Detection Limit Of Method Research Articles

Assessing cobalt and manganese in foods: A study on determination and health risk using inductively coupled plasma spectrometry

This study aimed to evaluate the concentration and health risk of cobalt (Co) and manganese (Mn) in food using inductively coupled plasma mass spectroscopy (ICP-MS) and ICP optical emission spectroscopy (ICP-OES), respectively. Methods were validated for six food classes based on composition and calorie content. The method limit of quantification (MLOQ) ranged from 0.0766 to 0.2525 μg/kg for Co and 0.0202–0.0832 mg/kg for Mn. Out of 351 food items, Co and Mn were detected above the method limit of detection (MLOD) in 266 and 222 samples, respectively, with highest levels in nuts, seeds, grains, beans, sauces, and seasonings. Pearson correlation analysis showed a significant positive correlation (p < 0.01) between Co and Mn in agricultural (r = 0.390) and processed food (r = 0.543) categories. Exposure to Co and Mn through dietary intake remained within acceptable limits (target hazard quotient (THQ) < 1), suggesting that lifetime consumption is unlikely to elevate potential health risks. In conclusion, this comprehensive study validated methods for Co and Mn analysis and assessed their concentrations and potential health risks across various food categories.

Evaluation of Lead Ion in the Wastewater of the Lifting and Treatment Stations Using ICP-MS and CPE Methods

To pre-concentrate trace amounts of lead before determining it by UV-vis spectrophotometer, a new method for micelle-mediated phase separation has been created. The process depends on the extraction of lead from iodine media using Triton X-114 in the cloud point extraction method without the need for any chelating agents, where the optimal conditions for the method were achieved, which temperature 50 °C, pH 4, and 30 mmol L−1 concentration of KI, 0.3 mL of 2% (v/v) Triton X-114, and time of 10 min in the water bath. Linearity was followed between 1 and 16 µg/mL of lead concentration. The method's lead detection limit is 0.1 µg/mL and %RSD 3.633. Additionally, the interference impact of certain cations was evaluated. The proposed technique was successfully applied to determine the lead ion in the wastewater in ten different stations in the center and district of Al-Hur in Karbala City. The lead ion of the wastewater of the stations under study was also determined directly using inductively coupled plasma-mass spectrometry (ICP-MS) technology comparing its results with the new method and performing the statistical analysis of both methods. The p-value was less than 0.05, showing significant differences between both methods.

Triethanolamine-based esterquat in sediments: New analytical method, environmental occurrence, and homologue composition

The cationic surfactant triethanolamine-based esterquat (TEAQ) is a main ingredient in commercial fabric softeners and is produced and used in large quantities. However, little information is available for its occurrence in the environment, particularly in sediments. Here, we developed an analytical method for quantifying TEAQ in sediment and investigated TEAQ contamination in Japanese river and lake sediments. In our analytical method, TEAQ concentrations were measured by liquid chromatography–tandem mass spectrometry using a polymer-based size-exclusion column, which resulted in excellent peak shapes. TEAQ was detected at significant levels in procedural blanks, resulting in a method limit of detection in the sediment of 8.9–97 μg/kg-dry for TEAQ monoesters and 0.6–24 μg/kg-dry for TEAQ diesters. TEAQ was detected in 22 out of 26 sediment samples, with the sum of all homologue concentrations being up to 1340 μg/kg-dry. The concentration of TEAQ in sediments was high at locations where the concentrations of benzalkoniums and the organic carbon content were also high. TEAQ was detected in 8 out of 14 commercial fabric softeners at concentrations of 1.7–7.4 wt%. TEAQ homologues containing only saturated fatty acids accounted for 83 ± 5% of the total TEAQ in the sediments, whereas those with unsaturated fatty acids accounted for 71 ± 14% of the total TEAQ in a commercial technical mixture and the softener products. The results of this study will be useful for the environmental risk assessment of esterquats.

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

BackgroundDried 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. ResultsWe 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 noveltyTo 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.

