Optimization and validation of high throughput methods for the determination of 132 organic contaminants in green and roasted coffee using GC-QqQ-MS/MS and LC-QqQ-MS/MS.

Recently some major safety concerns have been raised on organic contaminants in widely consumed plants such as coffee. Hence, this study aimed to develop specifically optimized methods for determining organic contaminants, such as pesticides and polychlorinated biphenyls (PCBs), in coffee using GC-MS/MS and LC-MS/MS. QuEChERS method was used as a base extraction method, and 27 experiments were studied using design of experiments with categorical variables (extraction buffers, cleanup sorbents, and coffee roasting degree) to find the optimum method for each matrix type. The optimum method for green coffee was acetate buffer and chitosan for clean-up, while no-buffer extraction and the PSA + C18 method were ideal for light and dark-roasted coffee. The optimized methods were validated in accordance with SANTE/11312/2021. Furthermore, ten real samples (4 green, and 6 roasted) from the markets were analysed; ortho-phenylphenol was found in all the roasted coffee samples, and carbendazim was found in one green coffee sample.

Irradiated and radioactively contaminated foods: Analysis of EU RASFF notifications from 1997 to 2022.

Food irradiation technique is an authorized tool used on a commercial scale in many countries to preserve different types of foodstuffs from deterioration caused by microorganisms, insects, and metabolic activity to prolong their shelf life without leaving any residual effect on processed foods, unlike preservatives and pesticides. This study was carried out to analyse the EU Rapid Alert System for Food and Feed (RASFF) notifications on food radiation from 1997 to 2022 in order to identify the most frequently reported products, their origin countries and associated reasons for notification, as well as the most notifying countries, product categories, notification classification, risk decisions, and actions taken. A total of 488 notifications were recorded during this time period. China was the most frequently notified origin country, accounting for 19.88% of all notifications, followed by the United States (11.68%), Russia (7.99%), Vietnam (7.17%), and Poland (5.53%). The top notified product categories were "dietetic foods, food supplements, and fortified foods" (37.09%), followed by fruits and vegetables (23.16%), herbs and spices (8.81%), and prepared dishes and snacks (5.53%). The top 5 notified products were food supplements (25.00%), mushrooms (20.70%), noodles (7.58%), tea (4.51%), and spices (3.69%). The four main reasons for food radiation notifications were unauthorized irradiation (57.58%), too high levels of radioactivity (22.34%), unlabeled irradiation (19.47%), and unauthorized facilities (14.96%). Too many notifications included more than one reason for the notification. Out of 109 notifications related to too-high levels of radioactivity (up to 10755 Bq/kg), 101 were due to the presence of 137Cs, 134Cs, 60Co, and 48Cd in mushrooms, mainly originating from Poland (25), Bulgaria (24), Ukraine (15), and Belarus (12). Such studies provide the necessary data to ensure food safety and encourage countries to implement comprehensive procedures to protect consumers health.

Comparative study between the top six heavy metals involved in the EU RASFF notifications over the last 23 years.

From the Rapid Alert System for Food and Feed (RASFF) database, a total of 4728 notifications regarding the six most frequently notified heavy metals (i.e., arsenic, cadmium, lead, mercury, chromium, and nickel) were tracked from January 1, 2000, to December 31, 2022, and analyzed based on year, notification classification, notifying countries, countries of origin, product types, product categories, risk decision, and action taken. Human risk assessment owing to consumption of mercury- and cadmium-contaminated seafood was estimated as well. Results revealed that the highest numbers of notifications were on mercury (36.6%), cadmium (25.1%), and lead (14.1%). Interestingly, the number of total notifications was at its peak between 2011 and 2014; from 2015 onward, it started to decrease considerably. Alert, border rejection, and information notifications represented 29.6%, 21.9%, and 48.5% of the total notifications, respectively. Chromium and nickel resulted in 33.8% and 23.3% of border rejection notifications, respectively. About 52.0% of the alert notifications were on mercury. Serious notifications represented 34.9% of the total notifications. Mercury and cadmium notifications accounted for 54.9% and 25.8% of serious notifications, respectively. Italy was the most notifying country, recording the highest number of notifications on cadmium (29.0%), mercury (52.6%), chromium (81.0%), and nickel (78.7%). China was the most notified origin country with regards to arsenic (18.7%), cadmium (12.8%), lead (27.6%), chromium (71.2%), and nickel (66.9%) notifications. Notifications on food, food contact materials (FCM), and feed represented 71.9%, 23.4%, and 4.7%, respectively, of the total notifications. About 91.5% of mercury notifications were on fish and fish products; 24.3% of arsenic notifications related to fruits and vegetables; and 20.1% of cadmium notifications corresponded to cephalopods and products thereof. Notified products were largely withdrawn from the markets according to arsenic (20.3%), lead (17.9%), and mercury (18.0%) notifications and re-dispatched because of cadmium (20.5%), chromium (42.1%), and nickel (49.5%) notifications. The target hazard quotient (THQ) values for mercury in swordfish, sharks, and tuna and cadmium in squid were all also below the threshold value of 1, implying that there is no significant risk for consumers. Overall, media coverage of RASFF alerts and actions may raise awareness of heavy metal contamination among the general public and industry professionals. The primary dietary advice of our study is to stay away from species with high mercury contents. Also, identifying the most dangerous heavy metals (HMs) and the most polluting products can help researchers prioritize their efforts in finding sustainable solutions for them.

