Occurrence, distribution, and risk assessment of pesticides in surface water and sediment in Jiangsu Province, China.

The occurrence and distribution of 157 pesticides were investigated in surface water and sediment in Jiangsu Province, China. Gas chromatography-mass spectrometry was used to analyze and quantify these pesticides, and the risk quotient method was used to evaluate their respective environmental risk. The results showed that 91 pesticides were detected in surface water. The organophosphates (OPPs), fungicides, and amide herbicides were predominant. The total concentration in surface water ranged from 63.7 to 22,463 ng/L, 3.90 to 7262 ng/L, and ND to 34,120 ng/L, respectively. The mean concentration was 3479 ng/L, 1644 ng/L, and 1878 ng/L, respectively. The concentration range of detected pesticides in the Yangtze River Basin was generally lower than that in the Huai River Basin. In sediment samples, a total of 63 pesticides were detected. OPPs and amide herbicides were also ranked highest; the total concentration in sediment samples ranged from 2951 to 47,739 ng/g and 106 to 12,996 ng/g, respectively. And the mean concentrations was 6971 ng/g and 5130 ng/g, respectively. Suqian City had the highest concentration for OPPs and amide herbicides in the Huai River Basin, followed by Huai'an City, while Nanjing City and Yangzhou City ranked highest in the Yangtze River Basin. The spatial distribution of pesticides in Jiangsu Province indicated a concentration significantly higher in the western and northern regions than in the eastern and southern regions, and a concentration generally higher in lakes than in rivers. The risk assessment results showed that OPPs, fungicides, amide herbicides, organochlorines, and triazine herbicides in most surface water samples posed a high risk and had regional pollution characteristics. In sediment samples, organochlorines, carbamates, other herbicides, and other insecticides posed a high risk in northern Jiangsu Province, whereas OPPs, amide herbicides, and triazine herbicides posed high risks everywhere in Jiangsu Province.

Melamine in Iranian foodstuffs: A systematic review, meta-analysis, and health risk assessment of infant formula.

The presence of melamine in food is one of the most significant threats to consumer health and food safety now confronting the communities. The goal of this systematic review and meta-analysis was to determine the melamine content of different food products available on the Iranian market. The pooled melamine concentration (95% confidence interval) on 484 samples of animal-based foodstuffs was as follows: 0.22 (0.08, 0.36 mg kg-1) for milk, 0.39 (0.25, 0.53 mg kg-1) for coffee mate, 1.45 (1.36, 1.54 mg kg-1) for dairy cream, 0.90 (0.50, 1.29 mg kg-1) for yoghurt, 1.25 (1.20, 1.29 mg kg-1) for cheese, 0.81 (-0.16, 1.78 mg kg-1) for hen eggs, 1.28 (1.25, 1.31 mg kg-1) for poultry meat, 0.58 (0.35, 0.80 mg kg-1) for chocolates, and 0.98 (0.18, 1.78 mg kg-1) for infant formula. Based on the results of health risk assessment study on toddlers under 2 years old who ingested infant formula (as a melamine-sensitive group), all groups of toddlers are at an acceptable level of non-carcinogenic risk (THQ ≤ 1). Toddlers were classified according to their ILCR (carcinogenic risk) levels due to infant formula consumption as follows: under 6 months (0.0000056), 6-12 months (0.0000077), 12-18 months (0.0000102), and 18-24 months (0.0000117). The melamine carcinogenicity in infant formula for children had an ILCR value of 0.000001-0.0001 in the investigation, which was considerable risk. According to the findings, Iranian food products (notably infant formula) should be analyzed for melamine contamination on a regular basis.

Occurrence, fate, seasonal variability, and risk assessment of twelve triazine herbicides and eight related derivatives in source, treated, and tap water of Wuhan, Central China.