Quality assurance and quality control of atmospheric organosulfates measured using hydrophilic interaction liquid chromatography (HILIC)

Abstract. ​​​​​​​As a crucial constituent of fine particulate matter (PM2.5), secondary organic aerosols (SOAs) influence public health, regional air quality, and global climate patterns. This paper highlights the use of hydrophilic interaction liquid chromatography (HILIC) which effectively retains strongly polar analytes that might exhibit incomplete or no retention in reverse chromatography, resulting in superior separation efficiency. A HILIC column was used to analyze six standards, environmental standards (1648a and 1649b), and samples collected in urban environments in Guangzhou in the Pearl River Delta region, which serve as valuable reference points for evaluating the organic composition of the atmospheric environment. The results indicate a high degree of accuracy in the analytical method. Sodium octyl-d17 sulfate serves as the internal standard, with a linear correlation coefficient of the six standards, boasting a linear correlation coefficient r ranging from 0.993–0.9991 and a slope, k, of the linear equation from 0.966–1.882. The instrument detection limits (IDLs) are established at 0.03–0.20 µg mL−1, while the method detection limits (MDLs) fall within the range of 0.30–1.75 ng m−3, demonstrating the method's exceptional sensitivity. Since isoprene-derived organosulfates (iOSs) are highly polar due to containing a hydrophilic bond to the hydroxyl group and a hydrophobic bond to the sulfate, and as such showed strong retention using this method, this technique employs sodium ethyl sulfate and sodium octyl sulfate standards for semi-quantitative compound analysis of iOSs. The error in sample analysis (EA) ranged from 12.25 %–95.26 %, and the two standards maintained a consistent recovery rate between 116 %–131 % and 86.4 %–127 %. These findings indicate a high level of precision when semi-quantifying compounds with similar structural characteristics, affirming the analysis method's minimal relative error and underscoring its repeatability, process stability, and the reliability of its results for iOSs. To enhance the method's reliability assessment, the study analyzed polar organic components of standard particulate matter samples (1648a and 1649b), providing precise determinations of several iOSs using this method. Methyltetrol sulfate (m/z 215, C5H11SO7-) is the highest concentration in the ambient samples, up to 67.3 ng m−3 in the daytime. These results serve as valuable reference points for assessing the organic composition of the atmospheric environment.

Rapid and Convenient Potentiometric Method for Determining Fluorosulfate, a Byproduct of the Fumigant and Greenhouse Gas Sulfuryl Fluoride.

A fluorosulfate ion (FSO3-) is a hydrolysis product of sulfuryl fluoride (SO2F2), which is widely used to fumigate buildings, soil, construction materials, and postharvest commodities, and is a potent greenhouse gas. It is a potential marker for biological exposure to SO2F2 and for monitoring the progress of reactions used to scrub SO2F2 from fumigation vent gases. Here, we report a simple and inexpensive potentiometric method for determining FSO3- using a commercial nitrate-selective electrode and discuss its application. The method is suitable for solutions between 0.0025 mM and 660 mM FSO3- at initial pH between 5 and 9. Halide interference depends on its molar ratio to FSO3- and follows the sequence, F- < Cl- < Br- ≪ I-. Halide interference can be eliminated by adding silver sulfate. Interference by bicarbonate can be eliminated by H2SO4 pretreatment, and interference by phosphate or pyrophosphate by MgSO4 addition. Sulfate does not interfere, as it does in ion chromatography. Satisfactory method detection limits for FSO3- in spiked aqueous extracts of 11 fruits were obtained. The method accurately quantified the yield of FSO3- relative to that of F- in base hydrolysis of SO2F2. This study demonstrates that the developed method is highly selective, convenient, and sensitive and thus can be of great value in practice.