Remediation of pesticides contaminated water using biowastes-derived carbon rich biochar.

The competition impact and feedstock type on the removal of water pesticides using biochar have not yet been sufficiently investigated. Therefore, here we investigated the potentiality of three different biochars (BCs) derived from rice husk (RHB), date pit (DPB), and sugarcane bagasse (SBB) biowastes for the simultaneous removal of ten pesticides from water in a competitive adsorption system. The BCs structural characterization and morphology were investigated by XRD, FTIR spectroscopy and SEM analysis. The potential adsorption mechanisms have been investigated using various isothermal and kinetic models. RHB showed the highest removal percentages (61% for atrazine/dimethoate and 97.6% for diuron/chlorfenvinphos) followed by DPB (56% for atrazine/dimethoate and 95.4% for diuron/chlorpyrifos) and then SBB (60.8% for atrazine/dimethoate and 90.8% for chlorpyrifos/malathion). The higher adsorption capacity of RHB and DPB than SBB can be due to their high total pore volume and specific surface area (SSA). Langmuir model described well the sorption data (R2 = 0.99). Adsorption equilibrium was achieved after 60 min for RHB, and 120 min for both DPB and SBB. The optimum adsorbent dose (g/L) was 10 for RHB and 4 for DPB and SBB. The removal efficiency of pesticides was enhanced by decreasing pH from 9 to 5 by RHB and to 3 by DPB and SBB. XRD and FTIR spectroscopy confirmed that BCs contain some active adsorption groups and metal oxides such as MgO, SiO, Al2O3, CaO, and TiO2 that can play an effective role in the pesticides sorption. BET-N2 adsorption analysis demonstrated that the BC pore size contributes significantly to pesticide adsorption. These findings indicate that RHB, DPB, and SBB have ability for adsorption of water pesticides even under acidic conditions. Therefore, the rice husk, date pit, and sugarcane bagasse biowastes could be pyrolyzed and reused as effective and low-cost sorbents for elimination of hazardous substances such as pesticides in the aqueous environments.

Improved analysis of folpet and captan in foods using liquid chromatography-triple quadrupole linear ion trap mass spectrometry: applying mass filtering, collision, and trapping conditions.

Accurate and highly sensitive analysis of folpet and captan was accomplished using liquid chromatography-triple quadrupole linear ion trap mass spectrometry (LC-QqQIT) with selective ion mode; mass filtering, collision, and trapping condition. Dimensional mass spectrometry (MS3) parameters were optimized for the residue detection of folpet and captan in six food commodities (apples, tomatoes, sweet pepper, wheat flour, sesame seeds, and fennel seeds). The sample preparation method was based on the known QuEChERS protocol, except a mixture of acetonitrile/acetone was used for the sample extraction from the sesame seeds. The robustness and reliability of the developed MS3 method were demonstrated by performing a full validation, according to SANTE/11312/2021, at 0.01-0.25 mg/kg. Recovery ranged from 83 to 118% with a relative standard deviation below 19% in all the tested commodities, and limits of quantifications (LOQs) were 0.01 mg/kg in apples and tomatoes; 0.03 mg/kg in sweet pepper; and 0.05 mg/kg in wheat flour, sesame seeds, and fennel seeds. Monitoring results showed that about 90% of apples contained captan residue, and in sweet pepper, concentrations of captan and folpet as high as 1.57 and 0.97 mg/kg were found, respectively. The novel developed MS3 method enabled more reliable identification of these commonly problematic fungicides at lower LOQs than previously reported methods.