Triazine herbicides have been widely used, are frequently detected in aqueous environments and soils, and can cause acute or chronic toxicity to living organisms. We collected source water samples (n = 20) originating from the Hanshui River and the Yangtze River of Wuhan section, treated water samples (n = 20), and tap water samples (n = 169) in Wuhan, Central China during 2019 for determination of twelve triazine herbicides and their eight derivatives (collectively defined as TZs) and characterizing their fate during water treatment. Eighteen of the twenty TZs were detected in the source water. Atrazine (ATZ) had the highest concentrations (median: 22.4 ng/L) in the source water samples while DACT had the highest concentrations (median: 31.4 ng/L) in the treated water. "Tryns" (ametryn, prometryn, simetryn, terbutryn) were efficiently removed by conventional water treatment, while other target analytes were not; interestingly, hydroxypropazine and prometon increased significantly accompanied by prometryn disappearance, which implicated potential transformation pathways. In addition, "tryns" might be transformed into "tons" (atraton, prometon, secbumeton, terbumeton) by ozonation. In the tap water samples, diaminochlorotriazine had the highest concentrations (median: 34.9 ng/L) among the target analytes, followed by ATZ (18.3 ng/L), hydroxyatrazine (5.17 ng/L), deethylatrazine (5.00 ng/L), hydroxypropazine (3.20 ng/L), deisopropylatrazine (2.05 ng/L), hydroxydesethylatrazine (1.68 ng/L), and others. The TZs had the highest cumulative concentration in July in the tap water samples (median: 89.7 ng/L). This study found that ozonation in combination with activated carbon was more efficient in removing triazine herbicides, although "tryns" could also be transformed during conventional treatment. Ecological risk assessment showed moderate risks posed by hydroxyterbuthylazine, prometryn, and simetryn; the Hanshui River had higher risks than the Yangtze River, and July had higher risks than February. Human exposure to the TZs via water ingestion was low compared to the reference doses. This study characterized the occurrence of some new emerging TZs in the source water, their fate during drinking water treatment, and their seasonal variability in the tap water.

Assessment of the bioaccessibility of PAHs and other hazardous compounds present in recycled tire rubber employed in synthetic football fields.

Recycled tire crumb rubber (RTCR) surfaces contain harmful and carcinogenic substances, which can be ingested by the users of these facilities, mainly athletes and children. In this work, the potential in-vitro oral bioaccessibility of eighteen polycyclic aromatic hydrocarbons (PAHs) from RTCR employed as infill in synthetic football fields was studied in human synthetic body fluids (saliva, gastric, duodenal and bile), prepared according the Unified Bioaccessibility Method. Solid-phase extraction (SPE) using commercial sorbents and a new green material based on cork (cork industry by-product) were used to isolate the bioaccessible PAHs before gas chromatography-tandem mass spectrometry analysis. The method was optimized and validated attending the analytical figures of merit. The feasibility of cork biosorbent for the extraction of the compounds was demonstrated, as well as the suitability of the UBM method to perform the digestion with good precision. The application to real samples collected from football fields demonstrated the presence of 17 of the 18 target PAHs in the biofluids. Most volatile PAHs such as NAP, ACY, ACE, FLU, PHN and ANC, achieved the highest bioaccessibility percentage levels. The carcinogenic B[a]P was detected in 75 % of the samples at concentrations up to 2.5 ng g-1 (bioaccessible fraction). Children exposure assessment was carried out to identify potential risk. Other hazardous and environmentally problematic compounds such as N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-quinone), recently related with the dead of coho salmon, and hexamethoxymethylmelamine (HMMM), among others, were also detected. This is the first study in which the bioaccesibility from real crumb rubber samples of 15 out of the 16 PAHs considered as priority pollutants by the United States Environmental Protection Agency (EPA) and the presence of 6PPD-quinone and HMMM in the bioaccessible fractions is reported.

Exposure to melamine and its derivatives in Chinese adults: The cumulative risk assessment and the effect on routine blood parameters.

Melamine (MEL) and its derivatives, ammeline (AMN), ammelide (AMD), cyanuric acid (CYA) are widely existed in environmental media. Animal studies have reported the cumulative risk assessment (CRA) of simultaneous exposure to MEL and its derivatives and explored the associations between exposure and routine blood parameters. Such information is largely unknown in human studies. In this study, we detected the urinary concentrations of MEL and its derivatives in 239 Chinese adults to conduct the CRA by evaluating their hazard quotients (HQ) and hazard Index (HI), and also explored the possible associations between exposure and measured routine blood parameters in study population. The detectable frequencies of MEL, AMN, AMD and CYA were 96.65%, 41.00%, 97.91% and 97.07%, respectively. The median values of creatinine (Cr)-adjusted MEL, AMN, AMD, CYA and the total concentrations of MEL and its derivatives (∑MEL) were 11.41 µg/g Cr, not detected (ND), 2.64 µg/g Cr, 15.30 µg/g Cr, 35.02 µg/g Cr, respectively. There were 9 (3.77%) participants with estimated daily intakes (EDIs) of CYA exceeding the tolerable daily intake (TDI) of 2500 ng/kg bw/day, and 12 (5.02%) participants with HI of ∑MEL exposure exceeding 1 based on the strictest TDI value. Urinary concentrations of MEL and its derivatives were positively associated with specific routine blood parameters, including hematocrit, hemoglobin, mean corpuscular volume, mean corpuscular hemoglobin concentration, mean corpuscular hemoglobin, white blood cell, neutrophil count (P < 0.05). Meanwhile, exposure to MEL and its derivatives increased the risk of red blood cell abnormality (P < 0.05). Our study is the first study to provide evidence-based data on the CRA of exposure to MEL and its derivatives in Chinese adults, and to propose a possible association between such exposure and routine blood parameters in human.

