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The metabolism of nitric oxide plays an increasingly interesting role in the physiological response of the human body to extreme environmental conditions, such as underwater, in an extremely cold climate, and at low oxygen concentrations. Field studies need the development of analytical methods to measure nitrite and nitrate in plasma and red blood cells with high requirements of accuracy, precision, and sensitivity. An optimized spectrophotometric Griess method for nitrite–nitrate affords sensitivity in the low millimolar range and precision within ±2 μM for both nitrite and nitrate, requiring 100 μL of scarcely available plasma sample or less than 50 μL of red blood cells. A scheduled time-efficient procedure affords measurement of as many as 80 blood samples, with combined nitrite and nitrate measurement in plasma and red blood cells. Performance and usefulness were tested in pilot studies that use blood fractions deriving from subjects who dwelt in an Antarctica scientific station and on breath-holding and scuba divers who performed training at sea and in a land-based deep pool facility. The method demonstrated adequate to measure low basal concentrations of nitrite and high production of nitrate as a consequence of water column pressure-triggered vasodilatation in deep-water divers.
Andrea Brizzolari; Michele Dei Cas; Danilo Cialoni; Alessandro Marroni; Camillo Morano; Michele Samaja; Rita Paroni; Federico Rubino. High-Throughput Griess Assay of Nitrite and Nitrate in Plasma and Red Blood Cells for Human Physiology Studies under Extreme Conditions. Molecules 2021, 26, 4569 .
AMA StyleAndrea Brizzolari, Michele Dei Cas, Danilo Cialoni, Alessandro Marroni, Camillo Morano, Michele Samaja, Rita Paroni, Federico Rubino. High-Throughput Griess Assay of Nitrite and Nitrate in Plasma and Red Blood Cells for Human Physiology Studies under Extreme Conditions. Molecules. 2021; 26 (15):4569.
Chicago/Turabian StyleAndrea Brizzolari; Michele Dei Cas; Danilo Cialoni; Alessandro Marroni; Camillo Morano; Michele Samaja; Rita Paroni; Federico Rubino. 2021. "High-Throughput Griess Assay of Nitrite and Nitrate in Plasma and Red Blood Cells for Human Physiology Studies under Extreme Conditions." Molecules 26, no. 15: 4569.
Glutathionyl hemoglobin is a minor form of hemoglobin with intriguing properties. The measurement of the redox potential of its reactive β-93-Cysteine is useful to improve understanding of the response of erythrocytes to transient and chronic conditions of oxidative stress, where the level of glutathionyl hemoglobin is increased. An independent literature experiment describes the recovery of human erythrocytes exposed to an oxidant burst by measuring glutathione, glutathione disulfide and glutathionyl hemoglobin in a two-hour period. This article calculates a value for the redox potential E0 of the β-93-Cysteine, considering the erythrocyte as a closed system at equilibrium described by the Nernst equation and using the measurements of the literature experiment. The obtained value of E0 of −121 mV at pH 7.4 places hemoglobin as the most oxidizing thiol of the erythrocyte. By using as synthetic indicators of the concentrations the electrochemical potentials of the two main redox pairs in the erythrocytes, those of glutathione–glutathione disulfide and of glutathionyl–hemoglobin, the mechanism of the recovery phase can be hypothesized. Hemoglobin acts as the redox buffer that scavenges oxidized glutathione in the oxidative phase and releases it in the recovery phase, by acting as the substrate of the NAD(P)H-cofactored enzymes.
Federico Rubino. The Redox Potential of the β-93-Cysteine Thiol Group in Human Hemoglobin Estimated from In Vitro Oxidant Challenge Experiments. Molecules 2021, 26, 2528 .
AMA StyleFederico Rubino. The Redox Potential of the β-93-Cysteine Thiol Group in Human Hemoglobin Estimated from In Vitro Oxidant Challenge Experiments. Molecules. 2021; 26 (9):2528.
Chicago/Turabian StyleFederico Rubino. 2021. "The Redox Potential of the β-93-Cysteine Thiol Group in Human Hemoglobin Estimated from In Vitro Oxidant Challenge Experiments." Molecules 26, no. 9: 2528.