Occurrence and ecotoxicological risk assessment of pesticides in sediments of the Rosetta branch, Nile River, Egypt.

This study aimed to (1) monitor the occurrence and spatiotemporal variations of 100 pesticides in sediments collected monthly from July 2018 to June 2019 from sampling sites in El-Rahawy, Sabal, and Tala, along the Rosetta branch of the Nile River, Egypt, and (2) perform an ecological risk assessment for aquatic organisms upon exposure to the detected sediment pesticides based on the risk quotient (RQ) method. Out of the 100 pesticides monitored, 16 pesticides belonging to seven chemical families were detected, and 55% of the sediment samples were contaminated with one or more pesticide residues. The mean concentration (mg/kg dry weight (dw)) and detection frequency (%) of the four most frequently detected pesticides in the sediment samples were as follows: chlorpyrifos (0.18 mg/kg dw and 34%), p,p'-DDE (0.018 mg/kg dw and 30%), cypermethrin (0.03 mg/kg dw and 14%), and deltamethrin (0.026 mg/kg dw and 13%). The spatial distribution exhibited that El-Rahawy had the highest pesticide load (2.86 mg/kg dw) among the studied sites, whereas the temporal variations revealed that the highest total pesticide concentrations were detected in winter season (1.73 mg/kg dw). Meanwhile, 12 pesticides showed high RQs (>1), posing a potential ecological risk to aquatic species that live and feed on such sediments.

Size-exclusion chromatography selective cleanup of aflatoxins in oilseeds followed by HPLC determination to assess the potential health risk.

Aflatoxins (AFs) are one of the most harmful carcinogenic natural toxins that affect food. Crops containing reasonably high oil content may be affected by Aspergillus species and consequently by AF contamination. In this study, a proposed testing method for AF detection in oilseed was developed, validated, and used for a market survey to assess the probabilistic risk exposure caused by consuming contaminated oilseeds including corn, sunflower seed, and soybean. The test method was optimized for selective extraction and then validated for fitness of purpose; the limits of quantification (LOQs) were 0.2, 0.4, 0.2, and 0.2 µg kg-1 for aflatoxin G1 (AFG1), aflatoxin B1 (AFB1), aflatoxin G2 (AFG2), and aflatoxin B2 (AFB2), respectively. The method was linear from the LOQs up to 20 µg kg-1, and its budget of measurement uncertainties were estimated at 25, 24, 26, and 30 for AFG1, AFB1, AFG2, and AFB2, respectively. The contamination levels were from  10,000 body weight (BW) day-1, respectively. The main finding of the present study highlights the possibility of some risk of AF exposure from corn consumption, which may represent a health concern.

Occurrence, human health, and ecotoxicological risk assessment of pesticides in surface waters of the River Nile's Rosetta Branch, Egypt.

In Egypt, the shortage of freshwater resources and their pollution constitutes a growing concern. Therefore, the objectives of this study were to (i) monitor the occurrence and spatiotemporal variations of 100 pesticides in surface water samples collected monthly (from July 2018 to June 2019) from El-Rahawy, Sabal, and Tala sampling sites along the Rosetta branch of the River Nile in Egypt, (ii) identify potential non-carcinogenic health risks for the local people through the lifetime consumption of contaminated drinking water, and (iii) perform an ecological risk assessment of aquatic organisms upon exposure to pesticides detected in surface waters based on the risk quotients (RQs) method. Of the 100 pesticides analyzed, 22 belonging to 11 chemical families were detected, and 75.5% of surface water samples were contaminated with one or more pesticide residues. The most frequently detected pesticide was malathion (57%), followed by chlorpyrifos (54%), atrazine (23%), and carbendazim (20%). Spatial distribution showed that the El-Rahawy site had the highest pesticide load (38.47 µg/L), and Sabal had the lowest (16.29 µg/L). Temporal variations revealed that the highest total pesticide concentrations were detected in summer (27.98 µg/L) compared to spring (23.16 µg/L), winter (19.18 µg/L), and autumn (11.85 µg/L). For non-carcinogenic risks of pesticides detected in surface water, the target hazard quotient (THQ) values were less than one. This implies that there is no potential human risk from exposure to drinking water at the sites under study. However, 13 pesticides presented high-risk quotients (RQ > 1), posing potential ecological risks to aquatic organisms.