A low-cost and effective bagasse-based magnetic porous biochar as an adsorbent for solid phase extraction of triazine herbicides in brown sugar.

A rapid and sensitive approach for enriching and extracting triazines from brown sugar samples was developed by combining magnetic dispersive solid-phase extraction and HPLC/UV. In this work, a magnetic porous biochar (MPB) derived from low-cost bagasse was prepared and successfully employed as an adsorbent. A particular emphasis was placed on optimizing the extraction conditions, including the amount of MPB, extraction time, pH, type and volume of eluent, and salt concentration. Under optimized MSPE conditions, the method showed satisfactory linearity over concentration ranges of 2-200 µg L-1 for four triazines, with correlation coefficient values no less than 0.9981. Low limits of detection (0.27-0.33 µg L-1), good recoveries (81.7-100.7%), and satisfactory repeatability (RSDs ≤ 8.1%) were also demonstrated with respect to the analytical performance. The results demonstrated that the developed method was simple, rapid, sensitive, and efficient, indicating that it could extract and enrich trace triazines from real samples.

Ecological risk assessment of booster biocides in sediments of the Brazilian coastal areas.

Although booster biocides (Irgarol, diuron, chlorothalonil, dichlofluanid, and DCOIT) have been detected in sediments along the Brazilian coastal areas, the risk associated to their occurrence and levels is still unknown. Thus, the ecological risk of booster biocides to sediment-dwelling organisms from the Brazilian coast was assessed using a risk characterization approach through the Risk Quotient (Measured environmental concentration (MEC)/Predicted no effect concentrations (PNECs)). Sedimentary PNECs for Irgarol, diuron, chlorothalonil and DCOIT were derived based on published ecotoxicological data from both freshwater and marine studies, while a NORMAN methodology was used to derived it for dichlofluanid. Results showed that DCOIT, diuron, Irgarol, chlorothalonil, and dichlofluanid can pose high risk on 47%, 35%, 15%, 1% and 1%, respectively, of the 113 Brazilian sites appraised. Considering the trend of expansion of navigation/maritime activities, DCOIT may worsen its impact over the coastal areas of Brazil, especially ports, but also ship/boatyards, marinas, and maritime traffic zones. The present study is an important contribution to support advance on policy formulation concerning booster biocides worldwide, particularly considering the lack of regulation on the use of antifouling biocides in Brazil.

Highly-selective complex matrices removal via a modified QuEChERS for determination of triazine herbicide residues and risk assessment in bivalves.

A modified quick, easy, cheap, effective, rugged, and safe (QuEChERs) method for determining triazine herbicide residues in bivalves (Mussels, Scallops, Cockles) was developed. The use of molecularly imprinted polymers (MIPs) as a selective purification material during dispersive-solid phase extraction (d-SPE) increased the removal rate of pigments interference. With 4% acidic acetonitrile as the organic modifier, the modified QuEChERs method achieved good extraction rate of herbicide residues. The satisfactory recoveries (80%-118%) and RSDs (1.0%-11.6%) of herbicide residues were obtained at three spiked levels. The limits of quantification of herbicide residues ranged from 0.10 µg/kg to 1.59 µg/kg. Further, the herbicide residues in bivalves collected in the eastern coasts of China was analyzed. The developed QuEChERs procedure coupled with GC-MS/MS was successfully applied to the herbicide residues detection in bivalves, and due to the extensive use of herbicides and the large consumption of bivalves in globally, the ongoing risk evaluation is needed.

