Andrea Macaluso

Toxic Metals in Pelagic, Benthic and Demersal Fish Species from Mediterranean FAO Zone 37

Fish represents a nutrient-rich food but, at the same time, is one of the most important contributor to the dietary intake of heavy metals. The aim of this study was to assess residual levels of Pb, Cd and Hg in different species, caught from FAO zones 37 1.3 and 37 2.2, particularly small pelagic, benthic and demersal fishes. The results obtained showed the absence of toxic metal in fishes from FAO zone 37 1.3. Relating to FAO zone 37 2.2, instead, in all samples we observed the absence of Pb, small concentrations of Cd (0.081xa0±xa00.022xa0mg/kg) and higher Hg residual levels (0.252xa0±xa00.033xa0mg/kg). Particularly, the trend of Cd contamination was similar in all species whereas Hg showed high levels in demersal, intermediate in pelagic and low in benthic species. However, only Cd concentrations exceed the MRL in mackerel, mullet, sea-bream fishes, according to Regulation CE n. 629/2008 and n. 488/2014.

Aflatoxin M1 in raw, UHT milk and dairy products in Sicily (Italy)

A survey on 73 milk samples from different animal breeds and 24 dairy products samples from Sicily, Italy, was carried out for the presence of aflatoxin M1 (AFM1) by LC-fluorescence detection after immunoaffinity cleanup. AFM1 was detected in 48% and 42% of the milk and dairy samples at concentration ranges between <5.0–16.0 and <5.0–18.0 ng L−1, respectively. Within the raw milk samples, 92% had an AFM1 content below 5.0 ng L−1, in 7% of the cases it was in the range 5.0–10.0 ng L−1 and 1% was contaminated between 10.0 and 20.0 ng L−1. For the dairy products, ultra-high-temperature treated (UHT) milk, milk cream and cheese, the incidence was 42%, of which 83% contained less than 5.0 ng L−1 and 17% contained 10.0–20.0 ng L−1 AFM1. The levels of contamination found justify continuous monitoring for public health and to reduce consumer exposure.

Evaluation of mercury levels in pangasius and cod fillets traded in Sicily (Italy).

Predator fishes at the top of the aquatic food chain can accumulate large concentrations of metals and their consumption, consequently, makes a significant contribution, in particular, to mercury intake. The aim of this study was to determine mercury levels in fillets of two predatory species: pangasius (Pangasius hypophthalmus) from the Vietnam region of Megong and Chao Pharayai and cod (Gadus morhua) from the Baltic and North Sea, both being commercially important in the Italian market. A comparative analysis of these two imported fish species was carried out as a risk assessment for consumer safety. The results showed the presence of higher mercury levels in pangasius (0.41u2009±u20090.08u2009mgu2009kg−1) than in cod (0.11u2009±u20090.004u2009mgu2009kg−1) fillets. These data underline the importance of monitoring on imported fish before marketing, to evaluate better the risk of mercury exposure through fish and seafood consumption, and of selecting safer fishes for consumption by those groups more sensitive to the toxic effects of this metal.

Fatty acids determination in Bronte pistachios by gas chromatographic method

Abstract A gas chromatographic with flame ionization detector (GC-MS FID) method for the identification and quantification of fatty acids based on the extraction of lipids and derivatisation of free acids to form methyl esters was developed and validated. The proposed method was evaluated to a number of standard FAs, and Bronte pistachios samples were used for that purpose and to demonstrate the applicability of the proposed method. In this regard, repeatability, mean and standard deviation of the analytical procedure were calculated. The results obtained have demonstrated oleic acid as the main component of Bronte pistachios (72.2%) followed by linoleic acid (13.4%) and showed some differences in composition with respect to Tunisian, Turkish and Iranian pistachios.

Simultaneous Determination of As, Cu, Cr, Se, Sn, Cd, Sb and Pb Levels in Infant Formulas by ICP-MS after Microwave-Assisted Digestion: Method Validation

The growing importance of chemical measurements has greatly pressured the development of measures to improve the quality of analytical results and to guarantee quality to the end users. In this work an ICP-MS method was validated for the simultaneous determination of essential trace elements (Chromium, Selenium and Copper) and non-essential toxic elements (Cadmium, Antimony, Arsenic, Tin and Lead) in infant formula available in Sicily. The extraction of samples was performed by a microwave assisted digestion with HNO3 to stabilize these elements. Several parameters have been taken into account and evaluated for the validation of method: selectivity/specificity, trueness by recovery, repeatability and within-laboratory reproducibility at three levels of concentration, instrumental detection limit, limit of determination (LOD), limit of quantification (LOQ), range of linearity, standard measurement uncertainty. Results indicate that this method could be used in the laboratory for the routine determination of these 8 essential and non-essential elements in infant formulas with acceptable analytical performance.

Toxic metal levels in cocoa powder and chocolate by ICP-MS method after microwave-assisted digestion

The Commission Regulation (EC) Regulation N. 488/2014, established the concentration limits for cadmium in specific products based on cocoa and chocolate products as from January 2019. Based on this information there is a need to determine ultratrace levels of elements that might be presents in cocoa and chocolate products. In this work, the concentrations of Arsenic, Antimony, Cadmium, Chromium, Lead, Selenium and Vanadium were evaluated in cocoa powder and chocolate by the validation of an ICP-MS method. Good selectivity/specificity, recovery, repeatability and within-laboratory reproducibility, LOD, LOQ, range of linearity, standard measurement uncertainty parameters for method validation were achieved, in accordance with Commission Regulation. The cocoa powder revealed the maximum metal concentrations of 0.303u202f±u202f0.035u202fmg/kg for cadmium, 1.228u202f±u202f0.146u202fmg/kg for lead and 0.094u202f±u202f0.013u202fmg/kg for arsenic. A significant difference was found between cocoa powder and chocolate samples (pu202f<u202f.05).