Occurrence and human health risks of pesticides and antibiotics in Nile tilapia along the Rosetta Nile branch, Egypt.

Nile tilapia (Oreochromis niloticus) samples were collected at monthly intervals between July 2018 and June 2019 from 3 sampling sites (El-Rahawy, Sabal and Tala) situated along the Rosetta branch of the Nile, Egypt, to monitor the presence of 100 pesticides and 5 antibiotics using different extraction procedures followed by GC-MS/MS and LC-MS/MS. Potential human health risks via the consumption of contaminated fish was also assessed. Of the 72 analyzed fish muscle samples; 86% and 21% were contaminated with pesticides and antibiotics, respectively. Chlorpyrifos (ranging from < LOQ to 0.08 mg/kg) was the most frequently detected pesticide followed by p,p'-DDE (ranging from < LOQ to 0.04 mg/kg) in 83 and 45% of the fish muscle samples, respectively. Nitrofurazone (ranging from 8.6 to 52 µg/kg) was the most frequently detected antibiotic, followed by nitrofurantoin (ranging from 1.1 to 2 µg/kg) and chloramphenicol (ranging from < LOQ to 0.17 µg/kg). These antibiotics were found in 12, 6 and 5% of the fish muscle samples, respectively. The spatial distribution of the detected pesticides and antibiotics in fish samples along the Rosetta branch showed that the highest mean concentrations were found in the Sabal area, followed by samples from Tala and El-Rahawy. An investigation into seasonal variations revealed that the highest mean concentrations of pesticides and antibiotics in fish samples were detected in winter and spring, respectively. According to target hazard quotient (THQ) calculations for the detected pollutants in Nile tilapia muscle, all pollutants gave THQ values lower than 1, indicating that the consumption of this fish from the study sites is unlikely to cause any detrimental effects to consumers.

Metal Ion Removal from Wastewaters by Sorption on Activated Carbon, Cement Kiln Dust, and Sawdust.

This study assessed the efficiency of activated carbon, cement kiln dust (CKD), and sawdust for the removal of cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) from aqueous solutions under mono-metal and competitive sorption systems and the removal of Cd, Cu, and Zn from different industrial wastewaters. Batch equilibrium experiments were conducted in a mono-metal and competitive sorption system. The efficiency of the sorbents in the removal of Cd, Cu, and Zn from industrial wastewaters was also investigated. Cement kiln dust expressed the highest affinity for the metals followed by activated carbon and sawdust. Competition among the metals changed their distribution coefficient (Kd) with the sorbents. Sorption of Pb and Cu was higher than Cd and Zn. The average metal removal from the wastewaters varied from 74, 61, and 60% for Cd, Cu, and Zn, respectively, to nearly 100%. The efficiencies of CKD and activated carbon in removing metals were higher than sawdust, suggesting their potential as low-cost sorbents for the removal of toxic metals from wastewaters.

Histopathology and cytotoxicity as biomarkers in treated rats with cadmium and some therapeutic agents.

The present study aimed to investigate the protective role of ascorbic acid (vitamin C) and zinc (Zn) against cadmium (Cd) induced histopathological changes in tissues of liver, kidney, lung and testis of rats as well as chromosomal aberrations. For this purpose, 60 male albino rats were divided into six groups; each group contained 10 animals. The first group served as control and was given only distilled water. The second and third groups received distilled water supplemented with 2 g ascorbic acid/l and 500 mg Zn/l, respectively. The fourth group received a daily oral dose containing 3 mg Cd/kg b.w. (1/30 LD50). The fifth group received Cd + ascorbic acid (3 mg Cd/kg b.w. + 2 g ascorbic acid/l), while the sixth group received Cd + Zn (3 mg Cd/kg b.w. +500 mg Zn/l). The treatment in all groups lasted for 90 consecutive days. Rats exposed to cadmium showed severe histopathological changes in the liver, kidney, lung and testicular tissues as well as chromosomal aberrations such as: break, ring, centromeric separation and polyploidy. Co-treatment with zinc partially improved the histopathological changes and chromosomal aberrations while co-treatment with vitamin C exhibited a more protective role and markedly reduced tissues damage induced by Cd.

Heavy metals removal from aqueous solutions and wastewaters by using various byproducts.