Evaluation of cyromazine transferred from feed to chicken products and subsequent assessment of dietary risks to Chinese consumers.

In this work, levels of cyromazine and its metabolite melamine in chicken products and its transfer factors (TFs) and dietary risks assessment for Chinese consumers are presented. Cyromazine was added to chicken feed at doses of 5, 25, and 50 mg/kg for 42 days. Cyromazine residues were found in frequently consumed chicken products (meat, heart, liver, gizzard, and eggs), with liver and eggs displaying the highest concentrations (0.935 and 1.281 mg/kg, respectively). Low levels of melamine residues (<0.029 mg/kg) were detected in chicken products from chickens treated with 25 and 50 mg/kg cyromazine, but not in eggs from chickens treated with 5 mg/kg cyromazine. The TFs for the investigated chicken products varied from 0.0074 to 0.0229 across the dosage levels. The chronic exposure assessment showed that 0.001 to 0.190% of the acceptable daily intake (0.06 mg/kg body weight [b.w.]/day) of cyromazine was consumed through chicken products among the various age and gender groups of Chinese consumers. The acute exposure assessments of different age and gender groups were 0.0004% to 0.178% of the acute reference dose (0.1 mg/kg b.w.). Although the results suggest that the risk associated with cyromazine residues in chicken products was low in China, the possible risk associated with cyromazine residues in chicken products should not be ignored while cyromazine remains a legal feed additive. PRACTICAL APPLICATION: The present analytical method could be used for cyromazine and melamine detection in different chicken products, and dietary risk assessments of cyromazine provided a support for the work of regulatory bodies to conduct surveillance programs regarding food safety evaluation of cyromazine.

Assessment of Groundwater Contamination by Terbuthylazine Using Vadose Zone Numerical Models. Case Study of Valencia Province (Spain).

Terbuthylazine is commonly used as an herbicide to control weeds and prevent non-desirable grow of algae, fungi and bacteria in many agricultural applications. Despite its highly negative effects on human health, environmental modeling of this kind of pesticide in the vadose zone till reaching groundwater is still not being done on a regular basis. This work shows results obtained by two mathematical models (PESTAN and PRZM-GW) to explain terbuthylazine behavior in the non-saturated zone of a vertical soil column. One of the models use a one-dimensional analytical formulation to simulate the movement of terbuthylazine through the non-saturated soil to the phreatic surface. The second and more complex model uses a whole set of parameters to solve a modified version of the mass transport equation considering the combined effect of advection, dispersion and reactive transport processes. Both models have been applied as a case-study on a particular location in South Valencia Aquifer (Spain). A whole set of simulation scenarios have been designed to perform a parameter sensitivity analysis. Despite both models leading to terbuthylazine's concentration values, numerical simulations show that PRZM-GW is able to reproduce concentration observations leading to much more accurately results than those obtained using PESTAN.

A nationwide study of the occurrence and distribution of atrazine and its degradates in tap water and groundwater in China: Assessment of human exposure potential.

Despite frequent detection of atrazine (ATZ) and its degradates (including hydroxyatrazine, ATZ-OH; deethylatrazine, DEA; deisopropylatrazine, DIA; and deethyldeisopropylatrazine, DACT) in a variety of water bodies, documentation of their occurrence and distribution in tap water in China is still scarce. A nationwide survey about ATZ and its degradates (ATZs) in tap water from 31 provinces in 7 regions of mainland China and Hong Kong was conducted during June 2019. At least one of the analytes was found in all the water samples (n = 884). The median sum concentrations of ATZs (ΣATZs) was 21.0 ng/L (range: 0.02 ng/L-3.04 µg/L). The predominant compounds of ATZs in tap water were ATZ and DEA, with a detection frequency of 99.5% and 98.0%, respectively, followed by ATZ-OH (87.3%), DACT (84.0%), and DIA (78.1%). Significant regional variations (p < 0.05) were found in the concentrations of ATZs in tap water, and the highest concentration of ΣATZs (median: 254 ng/L, range: 0.44 ng/L-3.04 µg/L) was found in Northeastern China, followed by Eastern (37.2 ng/L, 0.02-706 ng/L), Northern (30.2 ng/L, 0.04-317 ng/L), Central (29.3 ng/L, 0.04-256 ng/L), Southern (25.0 ng/L, 0.04-297 ng/L), Southwestern (17.2 ng/L, 0.02-388 ng/L), and Northwestern China (3.22 ng/L, 0.06-214 ng/L). The level of ΣATZs in groundwater from rural area of China was about 1/3 of that found in tap water. ATZs cannot be removed by boiling tap water. The highest estimated daily intake of ΣATZs (248 ng/kg-body weight/day) was found in the infant population of Changchun, Jilin, Northeastern China.