Detection of soybean allergens based on isotope dilution mass spectrometry: Development, validation, and applications in complex food matrices

An effective and versatile method based on isotope dilution mass spectrometry (IDMS) has been developed for the detection of soybean allergens in complex food matrices. The sample treatment method and MRM conditions in MS have been optimized to achieve the highest extraction efficiency and maximum intensity. The signature peptides VLIVPQNFVVAAR from Gly m 6 G1 subunit, TISSEDEPFNLR from Gly m 5 beta subunit, QQQEEQPLEVR and LFEITPEKNPQLR from Gly m 5 alpha’ subunit were selected, and the corresponding isotopically labeled peptides were served as the internal standards to minimize the matrix effects. The standard solutions showed a good linearity ranging from 1 to 200 ng/mL. The recoveries were in the range of 84.61 %–115.63 % and relative standard deviations were in the range of 0.66 % to 12.77 %. The method detection limits (MDLs) and quantitation limits (MQLs) of Gly m 6 G1 subunit, Gly m 5 beta subunit, and Gly m 5 alpha’ subunit in four matrices were less than 2.5 μg/g and 10 μg/g. By utilizing the developed method, three soybean allergens were determined in soy milk and ham sausage which contained soybean. The butter cookies that were not made of soy were also detected to contain soybean allergens, possibly due to manufacturing contamination. Surprisingly, soybean allergens were detected in the sesame paste labeled as soybean free, showing the importance to re-evaluate the soybean allergens after production. Our work laid the groundwork for the development of a versatile and sensitive method to evaluate soybean allergens in food products.

P-chromophore stability of Mehlich-1 and Mehlich-3 under Braga &amp; Defelipo or Murphy &amp; Riley dosing methods

ABSTRACT The performance of colorimetric methods for P quantification has been overlooked by researchers for decades. We investigated the performance of two blue colorimetric methods for P quantification, Braga and Defelipo (B&amp;D) and Murphy and Riley (M&amp;R), using two commonly soil P extractants, Mehlich-1 (M1) and Mehlich-3 (M3). Specifically, we evaluated the color development time and its stability in different soil extractant solution proportions (1:1 or 1:4 v/v), the optimum wavelength, limits of detection, and element quantification. Our results indicate that M3 leads to lower limits of detection and quantification for both colorimetric methods, particularly for B&amp;D. For M1, the volumetric ratio (1:1 or 1:4) did not influence color development and both B&amp;D and M&amp;R methods showed a fast color development. However, B&amp;D showed greater color stability (from 5 to 600 min) and an optimum wavelength of 711 nm, while M&amp;R was stable from 27 to 600 min an optimum wavelength of 889 nm. For M3 soil extractant, there are important issues, such as M&amp;R being unstable and B&amp;D presenting slow color development. In addition, the spectral profile obtained from soil extractant was different from the one obtained by the calibration curve without soil for both M&amp;R and B&amp;D. Therefore, the adoption of original methods on P quantification in M3 extracting solution represents a potential source of error, leading to wrong P fertilizer recommendations. Thus, the best option for P quantification in M3 extracts seems to be the use of Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES).

Online sequential analysis of volatile and semivolatile organic compounds in water matrices by double robotic sample preparations and dual-channel mono and comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry system