Pesticides represent an economical, labor-saving, and efficient tool for pest management, but their intrinsic toxic properties may endanger workers and the general population. Risk assessment is necessary, and biological monitoring represents a potentially valuable tool. Several international agencies propose biological exposure indices (BEI), especially for substances which are commonly absorbed through the skin. Biological monitoring for pesticide exposure and risk assessment seems a natural choice, but biological exposure limits (BEL) for pesticides are lacking. This study aims at establishing equivalent biological exposure limits (EBEL) for pesticides using real-life field data and the Acceptable Operator Exposure Level (AOEL) of mancozeb as the reference. This study included a group of 16 vineyard pesticide applicators from Northern Italy, a subgroup of a more extensive study of 28 applicators. Their exposure was estimated using "patch" and "hand-wash" methodologies, together with biological monitoring of free ethylene-bis-thiourea (ETU) excretion in 24-hour pre- and post-exposure urine samples. Modeling was done using univariate linear regression with ETU excretion as the dependent variable and the estimated absorbed dose as the independent variable. The median skin deposition of mancozeb in our study population was 125 μg, leading to a median absorbed dose of 0.9 μg/kg. The median post-exposure ETU excretion was 3.7 μg. The modeled EBEL for mancozeb was 148 μg of free ETU or 697 μg of total ETU, accounting for around 75% of the maximum theoretical excretion based on a mass balance model. Although preliminary and based on a small population of low-exposed workers, our results demonstrate a procedure to develop strongly needed biological exposure limits for pesticides.
Stefan Mandić-Rajčević; Federico Maria Rubino; Claudio Colosio. Establishing health-based Biological Exposure Limits for pesticides: a proof of principle study using Mancozeb. 2020, 1 .
AMA StyleStefan Mandić-Rajčević, Federico Maria Rubino, Claudio Colosio. Establishing health-based Biological Exposure Limits for pesticides: a proof of principle study using Mancozeb. . 2020; ():1.
Chicago/Turabian StyleStefan Mandić-Rajčević; Federico Maria Rubino; Claudio Colosio. 2020. "Establishing health-based Biological Exposure Limits for pesticides: a proof of principle study using Mancozeb." , no. : 1.
Two scan modes of the triple quadrupole tandem mass spectrometer, namely Collision Induced Dissociation Precursor Ion scan and Neutral Loss scan, allow selectively pinpointing, in a complex mixture, compounds that feature specific chemical groups, which yield characteristic fragment ions or are lost as distinctive neutral fragments. This feature of the triple quadrupole tandem mass spectrometer allows the non-target screening of mixtures for classes of components. The effective (center-of-mass) energy to achieve specific fragmentation depends on the inter-quadrupole voltage (laboratory-frame collision energy) and on the masses of the precursor molecular ion and of the collision gas, through a non-linear relationship. Thus, in a class of homologous compounds, precursor ions activated at the same laboratory-frame collision energy face different center-of-mass collision energy, and therefore the same fragmentation channel operates with different degrees of efficiency. This article reports a linear equation to calculate the laboratory-frame collision energy necessary to operate Collision-Induced Dissociation at the same center-of-mass energy on closely related compounds with different molecular mass. A routine triple quadrupole tandem mass spectrometer can operate this novel feature (iso-energetic collision-induced dissociation scan; i-CID) to analyze mixtures of endogenous metabolites by Precursor Ion and Neutral Loss scans. The latter experiment also entails the hitherto unprecedented synchronized scanning of all three quadrupoles of the triple quadrupole tandem mass spectrometer. To exemplify the application of this technique, this article shows two proof-of-principle approaches to the determination of biological mixtures, one by Precursor Ion analysis on alpha amino acid derivatized with a popular chromophore, and the other on modified nucleosides with a Neutral Fragment Loss scan.
Federico Maria Rubino. Center-of-Mass iso-Energetic Collision-Induced Decomposition in Tandem Triple Quadrupole Mass Spectrometry. Molecules 2020, 25, 2250 .
AMA StyleFederico Maria Rubino. Center-of-Mass iso-Energetic Collision-Induced Decomposition in Tandem Triple Quadrupole Mass Spectrometry. Molecules. 2020; 25 (9):2250.
Chicago/Turabian StyleFederico Maria Rubino. 2020. "Center-of-Mass iso-Energetic Collision-Induced Decomposition in Tandem Triple Quadrupole Mass Spectrometry." Molecules 25, no. 9: 2250.
The densely packed storage of valuable nutrients (carbohydrates, lipids, proteins, micronutrients) in the endosperm of nuts and seeds makes the study of their complex composition a topic of great importance. Ceramides in the total lipid extract of some ground almonds and pistachios were searched with a systematic innovative discovery precursor ion scan in a triple quadrupole tandem mass spectrometry, where iso-energetic collision activated dissociation was performed. Five descriptors were used to search components with different C18 long chain bases containing different structural motifs (d18:0, d18:1, d18:2, t18:0, t18:1). The presence of hexoside unit was screened with a specific neutral loss experiment under iso-energetic collision activated dissociation conditions. The discovery scans highlighted the presence of two specific hexosyl-ceramides with a modified sphingosine component (d18:2) and C16:0 or C16:0 hydroxy-fatty acids. The hexosyl-ceramide with the non-hydroxylated fatty acid seemed specific of pistachios and was undetected in almonds. The fast and comprehensive mass spectrometric method used here can be useful to screen lipid extracts of several more seeds of nutraceutical interest, searching for unusual and/or specific sphingosides with chemically decorated long chain bases.