A low-cost and high-efficiency carbazole-based porous organic polymer as a novel sorbent for solid-phase extraction of triazine herbicides in vegetables.

In this study, a porous organic polymer (denoted as Car-DMB) was fabricated by a simple one-step crosslinking polymerization of carbazole and p-dimethoxybenzene for the first time. Then the Car-DMB was served as adsorbent of solid phase extraction to enrich triazine herbicides from white gourd, tomato and soybean milk samples prior to their determination by high performance liquid chromatography. Under the optimal conditions, the response linearity was in the range of 0.3-100.0 ng g-1 for white gourds and tomato samples, and 0.5-100.0 ng mL-1 for soybean milk, with the coefficient of determination higher than 0.996. The detection limits were 0.1-0.2 ng g-1 for white gourd and tomato samples, and 0.15-0.3 ng mL-1 for soybean milk. The adsorption mechanism of the Car-DMB for the triazines was attributed to the strong H-bonding and weak π-π interactions. The efficient extraction for several other compounds demonstrated that Car-DMB holds great potential for diverse analysis applications.

Determination, residue analysis, risk assessment and processing factor of pymetrozine and its metabolites in Chinese kale under field conditions.

A simple determination method for pymetrozine and its metabolites in Chinese kale was developed using liquid chromatography with tandem mass spectrometry. The method had good linearity (R2 > 0.99), accuracy (recoveries of 73.2-94.1%) and precision (relative standard deviation of 2.5-9.8%). Field results showed that half-lives of pymetrozine were 3.0-4.1 d in Chinese kale, and terminal residue concentrations were all below the United States Environmental Protection Agency's maximum residue limit (250 µg/kg) at harvest. Owing to risk quotient <100%, pymetrozine is unlikely to give rise to vital health concerns to humans following the recommended application guidelines. Moreover, effects of home processing on pymetrozine residues in Chinese kale were monitored. The processing factor values of four processes were between 0.19 and 0.60, which indicated that the used processes could remove pymetrozine residues from Chinese kale, especially pickling after washing process. The data could provide guidance to safe and reasonable use of pymetrozine and help Chinese governments establish a maximum residue limit for pymetrozine in Chinese kale.

Pharmacokinetics Comparison, Intestinal Absorption and Acute Toxicity Assessment of a Novel Water-Soluble Astragaloside IV Derivative (Astragalosidic Acid, LS-102).

BACKGROUND AND OBJECTIVES: Astragaloside IV (AGS IV) is the most important bioactive constituent of Radix Astragali. However, its disappointing clinical application is mainly caused by its very low solubility in biologic fluids, resulting in poor bioavailability after oral administration. We recently obtained a novel water-soluble derivative of AGS IV (astragalosidic acid, LS-102) that displayed significant cardioprotective potential against hypoxia-induced injury. The objective of this study was to investigate the intestinal absorption, main pharmacokinetic parameters and acute toxicity of LS-102 in rodents compared with AGS IV. METHODS: An oral dose of LS-102 and AGS IV (20 mg/kg) was administered to Sprague-Dawley (SD) rats, and blood samples were collected at predetermined time points. The plasma concentrations were detected by a validated UHPLC-MS/MS method, and pharmacokinetic parameters were calculated using a compartmental model. In the intestinal permeability study, the transport of LS-102 across Caco-2 cell monolayers was investigated at six concentrations from 6.25 to 250 µM. Moreover, the acute toxicity of LS-102 (40-5000 mg/kg) via a single oral administration was investigated in BALB/c mice. RESULTS: LS-102 was rapidly absorbed, attaining a maximum concentration of 248.7 ± 22.0 ng/ml at 1.0 ± 0.5 h after oral administration. The relative bioavailability of LS-102 was twice that of AGS IV. LS-102 had a Papp (mean) of 15.72-25.50 × 10-6 cm/s, which was almost 500-fold higher than that of AGS IV, showing that LS-102 had better transepithelial permeability and could be better absorbed in the intestinal tract. The acute toxicity study showed no abnormal changes or mortality in mice treated with LS-102 even at the single high dose of 5000 mg/kg body weight. CONCLUSIONS: Oral LS-102 produced a pharmacokinetic profile different from AGS IV with higher bioavailability, while the toxic tolerance was similar to previous estimates. Thus, we speculated that LS-102 might provide better clinical efficacy and be a potential candidate for the new drug development of Radix Astragali.