Water contamination with heavy metals (HM) represents a potential threat to humans, animals and plants, and thus removal of these metals from contaminated waters has received increasing attention. The present study aimed to assess the efficiency of some low cost sorbents i.e., chitosan (CH), egg shell (ES), humate potassium (HK), and sugar beet factory lime (SBFL) for removal of cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from wastewaters. For this purpose batch equilibrium experiments were conducted with aqueous solutions containing various concentrations of the metals and sorbents in a mono-metal and competitive sorption system. Sorption isotherms were developed, and sorption parameters were determined. The potential applicability of the tested sorbents in the removal of Cd, Cu, and Zn from contaminated wastewaters was also investigated by equilibrating different sorbents and water ratios. Chitosan expressed the highest affinity for the metals followed by SBFL, ES, and HK. Nearly 100% of the metals were removed from aqueous solutions with the lowest initial metal concentrations by the sorbents especially CH and SBFL. However, the sorption efficiency decreased as the initial metal concentrations increased. Competition among the four metals changed significantly their distribution coefficient (Kd) values with the sorbents. The selectivity sequence of the metals was: Pb > Cu > Zn > Cd. The metal removal from the wastewaters varied from 72, 69, and 60 to nearly 100% for Cd, Cu and Zn, respectively. The efficiency of the studied byproducts in removing metals from the wastewaters differed based on the source of contamination and metal concentrations. Cadmium removal percentages by HK and CH were higher than SBFL and ES. The HK and CH exhibited the highest removal percentage of Cu from water with high concentrations. The SBFL and ES revealed the highest removal percentage of Zn from water with high concentrations. The results, demonstrate a high potential of CH, SBFL, HK, and ES for the remediation of HM contaminated wastewaters.

Simultaneous ozone fumigation and fluoranthene sprayed as mists negatively affected cherry tomato (Lycopersicon esculentum Mill).

Ozone (O(3)) fumigated at 120 microg L(-1) for 12 hd(-1) was combined with 10 microM fluoranthene, and other treatments, including Mannitol solution to investigate the interaction of the two pollutants on tomato plant (Lycopersicon esculentum Mill). Using ten treatments including Mannitol solution and a control, exposure experiment was conducted for 34 d inside six growth chambers used for monitoring the resulted ecophysiological changes. Visible foliar injury, chlorophyll a fluorescence, leaf pigment contents, CO(2) uptake and water vapor exchange were monitored in tomato. Ozone or fluoranthene independently affected some ecophysiological traits of the tomato. In addition, simultaneous treatments with the duo had increased (additive) negative effects on the photosynthesis rate (A(max)), stomatal conductance (g(s)), chlorophyll pigment contents (Chl a, Chl b and Chl((a+b))) and visible foliar symptoms. Contrarily, alleviation of the negative effects of O(3) on the leaf chlorophyll a fluorescence variables by fluoranthene occurred. Mannitol solution, which functioned as a reactive oxygen species scavenger was able to mitigate some negative effects of the two pollutants on the tomato plants.

Negative effects of fluoranthene on the ecophysiology of tomato plants (Lycopersicon esculentum Mill) Fluoranthene mists negatively affected tomato plants.

Cherry tomato plants (Lycopersicon esculentum Mill) were sprayed with fluoranthene and mixture of fluoranthene and mannitol solutions for 30d. The exposure was carried out in growth chambers in field conditions, and the air was filtered through charcoal filters to remove atmospheric contaminants. Plants were sprayed with 10microM fluoranthene as mist until they reached the fruiting stage, and the eco-physiological parameters were measured to determine the effects of the treatments. We measured CO(2) uptake and water vapour exchange, chlorophyll fluorescence, leaf pigment contents, visual symptoms and biomass allocation. Fluoranthene which was deposited as mist onto leaves negatively affected both growth and the quality of tomato plants, while other treatments did not. The photosynthetic rate measured at saturated irradiance was approximately 37% lower in fluoranthene-treated plants compared with the control group. Other variables, such as stomata conductance, the photochemical efficiency of PSII in the dark, Chl a, Chl b, and the total chlorophyll contents of the tomato leaves were significantly reduced in the fluoranthene-treated plants. Tomato plants treated with fluoranthene showed severe visible injury symptoms on the foliage during the exposure period. Mannitol (a reactive oxygen scavenger) mitigated effects of fluoranthene; thus, reactive oxygen species generated through fluoranthene may be responsible for the damaged tomato plants. It is possible for fluoranthene to decrease the aesthetic and hence the economic value of this valuable crop plant.