Hair Mercury Levels Detection in Fishermen from Sicily (Italy) by ICP-MS Method after Microwave-Assisted Digestion

A number of ninety-six hair samples from Sicilian fishermen were examined for total mercury detection by an Inductively Coupled Plasma Mass Spectrometry (ICP-MS) method. The mercury levels obtained were compared with mercury levels of 96 hair samples from a control group, in order to assess potential exposure to heavy metals of Sicilian fishermen due to fish consumption and closeness to industrial activities. Furthermore, the mercury levels obtained from hair samples were sorted by sampling area in order to verify the possible risks linked to the different locations. The overall mean concentration in the hair of the population of fishermen was 6.45 ± 7.03u2009μgu2009g(-1), with a highest value in a fisherman of Sciacca (16.48u2009μgu2009g(-1)). Hair mercury concentration in fishermen group was significantly higher than in control group (p < 0.01). There was no significant difference in hair total mercury concentrations between sampling areas (p > 0.05). The results of this study indicate a greater risk of exposure to mercury in Sicilian fishermen, in comparison to the control population, due to the high consumption of fish and the close relationship with sources of exposure (ports, dumps, etc.).

Survey on the presence of non–dioxine‐like PCBs (NDL‐PCBs) in loggerhead turtles (Caretta caretta) stranded in south Mediterranean coasts (Sicily, Southern Italy)

A total of 71 loggerhead turtles (Caretta caretta) stranded along the coasts of Sicily (Southern Italy) were examined for non-dioxine like polychlorinated biphenyl (NDL-PCB) levels in muscle and adipose tissue by a gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS) method. The results revealed 6 high-indicator congener (∑6 PCBIND ) levels in 45% of the loggerhead turtles examined, with mean values of 980.39u2009±u20092508.39u2009ng/g wet weight in adipose tissue and 102.53u2009±u2009238.58u2009ng/g wet weight in muscle tissue. The hexachloro and heptachloro PCB congeners were the most abundant in both the sample types. The highest NDL-PCB levels were reached in an adipose tissue sample of a loggerhead turtle of 80u2009kg stranded along the coasts of Termini Imerese (14u2009183.85u2009ng/g wet wt). No significant correlation was found between modified Fultons K values of the loggerhead turtles and PCB contents (Su2009=u200947 151, pu2009>u20090.05). Furthermore, no significant differences were found between sexes (Wu2009=u2009365, pu2009> u20090.05). The PCB levels found in the present study were much higher than those found in the literature. The present study is the first report on the existence of NDL-PCBs in loggerhead turtles stranded in Sicilian coasts confirming C. caretta as a valuable indicator of contaminant exposure in the marine environment because of their specific biological and ecological characteristics. Environ Toxicol Chem 2017;36:2997-3002.

Aflatoxin M1 in cow, sheep, and donkey milk produced in Sicily, Southern Italy

Samples (nu2009=u2009485) of raw (nu2009=u2009394) or heat-treated (nu2009=u200991) milk of three different species (cow, nu2009=u2009170; sheep, nu2009=u2009133; donkey, nu2009=u200984), collected 2013–2016 in Western Sicily (Southern Italy), were analyzed for aflatoxin M1 (AFM1) by enzyme-linked immunosorbent assay (ELISA). Positive ELISA results were further analyzed by HPLC with fluorescence detection. Both methods had a detection limit for AFM1 in milk of 7xa0ngxa0kg−1. ELISA yielded 12.9 and 5% positives in cows and sheep milk, respectively, all samples of donkey milk were negative. Levels of AFM1 were in most cases at 0.007–<u20090.05xa0μgxa0kg−1, only two samples (sheep milk) slightly exceeded the European Union maximum level of 0.05xa0μgxa0kg−1. Only 6% of the samples were positive for AFM1 in a concentration range of 0.008–0.15xa0μgxa0kg−1. Only milk samples collected directly from farms were positive. Overall, the levels were much lower than previously reported for Southern Italy cow and sheep milk samples purchased in retail stores. The results of this work indicate a continuous improvement of the feeding techniques on dairy farms of Southern Italy, which is essential to ensure consumers’ protection.

Determination of Ten Corticosteroids in Illegal Cosmetic Products by a Simple, Rapid, and High-Performance LC-MS/MS Method

The aim of our present work was the development of a rapid high-performance liquid chromatography method with electrospray ionization and tandem mass spectrometry detection (LC-ESI-MS/MS) for the determination of several corticosteroids in cosmetic products. Corticosteroids are suspected to be illegally added in cosmetic preparations in order to enhance the curative effect against some skin diseases. Sample preparation step consists in a single extraction with acetonitrile followed by centrifugation and filtration. The compounds were separated by reversed-phase chromatography with water and acetonitrile (both with 0.1% formic acid) gradient elution and detected by ESI-MS positive and negative ionization mode. The method was validated at the validation level of 0.1u2009mgu2009kg−1. Linearity was studied in the 5–250u2009μgu2009L−1 range and linear coefficients (r2) were all over 0.99. The accuracy and precision of the method were satisfactory. The LOD ranged from 0.085 to 0.109u2009mgu2009kg−1 and the LOQ from 0.102 to 0.121u2009mgu2009kg−1. Mean recoveries for all the analytes were within the range 91.9–99.2%. The developed method is sensitive and useful for detection, quantification, and confirmation of these corticosteroids in cosmetic preparations and can be applied in the analysis of the suspected samples under investigation.