfully performed through univariate calibration curves. For river water sample, multivariate curve resolution and alternating least squares was implemented and the second-order advantage was achieved in samples containing uncalibrated interferences and uncorrected background signals. The calibration curves showed good linearity (r(2) > 0.994).The limits of detection for pseudoephedrine and methamphetamine were 0.06 and 0.08 µg/L and the average recovery values were 104.7 and 102.3% in river water, respectively.