Monitoring residue levels and dietary risk assessment of pymetrozine for Chinese consumption of cauliflower.

The present study investigates the occurrence of pymetrozine residues in cauliflower samples obtained from six cauliflower-producing areas of China during fixed time periods in 2017 and estimates the dietary risk of pymetrozine in cauliflower. A liquid chromatography with tandem mass spectrometry method was developed and validated to detect pymetrozine in cauliflower. The samples were extracted using 20 mL of acetonitrile and purified with dispersive solid-phase extraction using C18 as sorbent. The limit of quantification of pymetrozine was 0.008 mg/kg in cauliflower. The recoveries of the analyte were 82.04-95.18% with RSD <8.45%. The calibration curves for pymetrozine showed good linearities in the concentration range 0.004-2.0 mg/L with determination coefficients (R2 ) >0.999. Pymetrozine dissipated rapidly in cauliflower with a half-life of <4 days. The terminal residues of pymetrozine were <0.008-0.0881 mg/kg in cauliflower at 7, 10 and 14 days after spraying from six sites. The routine washing process removed about half amount of the pymetrozine in cauliflower; the reduction ratios were 51.0-52.8%. The dietary risk assessment indicated that pymetrozine did not exhibit obvious dietary health risks in cauliflower when good agricultural practices were implemented.

Ecotoxicological Assessment of Immersion Samples from Facade Render Containing Free or Encapsulated Biocides.

To protect house facades from fouling by microorganisms, biocides can be added to a render or paint before it is applied. During driving rain events, these biocides gradually leach out and have the potential to pollute soil or aquatic ecosystems. We studied the leaching behavior of biocides and toxicity of leachates from renders with either free or encapsulated biocides. Both render types contained equal amounts of terbutryn, 2-octyl-3(2H)-isothiazolinone (OIT), and 4,5-dichloro-2-n-octyl-4-isothiazolino-3-one (DCOIT). Nine leachate samples were generated over 9 immersion cycles according to a European standard, and biocides were quantified. The first and ninth leachate samples were tested using bioassays with algae, bacteria, and water fleas, the first sample was also tested with earthworms and springtails. Encapsulation reduced leaching of terbutryn, OIT, and DCOIT by 4-, 17-, and 27-fold. For aquatic organisms, the toxicity of water from render containing encapsulated biocides was always lower than that of render with free biocides. Furthermore, toxicity decreased by 4- to 5-fold over the 9 immersion cycles. Inhibition of photosynthesis was the most sensitive endpoint, followed by algal growth rate, bacterial bioluminescence, and water flea reproduction. Toxicity to algae was due to terbutryn and toxicity to bacteria was due to OIT. None of the samples affected soil organisms. Results demonstrate that combining standardized leaching tests with standardized bioassays is a promising approach to evaluate the ecotoxicity of biocides that leach from facade renders. Environ Toxicol Chem 2018;37:2246-2256. © 2018 SETAC.

Variance of Commercial Powdered Milks Analyzed by Proton Nuclear Magnetic Resonance and Impact on Detection of Adulterants.

Proton nuclear magnetic resonance spectra for 66 commercial powdered milk samples were analyzed by principal component analysis, soft independent modeling of class analogy, and pooled, crossed analysis of variance. It was found that the sample type (skim milk powder or non-fat dry milk), the supplier, the production site, the processing temperature (high, medium, or low temperature), and the day of analysis provided statistically significant sources of variation. Interestingly, inexact alignment (deviations of ±0.002 ppm) of the spectral reference peak was a significant source of variation, and fine alignment was necessary before the variation arising from the other experimental factors could be accurately evaluated. Using non-targeted analysis, the lowest detectable adulteration for dicyandiamide, melamine, and sucrose was 0.05%, the lowest detectable adulteration for maltodextrin and urea was 0.5%, the lowest detectable adulteration for ammonium sulfate and whey was 5%, and the lowest adulteration for soy protein isolate was undetectable using methods described herein. The measurement of variance and detection of adulteration were relatively unaffected by the resolution. Similar results were obtained with unbinned data (0.0003 ppm resolution) and binning of 333 data points (0.1 ppm resolution).