The monitoring of organic compounds in aquatic matrices poses challenges due to its complexity and time-intensive nature. To address these challenges, we introduce a novel approach utilizing a dual-channel mono (1D) and comprehensive two-dimensional (2D) gas chromatography coupled with time-of-flight mass spectrometry (GC × GC–TOFMS) system, integrated with a robotic pretreatment platform, for online monitoring of both volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) in water matrices. Employing the robotic platform, we establish a suite of online liquid–liquid extraction (LLE) pretreatment processes for water samples, marking the first instance of such procedures. Leveraging the automatic headspace (HS) module, dual robotic preparations of HS and LLE are sequentially executed to extract VOCs and SVOCs from water matrices. The GC × GC–TOFMS system is distinguished by its dual-channel analytical column configuration, facilitating sequential analysis of VOCs in GC–TOFMS mode and SVOCs in GC × GC–TOFMS mode. Quantitative detection of 55 target VOCs and 104 SVOCs is achieved in a water sample using the instrument system. Our method demonstrates excellent correlation coefficients ranging from 0.990 to 1.000, method detection limits ranging from 0.08 to 4.78 μg L–1, relative standard deviations below 19.3 %, and recovery rates ranging from 50.0 % to 124.0 %. To validate the online monitoring capabilities of our system, we assess target SVOCs at three different concentration levels over a 3-day period. Most compounds exhibit recovery rates ranging from 70.0 % to 130.0 %. Furthermore, we apply our method to analyze a real water sample, successfully identifying over 100 target and nontarget VOCs/SVOCs, including alcohols, aldehydes, ketones, acids, esters, and phenols. These results highlight the efficacy of the proposed analysis system, capable of conducting two distinct analyses in automatic sequence, thereby enhancing the efficiency and accuracy of organic compound analysis in water matrices.

Automated infrared ashing with palladium nitrate as an ashing aid for the determination of selenium in plant foods by inductively coupled plasma mass spectrometry.

Based on the automatic light wave ashing instrument, palladium nitrate was used as an ashing aid for the first time to collect selenium in the process of food ashing pre-treatment, and a method for the determination of selenium in food by ashing method was established with inductively coupled plasma mass spectrometry. At the same time, the effects of magnesium nitrate, rhodium nitrate, and nickel nitrate as ashing aids on selenium collection were investigated using certified plant standard materials. The capture of selenium by magnesium nitrate, rhodium nitrate, and nickel nitrate as ashing aids did not exceed 50%. Using palladium nitrate as an ashing aid, six food standard materials were measured, with selenium recovery rates ranging from 97 to 106%. A complete analysis cycle can be completed within an hour. The method detection limit of selenium was 0.021μgg-1, and the relative standard deviation of five measurements was less than 7%. The experimental results show that palladium nitrate is an excellent ashing aid for capturing selenium, and it is far superior to the other three aids. In addition, the mechanism of palladium nitrate as an ashing aid for capturing selenium was discussed.

Biomonitoring urinary pesticide metabolites in preschool children by supported liquid extraction and ultra-high performance liquid chromatography-tandem mass spectrometry and their association with oxidative stress

Investigating pesticide exposure and oxidative stress in preschool children is essential for elucidating the determinants of environmental health in early life, with human biomonitoring of urinary pesticide metabolites serving as a critical strategy for achieving this objective. This study demonstrated biomonitoring of 2 phenoxyacetic acid herbicides, 2 organophosphorus pesticide metabolites, and 4 pyrethroid pesticide metabolites in 159 preschool children and evaluated their association with oxidative stress biomarker 8-hydroxydeoxyguanosine. An enzymatic deconjugation process was used to release urinary pesticide metabolites, which were then extracted and enriched by supported liquid extraction, and quantified by ultra-high performance liquid chromatography-tandem mass spectrometry with internal standard calibration. Dichloromethane: methyl tert‑butyl ether (1:1, v/v) was optimized as the solvent for supported liquid extraction, and we validated the method for linear range, recovery, matrix effect and method detection limit. Method detection limit of the pesticide metabolites ranged from 0.01 μg/L to 0.04 μg/L, with satisfactory recoveries ranging from 70.5 % to 95.5 %. 2,4,5-Trichlorophenoxyacetic acid was not detected, whereas the other seven pesticide metabolites were detected with frequencies ranging from 10.1 % to 100 %. The concentration of urinary pesticide metabolites did not significantly differ between boys and girls, with the median concentrations being 9.39 μg/L for boys and 4.90 μg/L for girls, respectively. Spearman correlation analysis indicated that significant positive correlations among urinary metabolites. Bayesian kernel machine regression revealed a significant positive association between urinary pesticide metabolites and 8-hydroxydeoxyguanosine. Para-nitrophenol was the pesticide metabolite that contributed significantly to the elevated level of oxidative stress.