Federico Maria Rubino; Michele Dei Cas; Monica Bignotto; Riccardo Ghidoni; Marcello Iriti; Rita Paroni. Discovery of Unexpected Sphingolipids in Almonds and Pistachios with an Innovative Use of Triple Quadrupole Tandem Mass Spectrometry. Foods 2020, 9, 110 .
AMA StyleFederico Maria Rubino, Michele Dei Cas, Monica Bignotto, Riccardo Ghidoni, Marcello Iriti, Rita Paroni. Discovery of Unexpected Sphingolipids in Almonds and Pistachios with an Innovative Use of Triple Quadrupole Tandem Mass Spectrometry. Foods. 2020; 9 (2):110.
Chicago/Turabian StyleFederico Maria Rubino; Michele Dei Cas; Monica Bignotto; Riccardo Ghidoni; Marcello Iriti; Rita Paroni. 2020. "Discovery of Unexpected Sphingolipids in Almonds and Pistachios with an Innovative Use of Triple Quadrupole Tandem Mass Spectrometry." Foods 9, no. 2: 110.
Food plants contain hundreds of bioactive phytochemicals arising from different secondary metabolic pathways. Among these, the metabolic route of the amino acid Tryptophan yields a large number of plant natural products with chemically and pharmacologically diverse properties. We propose the identifier “indolome” to collect all metabolites in the Tryptophan pathway. In addition, Tryptophan-rich plant sources can be used as substrates for the fermentation by yeast strains to produce pharmacologically active metabolites, such as Melatonin. To pursue this technological development, we have developed a UHPLC-MS/MS method to monitor 14 Tryptophan, Tryptamine, amino-benzoic, and pyridine metabolites. In addition, different extraction procedures to improve the recovery of Tryptophan and its derivatives from the vegetal matrix were tested. We investigated soybeans, pumpkin seeds, sesame seeds, and spirulina because of their botanical diversity and documented healthy effects. Four different extractions with different solvents and temperatures were tested, and water extraction at room temperature was chosen as the most suitable procedure to extract the whole Tryptophan metabolites pattern (called by us “indolome”) in terms of ease, high efficiency, short time, low cost, and sustainability. In all plant matrices, Tryptophan was the most abundant indole compound, while the pattern of its metabolites was different in the diverse plants extracts. Overall, 5-OH Tryptamine and Kynurenine were the most abundant compounds, despite being 100–1000-fold lower than Tryptophan. Melatonin was undetected in all extracts, but sesame showed the presence of a Melatonin isomer. The results of this study highlight the variability in the occurrence of indole compounds among diverse food plants. The knowledge of Tryptophan metabolism in plants represents a relevant issue for human health and nutrition.
Sara Vitalini; Michele Dei Cas; Federico Maria Rubino; Ileana Vigentini; Roberto Foschino; Marcello Iriti; Rita Paroni. LC-MS/MS-Based Profiling of Tryptophan-Related Metabolites in Healthy Plant Foods. Molecules 2020, 25, 311 .
AMA StyleSara Vitalini, Michele Dei Cas, Federico Maria Rubino, Ileana Vigentini, Roberto Foschino, Marcello Iriti, Rita Paroni. LC-MS/MS-Based Profiling of Tryptophan-Related Metabolites in Healthy Plant Foods. Molecules. 2020; 25 (2):311.
Chicago/Turabian StyleSara Vitalini; Michele Dei Cas; Federico Maria Rubino; Ileana Vigentini; Roberto Foschino; Marcello Iriti; Rita Paroni. 2020. "LC-MS/MS-Based Profiling of Tryptophan-Related Metabolites in Healthy Plant Foods." Molecules 25, no. 2: 311.
Oxygen (O2) is commonly used in clinical practice to prevent or treat hypoxia, but if used in excess (hyperoxia), it may act as toxic. O2 toxicity arises from the enhanced formation of Reactive Oxygen Species (ROS) that exceed the antioxidant defenses and generate oxidative stress. In this study, we aimed at assessing whether an elevated fraction of inspired oxygen (FiO2) during and after general anesthesia may contribute to the unbalancing of the pro-oxidant/antioxidant equilibrium. We measured five oxidative stress biomarkers in blood samples from patients undergoing elective abdominal surgery, randomly assigned to FiO2 = 0.40 vs. 0.80: hydroperoxides, antioxidants, nitrates and nitrites (NOx), malondialdehyde (MDA), and glutathionyl hemoglobin (HbSSG). The MDA concentration was significantly higher 24 h after surgery, and the body antioxidant defense lower, in the FiO2 = 0.80 group with respect to both the FiO2 = 0.40 group and the baseline values (p ≤ 0.05, Student’s t-test). HbSSG in red blood cells was also higher in the FiO2 = 0.80 group at the end of the surgery. NOx was higher in the FiO2 = 0.80 group than the FiO2 = 0.40 group at t = 2 h after surgery. MDA, the main end product of the peroxidation of polyunsaturated fatty acids directly influenced by FiO2, may represent the best marker to assess the pro-oxidant/antioxidant equilibrium after surgery.