Liquid chromatography-mass spectrometry method for evaluating the dissipation dynamics of cyromazine and its metabolite in Agaricus bisporus and dietary risk assessment.

Providing guidance on the reasonable use of pesticide in agricultural production is of particular importance for ensuring food safety. In the present study, a field trial was performed to study the dissipation and accumulative pattern of cyromazine (CA) and its metabolite in Agaricus bisporus (A. bisporus) cultivation. An ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was first developed and validated for the determination of CA and melamine (MEL) in the casing soil and fruiting body. During the cultivation period, the dissipation rates of CA in the casing soil were between 51.57 and 63.48% at three dose groups. The fruiting body presented higher accumulation ability for MEL compared with CA. The terminal residues of MEL never exceeded the maximum residue limits (MRLs) in food. In addition, the intake health risk from the CA and MEL residues in the fruiting body were negligible to humans. This study will help to provide valuable guidance on the application strategies of CA in A. bisporus cultivation.

Polyamide/titania hollow nanofibers prepared by core-shell electrospinning as a microextractive phase in a fabricated sandwiched format microfluidic device.

In this study, a low-cost microfluidic device from polymethyl methacrylate was fabricated by laser engraving technique. The device is consisted of a central chip unit with an aligned microchannel. Both sides of the engraved microchannel were sandwiched by two synthesized sheets from polyamide/titania (PA/TiO2) hollow nanofibers as extractive phases. The inlet and outlet of the device were connected to the polyether ether ketone tubes, while a peristaltic pump was used to deliver both sample and desorbing solvent through the microchannel. The recorded scanning electron microscopy images from the surface of the synthesized PA/TiO2 nanofibers, exhibit a good degree of homogeneity and porosity throughout their structures. Also, the presence of titanium was indicated by the energy dispersive X-ray analysis, while the recorded Fourier transform infrared spectra confirmed their chemical structures. The addition of titania in the composition of polyamide nanofibers, not only improved the mechanical stability of the extractive phase but also enhanced its extraction capability. The major parameters associated with the extraction performance were studied and eventually the method was validated by the use of a gas chromatography-mass spectrometry. The limits of detection for the selected triazines were between 0.01 and 0.03ngmL-1, while the limits of quantification ranged from 0.04 to 0.1ngmL-1. In addition, the interday and intraday reproducibility (RSD%) were lower than 6.6% (n=3). The calibration graph for atrazine was linear in the range of 0.2-50ngmL-1 while two linear ranges for ametryn and terbutryn (0.1-10 and 20-500ngmL-1) were achieved. Relative recoveries were between 89 and 98% with the regression coefficient range of 0.9969-0.9991.

Risk assessment of selected priority pollutants coming from boating activities.

In this work, we evaluated the risk posed to aquatic organisms in the coastal waters of Albania and Apulia (Italy) by two priority pollutants (PPs), Irgarol 1051 and Diuron, used as biocides in antifouling paints on boat hulls. With this aim, we carried out an extensive 3-year monitoring in ports and marinas along the coasts of both countries, which showed a widespread occurrence of both PPs, with Irgarol 1051 concentrations usually being lower than the Diuron ones. The measured concentrations were compared with regulatory Environmental Quality Standards (EQS) (Directive 2008/105/EC) and used to perform a probabilistic Ecological Risk Assessment (ERA), for a thorough evaluation of the potential adverse effects upon marine ecosystem. Irgarol 1051 amounts above the Annual Average Concentration (AA-EQS, 2.5 ng/L) were often detected in Apulia and, less frequently, in Albania. Moreover, in Apulia, sometimes the Maximum Allowable Concentrations (MAC-EQS, 16 ng/L) was exceeded. In Apulia, where levels exceeded MAC/AA-EQS, ERA found not negligible probabilities of exceeding the toxicity level (6-18 %). A less critical situation was observed for Diuron whose levels were always below the MAC-EQS (1800 ng/L) in both countries and, in Albania, also below the AA-EQS (200 ng/L). On the other hand, in Apulia, this limit was exceeded in some locations. Correspondingly, ERA determined a not negligible risk in these sites (probability of exceedance 4-7 %).