Biomonitoring of benzophenones in guano samples of wild bats in Poland.

Benzophenones (BPs) are substances used in the production of sunscreens, cosmetics, and personal care products. However, there is a lack of knowledge of BPs in wild animals. Therefore, the study aimed to assess the concentration of selected BPs commonly used in the cosmetic industry in guano samples collected from 4 colonies of greater mouse-eared bats (Myotis myotis). Liquid chromatography with tandem mass spectrometry (LC-MS/MS) was used to determine guano concentrations of benzophenone 1 (BP-1), benzophenone 2 (BP-2), benzophenone 3 (BP-3) and benzophenone 8 (BP-8). BP-1 levels above the method quantification limit (MQL) were noted in 97.5% of samples and fluctuated from <0.1 ng/g to 259 ng/g (mean 41.50 ng/g, median 34.8). The second most common was BP-3, which fluctuated from <0.1 ng/g to 19 ng/g (mean 6.67 ng/g, median 5.05), and its levels higher than MQL were observed in 40% of samples. BP-2 and BP-8 concentrations did not exceed the method detection limit (0.04 ng/g) in any analyzed sample. There were visible differences in the BP-1 and BP-3 levels among the studied bat colonies. Mean BP-1 concentration fluctuated from 11.23±13.13 ng/g to 76.71±65.51 ng/g and differed significantly between the colonies. Mean BP-3 concentration fluctuated from 5.03±6.03 ng/g to 9.18±7.65 mg/g, but it did not differ significantly between the colonies. The results show that guano is a suitable matrix for the assessment of wildlife exposure to BPs. This could be particularly advantageous in protected species, where not disturbing and stressing the animals are crucial.

Genotyping Plasmodium falciparum gametocytes using amplicon deep sequencing

BackgroundUnderstanding the dynamics of gametocyte production in polyclonal Plasmodium falciparum infections requires a genotyping method that detects distinct gametocyte clones and estimates their relative frequencies. Here, a marker was identified and evaluated to genotype P. falciparum mature gametocytes using amplicon deep sequencing.MethodsA data set of polymorphic regions of the P. falciparum genome was mined to identify a gametocyte genotyping marker. To assess marker resolution, the number of unique haplotypes in the marker region was estimated from 95 Malawian P. falciparum whole genome sequences. Specificity of the marker for detection of mature gametocytes was evaluated using reverse transcription-polymerase chain reaction of RNA extracted from NF54 mature gametocytes and rings from a non-gametocyte-producing strain of P. falciparum. Amplicon deep sequencing was performed on experimental mixtures of mature gametocytes from two distinct parasite clones, as well as gametocyte-positive P. falciparum field isolates to evaluate the quantitative ability and determine the limit of detection of the genotyping approach.ResultsA 400 bp region of the pfs230 gene was identified as a gametocyte genotyping marker. A larger number of unique haplotypes was observed at the pfs230 marker (34) compared to the sera-2 (18) and ama-1 (14) markers in field isolates from Malawi. RNA and DNA genotyping accurately estimated gametocyte and total parasite clone frequencies when evaluating agreement between expected and observed haplotype frequencies in gametocyte mixtures, with concordance correlation coefficients of 0.97 [95% CI: 0.92–0.99] and 0.92 [95% CI: 0.83–0.97], respectively. The detection limit of the genotyping method for male gametocytes was 0.41 pfmget transcripts/µl [95% CI: 0.28–0.72] and for female gametocytes was 1.98 ccp4 transcripts/µl [95% CI: 1.35–3.68].ConclusionsA region of the pfs230 gene was identified as a marker to genotype P. falciparum gametocytes. Amplicon deep sequencing of this marker can be used to estimate the number and relative frequency of parasite clones among mature gametocytes within P. falciparum infections. This gametocyte genotyping marker will be an important tool for studies aimed at understanding dynamics of gametocyte production in polyclonal P. falciparum infections.