Sara Ottolenghi; Federico Maria Rubino; Giovanni Sabbatini; Silvia Coppola; Alice Veronese; Davide Chiumello; Rita Paroni. Oxidative Stress Markers to Investigate the Effects of Hyperoxia in Anesthesia. International Journal of Molecular Sciences 2019, 20, 5492 .
AMA StyleSara Ottolenghi, Federico Maria Rubino, Giovanni Sabbatini, Silvia Coppola, Alice Veronese, Davide Chiumello, Rita Paroni. Oxidative Stress Markers to Investigate the Effects of Hyperoxia in Anesthesia. International Journal of Molecular Sciences. 2019; 20 (21):5492.
Chicago/Turabian StyleSara Ottolenghi; Federico Maria Rubino; Giovanni Sabbatini; Silvia Coppola; Alice Veronese; Davide Chiumello; Rita Paroni. 2019. "Oxidative Stress Markers to Investigate the Effects of Hyperoxia in Anesthesia." International Journal of Molecular Sciences 20, no. 21: 5492.
P-Cresyl sulfate is one of the bound uremic toxins whose level increases in the sera of patients with the severity of chronic kidney disease and is therefore used as a standard for clinical investigations. Our first attempts to obtain p-cresyl sulfate led exclusively to the product of sulfonation of the aromatic ring instead of sulfation on the OH moiety. Nevertheless, this initial discouraging result allowed us to handle both p-cresyl sulfate and 2-hydroxy-5-methylbenzenesulfonic acid obtained by different synthetic pathways. Interestingly, the comparison between the two isomers pointed out that the two molecules show the same fragmentation pattern and are indistinguishable by mass spectrometry. They cannot be separated on several commercially available columns. The only difference between the two compounds is a 10-fold higher ionization yield under negative ion electrospray ionization. NMR spectral studies definitely confirmed the different molecular structures. We present here an unambiguous biomimetic synthetic route for p-cresyl sulfate and the spectroscopic characterization of both the compounds by nuclear magnetic resonance and mass spectrometry.
Rita Paroni; Silvana Casati; Michele Dei Cas; Monica Bignotto; Federico Maria Rubino; Pierangela Ciuffreda. Unambiguous Characterization of p-Cresyl Sulfate, a Protein-Bound Uremic Toxin, as Biomarker of Heart and Kidney Disease. Molecules 2019, 24, 3704 .
AMA StyleRita Paroni, Silvana Casati, Michele Dei Cas, Monica Bignotto, Federico Maria Rubino, Pierangela Ciuffreda. Unambiguous Characterization of p-Cresyl Sulfate, a Protein-Bound Uremic Toxin, as Biomarker of Heart and Kidney Disease. Molecules. 2019; 24 (20):3704.
Chicago/Turabian StyleRita Paroni; Silvana Casati; Michele Dei Cas; Monica Bignotto; Federico Maria Rubino; Pierangela Ciuffreda. 2019. "Unambiguous Characterization of p-Cresyl Sulfate, a Protein-Bound Uremic Toxin, as Biomarker of Heart and Kidney Disease." Molecules 24, no. 20: 3704.
Claudio Colosio; Federico Maria Rubino; Angelo Moretto. Pesticides. International Encyclopedia of Public Health 2017, 454 -462.
AMA StyleClaudio Colosio, Federico Maria Rubino, Angelo Moretto. Pesticides. International Encyclopedia of Public Health. 2017; ():454-462.
Chicago/Turabian StyleClaudio Colosio; Federico Maria Rubino; Angelo Moretto. 2017. "Pesticides." International Encyclopedia of Public Health , no. : 454-462.
Stefan Mandic-Rajcevic; Federico Maria Rubino; Giorgio Vianello; Lorenzo Fugnoli; Elisa Polledri; Rosa Mercadante; Angelo Moretto; Silvia Fustinoni; Claudio Colosio. Dermal exposure and risk assessment of tebuconazole applicators in vineyards. La Medicina del lavoro 2015, 106, 1 .
AMA StyleStefan Mandic-Rajcevic, Federico Maria Rubino, Giorgio Vianello, Lorenzo Fugnoli, Elisa Polledri, Rosa Mercadante, Angelo Moretto, Silvia Fustinoni, Claudio Colosio. Dermal exposure and risk assessment of tebuconazole applicators in vineyards. La Medicina del lavoro. 2015; 106 (4):1.
Chicago/Turabian StyleStefan Mandic-Rajcevic; Federico Maria Rubino; Giorgio Vianello; Lorenzo Fugnoli; Elisa Polledri; Rosa Mercadante; Angelo Moretto; Silvia Fustinoni; Claudio Colosio. 2015. "Dermal exposure and risk assessment of tebuconazole applicators in vineyards." La Medicina del lavoro 106, no. 4: 1.
To ensure the preservation and quality of the goods, physical (i.e. radiation) or chemical pest control is needed. The dark side of such consents may bear health risks in international transport and production sharing. In fact, between 10% and 20% of all containers arriving European harbors were shown to contain volatile toxic substances above the exposure limit values. Possible exposure to these toxic chemicals may occur not only for the applicators but also the receiver by off gassing from products, packing materials or transport units like containers. A number of intoxications, some with lethal outcome, occur not only during the fumigation, but also during freight transport (on bulk carriers and other transport vessels), as well as in the logistic lines during loading and unloading. Risk occupations include dock-workers, seafarers, inspectors, as well as the usually uninformed workers of importing enterprises that unload the products. Bystanders as well as vulnerable consumers may also be at risk. Ongoing studies focus on the release of these toxic volatile substances from various goods. It was shown that the half-lives of the off-gassing process range between minutes and months, depending on the toxic substance, its chemical reactivity, concentration, the temperature, the contaminated matrix (goods and packing materials), and the packing density in the transport units. Regulations on declaration and handling dangerous goods are mostly not followed. It is obvious that this hazardous situation in freight transport urgently requires preventive steps. In order to improve awareness and relevant knowledge there is a need for more comprehensive information on chemical hazards and a broader implementation of the already existing regulations and guidelines, such as those from ILO, IMO, and national authorities. It is also necessary to have regular controls by the authorities on a worldwide scale, which should be followed by sanctions in case of disregarding regulations. Further, fumigated containers must have a warning sign corresponding to international recommendations and national regulations, and freight documents have to indicate any potential hazard during stripping the goods.
Xaver Baur; Lygia Therese Budnik; Zhiwei Zhao; Magne Bråtveit; Rune Djurhuus; Louis Verschoor; Federico Maria Rubino; Claudio Colosio; Jorgen R Jepsen. Health risks in international container and bulk cargo transport due to volatile toxic compounds. Journal of Occupational Medicine and Toxicology 2015, 10, 1 -18.
AMA StyleXaver Baur, Lygia Therese Budnik, Zhiwei Zhao, Magne Bråtveit, Rune Djurhuus, Louis Verschoor, Federico Maria Rubino, Claudio Colosio, Jorgen R Jepsen. Health risks in international container and bulk cargo transport due to volatile toxic compounds. Journal of Occupational Medicine and Toxicology. 2015; 10 (1):1-18.
Chicago/Turabian StyleXaver Baur; Lygia Therese Budnik; Zhiwei Zhao; Magne Bråtveit; Rune Djurhuus; Louis Verschoor; Federico Maria Rubino; Claudio Colosio; Jorgen R Jepsen. 2015. "Health risks in international container and bulk cargo transport due to volatile toxic compounds." Journal of Occupational Medicine and Toxicology 10, no. 1: 1-18.
Mercury, cadmium, arsenic and lead are among priority metals for toxicological studies due to the frequent human exposure and to the significant burden of disease following acute and chronic intoxication. Among their common characteristics is chemical affinity to proteins and non-protein thiols and their ability to generate cellular oxidative stress by the best-known Fenton mechanism. Their health effects are however diverse: kidney and liver damage, cancer at specific sites, irreversible neurological damages with metal-specific features. Mechanisms for the induction of oxidative stress by interaction with the cell thiolome will be presented, based on literature evidence and of experimental findings.
Federico Maria Rubino. Toxicity of Glutathione-Binding Metals: A Review of Targets and Mechanisms. Toxics 2015, 3, 20 -62.
AMA StyleFederico Maria Rubino. Toxicity of Glutathione-Binding Metals: A Review of Targets and Mechanisms. Toxics. 2015; 3 (1):20-62.
Chicago/Turabian StyleFederico Maria Rubino. 2015. "Toxicity of Glutathione-Binding Metals: A Review of Targets and Mechanisms." Toxics 3, no. 1: 20-62.