Investigations of Major α-Dicarbonyl Content in U.S. Honey of Different Geographical Origins.

α-Dicarbonyls are significant degradation products resulting from the Maillard reaction during food processing. Their presence in foods can indicate the extent of heat exposure, processing treatments, and storage conditions. Moreover, they may be useful in providing insights into the potential antibacterial and antioxidant activity of U.S. honey. Despite their importance, the occurrence of α-dicarbonyls in honey produced in the United States has not been extensively studied. This study aims to assess the concentrations of α-dicarbonyls in honey samples from different regions across the United States. The identification and quantification of α-dicarbonyls were conducted using reverse-phase liquid chromatography after derivatization with o-phenylenediamine (OPD) and detected using ultraviolet (UV) and mass spectrometry methods. This study investigated the effects of pH, color, and derivatization reagent on the presence of α-dicarbonyls in honey. The quantification method was validated by estimating the linearity, precision, recovery, method limit of detection, and quantification using known standards for GO, MGO, and 3-DG, respectively. Three major OPD-derivatized α-dicarbonyls including methylglyoxal (MGO), glyoxal (GO), and 3-deoxyglucosone (3-DG), were quantified in all the honey samples. 3-Deoxyglucosone (3-DG) was identified as the predominant α-dicarbonyl in all the U.S. honey samples, with concentrations ranging from 10.80 to 50.24 mg/kg. The total α-dicarbonyl content ranged from 16.81 to 55.74 mg/kg, with the highest concentration measured for Southern California honey. Our results showed no significant correlation between the total α-dicarbonyl content and the measured pH solutions. Similarly, we found that lower amounts of the OPD reagent are optimal for efficient derivatization of MGO, GO, and 3-DG in honey. Our results also indicated that darker types of honey may contain higher α-dicarbonyl content compared with lighter ones. The method validation results yielded excellent recovery rates for 3-DG (82.5%), MGO (75.8%), and GO (67.0%). The method demonstrated high linearity with a limit of detection (LOD) and limit of quantitation (LOQ) ranging from 0.0015 to 0.002 mg/kg and 0.005 to 0.008 mg/kg, respectively. Our results provide insights into the occurrence and concentrations of α-dicarbonyl compounds in U.S. honey varieties, offering valuable information on their quality and susceptibility to thermal processing effects.

Portable tri-color ratiometric fluorescence paper sensor for intelligent visual detection of dual-antibiotics and aluminium ion

The toxicological effect between co-existed antibiotics and metal ions was dangerous to the ecological environment and public health. However, the rapid quantification tools with convenience, accuracy and low cost for the detection of multiple targets were still challenging. Herein, a portable tri-color ratiometric fluorescence paper sensor was constructed by coupling of blue carbon dots and fluorescence imprinted polymer for down/up conversion simultaneous detection of tetracycline and sulfamethazine. Interestingly, the cascade detection of aluminum ion was also realized based on the individual detection system of tetracycline without the assistance of complex coupling reagents. The detection limits of smartphone method for the visual detection of tetracycline, sulfamethazine and aluminum ion were calculated as 0.014 μM, 0.004 μM and 0.019 μM, respectively. The portable fluorescence paper sensor was applied for the visual detection of tetracycline, sulfamethazine and aluminum ion in actual samples successfully with satisfactory recoveries. With the advantages of rapidness, low cost, and portability, the developed portable fluorescence paper sensor provided a new strategy for the visual real-time detection of multiple targets.