Tebuconazole (TEB) is a fungicide widely used in vineyards and is a suspected teratogen for humans. The aim of this research was to identify urinary biomarkers and the best sampling time for the biological monitoring of exposure to TEB in agricultural workers. Seven vineyard workers of the Monferrato region, Piedemont, Italy, were investigated for a total of 12 workdays. They treated the vineyards with TEB for 1-2 consecutive days, one of them for 3 days. During each application coveralls, underwears, hand washing liquids and head coverings were used to estimate dermal exposure. For biomonitoring, spot samples of urine from each individual were collected starting from 24 h before the first application, continuing during the application, and again after the application for about 48 h. TEB and its metabolites TEB-OH and TEB-COOH were measured by liquid chromatography/triple quadrupole mass spectrometry. TEB contamination of coveralls and total dermal exposure showed median levels of 6180 and 1020 μg. Urinary TEB-OH was the most abundant metabolite; its excretion rate peaked within 24 h after product application (post 24 h). In this time frame, median levels of TEB-OH and TEB-COOH ranged from 8.0 to 387.8 μg/l and from 5.7 to 102.9 μg/l, respectively, with a ratio between the two metabolites of about 3.5. The total amount of urinary metabolites (U-TEBeq) post 24 h was significantly correlated with both TEB on coveralls and total dermal exposure (Pearson's r=0.756 and 0.577). The amount of metabolites excreted in urine represented about 17% of total dermal TEB exposure. Our results suggest that TEB-OH and TEB-COOH in post-exposure urine samples are promising candidates for biomonitoring TEB exposure in agricultural workers.
Silvia Fustinoni; Rosa Mercadante; Elisa Polledri; Federico Maria Rubino; Stefan Mandic-Rajcevic; Giorgio Vianello; Claudio Colosio; Angelo Moretto. Biological monitoring of exposure to tebuconazole in winegrowers. Journal of Exposure Science & Environmental Epidemiology 2014, 24, 643 -649.
AMA StyleSilvia Fustinoni, Rosa Mercadante, Elisa Polledri, Federico Maria Rubino, Stefan Mandic-Rajcevic, Giorgio Vianello, Claudio Colosio, Angelo Moretto. Biological monitoring of exposure to tebuconazole in winegrowers. Journal of Exposure Science & Environmental Epidemiology. 2014; 24 (6):643-649.
Chicago/Turabian StyleSilvia Fustinoni; Rosa Mercadante; Elisa Polledri; Federico Maria Rubino; Stefan Mandic-Rajcevic; Giorgio Vianello; Claudio Colosio; Angelo Moretto. 2014. "Biological monitoring of exposure to tebuconazole in winegrowers." Journal of Exposure Science & Environmental Epidemiology 24, no. 6: 643-649.
Claudio Colosio; Stefan Mandic-Rajcevic; Giorgio Vianello; Eugenio Ariano; Federico Maria Rubino. Definition of AOEL-based provisional BEIs for pesticide exposure monitoring: a proposed approach for the protection of farmer's health. Toxicology Letters 2013, 221, S33 .
AMA StyleClaudio Colosio, Stefan Mandic-Rajcevic, Giorgio Vianello, Eugenio Ariano, Federico Maria Rubino. Definition of AOEL-based provisional BEIs for pesticide exposure monitoring: a proposed approach for the protection of farmer's health. Toxicology Letters. 2013; 221 ():S33.
Chicago/Turabian StyleClaudio Colosio; Stefan Mandic-Rajcevic; Giorgio Vianello; Eugenio Ariano; Federico Maria Rubino. 2013. "Definition of AOEL-based provisional BEIs for pesticide exposure monitoring: a proposed approach for the protection of farmer's health." Toxicology Letters 221, no. : S33.
Concentrations of 36 polychlorinated biphenyl (PCB) congeners were measured in serum of 372 Italian residents of general population living in Novafeltria, Pavia, and Milan. Total PCB level differed significantly between these sites ( p < 0.0001) with median concentrations of 836.50, 1354.57, and 2062.08 pmol/g lipid, respectively. However, there is no evidence for the difference in distribution of total PCB levels by genders. Total dioxin-like PCBs differed significantly ( p < 0.0001) between the sites (median 109.78, 50.88, and 166.99 pmol/g lipid, respectively) and genders of Novafeltria and Pavia ( p = 0.011 and 0.009, respectively). PCB 138, 153, 170, and 180 differed significantly between the places of residence ( p < 0.0001) with higher values in Milan population. In the overall population, total PCB and PCB 138, 153, 156, 170, and 180 correlated positively with age (correlations range between 0.320 and 0.569, p < 0.0001). In Novafeltria, the correlations ranged between 0.545 and 0.670, and in Pavia, the correlations ranged between 0.516 and 0.666. In Milan, correlations with age range between 0.327 and 0.417 for total PCB and congeners 138, 153, and 180. With an exception of PCB 170, there was no evidence of significant difference in the distribution of most abundant PCB congeners and total PCB across the body mass index categories.