Rapid determination of metallic additives in century eggs by microwave plasma‐atomic emission spectrometer and microwave‐assisted digestion

AbstractCentury eggs (also known as pídàn) are a widely used preserved food product in Taiwanese cuisine. Due to their peculiar appearance, pungent odor, and unusual texture, several consumers have raised concerns. Actually, some metallic additives are employed to control the quality of gelation of protein during the production of century eggs. Therefore, a method involving microwave plasma‐atomic emission spectrometer and microwave‐assisted digestion was proposed in this study. In addition, to clarify distribution information of metallic additives in century eggs, detailed analyses based on the egg structure were adopted. The linearities for Fe and Zn were obtained in the range of 0.1–5, and 0.02–1 mg L−1 for Cu and Pb. The method detection limits for test metals were 0.06–0.036 mg L−1. The measured values for the RM EGGS‐1 sample agreed reasonably well with the reference values, demonstrating that the developed method is practical for routine analysis with lower instrument procurement/running cost. The analytical results for century eggs collected from local markets revealed diverse distributions of metal ions in different parts. Remarkably, this method can readily identify the metallic additives used during the production processes even in the presence of complicated matrices.

Photo-crosslinked hydrogel as a sensing platform for sensitive detection of free bilirubin in urine samples

In cases of liver lesions or metabolic blockages, the accumulation of bilirubin in the blood can lead to hyperbilirubinemia, resulting in jaundice. Hence, the development of a rapid and highly selective assay strategy for accurately quantifying free bilirubin concentrations in humans is crucial for clinical diagnosis and treatment. In this study, a postsynthetic modification (PSM) strategy was used to obtain UiO-66-PSM (UP) by the aldimine condensation reaction of metal-organic framework UiO-66-NH2 with 2,3,4-trihydroxybenzaldehyde. UP itself possesses strong fluorescent properties. Subsequently, UiO-66-PSM-Fe (UPF) was synthesized by incorporating Fe3+ onto the UP surface using a one-pot method, where the interaction of Fe3+ with UP induced fluorescence quenching. Bilirubin has a strong binding affinity for Fe3+. Therefore, it can react with the UPF, losing Fe3+ and regaining fluorescence, and thus realizing the detection of bilirubin. In order to further improve the detection outcome and facilitate the application, UPF was loaded onto gelatin methacryloyl hydrogel to construct a fluorescence sensor. This enabled highly sensitive determination of bilirubin with a method limit of detection of 5.67 pM. Furthermore, genuine human urine samples were analyzed, demonstrating the practical application of the assay in discovering human health conditions associated with bilirubin.

Magnetic graphene oxide functionalized dimercaptosuccinic acid/putrescine as a selective and stable solid-phase extraction adsorbent for preconcentration and speciation of arsenic (III) in water samples

ABSTRACT It is challenging for environmental scientists to identify the trace value of arsenite (As(III)) as an essential hazardous material in the presence of arsenate (As(V)) and other metal ions. This paper proposes a method of magnetic solid-phase extraction (MSPE) for the trace analysis of As(III) using magnetite graphene oxide (MGO) covalently functionalised with dimercaptosuccinic acid (DMSA) and putrescine (PUT). The hydrothermally synthesised MGO/DMSA-PUT adsorbent was carefully characterised by using energy-dispersive X-ray spectroscopy analysis, Fourier transform infrared, dynamic light scattering, scanning electron microscopy, zeta potential analyser, X-ray diffraction, and vibrating sample magnetometer techniques in detail. Maximum adsorption capacity of MGO/DMSA-PUT for As(III) was determined 144 mg g−1 which considerably improved vs. graphene oxide with the adsorption capacity of 54.8 mg g−1. Sample pH of 6 with a volume of 50 mL, contact time of 5 minutes, initial concentration of 50 μg L−1, adsorbent dosage of 0.1 g and volume of eluent 3 mL were obtained as the optimised parameters for the developed MSPE procedure. According to experimental data obtained with hydride generation atomic absorption spectroscopy, the linear range and detection limit of the proposed method for As(III) measurement was found to be 0.4–5000 µg L−1 and 9.914 ng L−1, respectively. According to experimental results, a preconcentration limit (PL) of 1.72 µg L−1 was achieved for As(III), corresponding to a preconcentration factor of 965. Statistical analysis of standard reference materials confirmed the accuracy of the method against systematic and constant errors (>95% recovery with <5% RSD). Because of the selectivity of MGO/DMSA-PUT towards the As(III), the developed MSPE procedure is capable for successful speciation and determination of As(III) in water samples with satisfactory analytical results.

Occurrence, distribution and annual emissions of chlorinated paraffins in hazardous byproducts from municipal solid waste incineration plants in South China

Nowadays incineration technology has become the most mainstream way for the disposal of municipal wastes. Short chain chlorinated paraffins (SCCPs) and medium chain chlorinated paraffins (MCCPs) are currently classified as new persistent organic pollutants (POPs) and candidate POPs under the Stockholm Convention, respectively. However, the occurrence and contamination characteristics of these main hazardous byproducts (e.g., leachate, fly ash, and bottom ash) from municipal solid waste incineration (MSWI) plants have remained unknown. This study focused on the SCCPs and MCCPs (defined as CPs) contamination and their annual emissions from leachate, fly ash, and bottom ash among three typical MSWI plants in Shenzhen, South China. Compared to the dissolved phase of the leachate, higher concentrations of CPs were detected in the adsorbed phase. The total concentrations of CPs ranged from lower method detection limits (<MDLs) to 448 ng/g in fly ash and 124 to 7230 ng/g in bottom ash. The ratios of MCCPs to SCCPs were generally >1 in leachate (i.e., adsorbed phase) and bottom ash, while the opposite results were found in fly ash. The dominant SCCP congener groups were C10Cl6–7 in leachate and fly ash, and C13Cl6–7 in bottom ash. The dominant MCCP congener groups were C14Cl7–8 in leachate, fly ash and bottom ash samples. Principal component analysis (PCA) revealed the dominant CPs in fly ash were obviously different from those in leachate and bottom ash. Estimated total annual emissions of CPs from the three main hazardous byproducts generated from typical MSWI plants were estimated between 66.2 and 7510 kg/y and bottom ash contributed the most to the CP emissions. Overall, this study is the first report on CP contamination in hazardous byproducts from MSWI plants, and can provide basic data support for CP contamination control.

Development of a vortex-assisted switchable-hydrophilicity solvent-based liquid phase microextraction for fast and reliable extraction of Zn (II), Fe (II), Pb (II), and Cd (II) from various baby food products

This manuscript describes the development of a novel liquid phase microextraction (LPME) method for the extraction and determination of Zn (II), Fe (II), Pb (II), and Cd (II) in various infant/baby food and supplements products. The method is based on vortex-assisted extraction combined with a switchable-hydrophilicity solvent (SHS) sample preparation. The SHS, which undergoes reversible phase changes triggered by pH change, enables selective extraction and easy phase separation. A flame atomic absorption spectroscopy was used in the final determination step. Optimization studies revealed, that the optimal pH of the sample solution (after digestion) during analytes extraction is 5.5. A l-proline is added to the sample (375 mM) to ensure the complexation of the target metal cations. After the complexation step, 750 µL of SHS - a N, N-Dimethylcyclohexylamine along with 0.9 mL of 2 M of acetic acid solution is added (hydrophilicity switch-on stage) and mixed manually to obtain a homogeneous solution. In the last stage, 0.45 mL of 10 M NaOH solution (hydrophilicity switch-off stage) is added to the sample solution and a vortex for 100 s is applied to ensure the effective extraction and separation of the complex containing the analytes. At this stage, a cloudy solution is immediately obtained. Finally, the effective phase separation is obtained at the centrifugation step (4000 rpm for 2 mins). The method limit of detection was as 0.03, 0.009, 0.6, and 0.2 ng/L for Zn (II), Fe (II), Cd (II), and Pb (II) respectively with RSD% below 2.0 %. The analysis of certified reference materials and real samples proved the full applicability of the method for routine analysis, contributing to the field of heavy metal analysis and ensuring the safety of baby products. According to the AGREE methodology, this method can be named as green analytical chemistry method with a score of 0.77.