E J Mrema; Federico Maria Rubino; S Mandic-Rajcevic; E Sturchio; Roberta Turci; A Osculati; Gabri Brambilla; C Minoia; Claudio Colosio. Exposure to priority organochlorine contaminants in the Italian general population. Part 2. Human & Experimental Toxicology 2013, 33, 170 -184.
AMA StyleE J Mrema, Federico Maria Rubino, S Mandic-Rajcevic, E Sturchio, Roberta Turci, A Osculati, Gabri Brambilla, C Minoia, Claudio Colosio. Exposure to priority organochlorine contaminants in the Italian general population. Part 2. Human & Experimental Toxicology. 2013; 33 (2):170-184.
Chicago/Turabian StyleE J Mrema; Federico Maria Rubino; S Mandic-Rajcevic; E Sturchio; Roberta Turci; A Osculati; Gabri Brambilla; C Minoia; Claudio Colosio. 2013. "Exposure to priority organochlorine contaminants in the Italian general population. Part 2." Human & Experimental Toxicology 33, no. 2: 170-184.
Despite extensive use of organochlorinated pesticides (OCPs) such as dichlorodiphenyltrichloroethane (DDT) in Italy in the 1940s to 1970s, especially for public health control of malaria mosquitoes, information on their exposure levels among the general population is limited. These OCPs can be a source of health risk to human. A total of 137 blood samples were collected from residents of the general population of three Italian towns, Novafeltria, Pavia and Milan, to determine the levels of eight OCPs in blood serum. The concentrations of beta-hexachlorocyclohexane, hexachlorobenzene (HCB), 1,1-dichloro-2-( o-chlorophenyl)-2-( p-chlorophenyl)ethylene, 1,1-dichloro-2,2-bis( p-chlorophenyl)-ethylene ( p, p' -DDE), 1,1-dichloro-2-( o-chlorophenyl)-2-( p-chlorophenyl)ethane, 1,1-dichloro-2,2-bis (4-chlorophenyl)ethane, 1,1,1-trichloro-2-( o-chlorophenyl)-2-( p-chlorophenyl)-ethane and 1,1,1-trichloro-2,2-bis( p-chlorophenyl) ethane were measured by gas chromatography–mass spectrometry. Variations in serum concentrations of OCPs with respect to place of residence, gender, age and body mass index (BMI) were evaluated by non-parametric tests. p, p' -DDE and HCB were the most abundant and major contributors of total OCP concentration. Their levels differed significantly between the three towns with a trend Milan > Novafeltria > Pavia ( p < 0.0001). Females had significantly higher concentrations of HCB and p, p'-DDE than males in the overall population sample. HCB concentrations were significantly higher in females than in males of Milan ( p = 0.029). We observed positive correlations of p, p'-DDE and HCB with age in Novafeltria subjects ( r = 0.468, p = 0.004). Total OCP concentrations differed significantly across BMI categories ( p = 0.018) in overall population. We have demonstrated a clear pattern of the main OCPs in a fairly large population. Generally, our study provides information on OCPs exposure among the Italian general population and provides indications for further investigations.
Ej Mrema; Federico Maria Rubino; S Mandic-Rajcevic; E Sturchio; Roberta Turci; A Osculati; Gabri Brambilla; C Minoia; Claudio Colosio. Exposure to priority organochlorine contaminants in the Italian general population. Part 1. Eight priority organochlorinated pesticides in blood serum. Human & Experimental Toxicology 2013, 32, 1323 -1339.
AMA StyleEj Mrema, Federico Maria Rubino, S Mandic-Rajcevic, E Sturchio, Roberta Turci, A Osculati, Gabri Brambilla, C Minoia, Claudio Colosio. Exposure to priority organochlorine contaminants in the Italian general population. Part 1. Eight priority organochlorinated pesticides in blood serum. Human & Experimental Toxicology. 2013; 32 (12):1323-1339.
Chicago/Turabian StyleEj Mrema; Federico Maria Rubino; S Mandic-Rajcevic; E Sturchio; Roberta Turci; A Osculati; Gabri Brambilla; C Minoia; Claudio Colosio. 2013. "Exposure to priority organochlorine contaminants in the Italian general population. Part 1. Eight priority organochlorinated pesticides in blood serum." Human & Experimental Toxicology 32, no. 12: 1323-1339.
Protection of crops from pests and from ravenous animals was long accomplished with the use of ‘natural’ means, before the introduction of ‘modern’ synthetic chemicals as pesticides in the twentieth century. The widespread use of synthetic organic chemicals as pesticides in the last several decades has contributed to the ‘background’ contamination of all environmental and biological compartments with trace amounts of small organic compounds, the combined effect of which on the health of humans and on the general well-being of complex ecological systems is far from being understood. In particular, it is claimed that the presence of trace amounts of such compounds in human food may contribute to impair the health of sensitive individuals, especially in the developmental and early-age stages of life, although there is not a clear-cut consensus on this problem. The request from consumers, mainly in developed Western countries, of food produced under perceived healthier conditions than those of mass-production, has prompted a backslash of interest in traditional, lower-yield techniques such as ‘organic farming’ and thus the necessity to protect consumers from unsubstantiated claims of food quality through the issuing of voluntary codes by producers and of guidelines such as Codex Alimentarius at the level of international Organizations. Another driving force into a renaissance of ‘traditional’ farming techniques is understanding that they can be successfully merged to ‘modern’ ones to achieve better productions with lower environmental impact, lower consumption of selective but expensive Plant Protection Products, lower contamination of food with residues. Another trigger to seek alternatives to the conventional means of pest fighting is acknowledgement that later generations may develop resistance to current pesticides in a continuous ‘chemical war’ between human scientific intellect and natural evolution of organisms. Traditional agricultural wisdom long recognized the power of coenobioses and used co-cultivation of different crops as a means to deter parasites by exploiting the natural emission of insect repellents and mutual fight between natural hosts of crops and invading organisms. Of course, since even ‘natural’ substances long employed to fight parasites of plants and food are intrinsically toxic not only to target species but also to several others, including the human, risk assessment of their use is mandatory to fully benefit of their strength without unnecessary risk for producers, consumers and the global environment. The recent exploitation of natural as well as of engineered organisms and of their toxic products as pesticides is another means the reach and limitations of which need to be fully understood. Examples of how these seemingly conflicting requirements have been or can be harmonized will be presented and discussed.
Federico M. Rubino; Stefan Mandic-Rajcevic; Ezra J. Mrema; Claudio Colosio. Principles and Application of the Integrated Pest Management Approach. Biological Pesticides. Green Defense Technology 2013, 413 -432.
AMA StyleFederico M. Rubino, Stefan Mandic-Rajcevic, Ezra J. Mrema, Claudio Colosio. Principles and Application of the Integrated Pest Management Approach. Biological Pesticides. Green Defense Technology. 2013; ():413-432.
Chicago/Turabian StyleFederico M. Rubino; Stefan Mandic-Rajcevic; Ezra J. Mrema; Claudio Colosio. 2013. "Principles and Application of the Integrated Pest Management Approach. Biological Pesticides." Green Defense Technology , no. : 413-432.
The use of synthetic chemicals such as plant protection products (PPPs or ‘pesticides’), especially in the last 60–70 years, greatly contributed to an impressive progress in the availability of food to an increasingly numerous mankind. However, the long-term consequences of the deliberate and unavoidable dispersion of these chemicals into the environment were long overlooked and generated health consequences to professional applicators, to bystander general population and to food consumers. An increased awareness of the potential threats of uncontrolled use of substances of poorly known toxicity led to a substantial change in the approach, gradually resulting into an improved legislation in Western Europe and in other developed countries, to the point that today licensed PPPs are among the substances of which the chemical and toxicological properties are best known, much before their introduction into the market and even better than requested for human pharmaceutical drugs. We will trace the pathway which leads to the birth of new PPPs and to their authorization according to the legislation of the European Union. In particular, while active substances are licensed for use in a ‘positive list’ at EU level, the different formulations suitable for use on different cultivations are authorized for the different geographical areas of EU with a ‘mutual recognition’ procedure between member States. Protection of agricultural workers, of consumers, of the environment are embedded into the authorization procedure by requesting that targeted studies run under normalized conditions are conducted prior to marketing. Several chemical and toxicological parameters which are pivotal to risk assessments towards humans, non-target plants and animals are measured and health-based safety levels are established for agricultural workers, for bystanders, for the general population, for the residual presence of the active substance and of its decomposition products in food and in natural drinkable water. For enhanced safety, authorization is released in 10-year periods, in order that unexpected harmful consequences for man and environment can be timely examined and, in case, tackled. The financial cost of this procedure is, of course, not without consequences. Since authorizations are issued in 10-year periods and are subject to voluntary rejuvenation by the licensees, there is a pressure to invest in newer, more profitable active substances rather than to keep into market older ones, which may be as efficient and cheaper, but for which the faintest evidence of health or environmental hazard may prematurely terminate corporate interest. The genesis of EU legislation will be discussed and examples will be brought to highlight key issues.
Stefan Mandic-Rajcevic; Federico M. Rubino; Claudio Colosio. General Approaches and Procedures for Pesticide Legislation. Green Defense Technology 2013, 449 -470.
AMA StyleStefan Mandic-Rajcevic, Federico M. Rubino, Claudio Colosio. General Approaches and Procedures for Pesticide Legislation. Green Defense Technology. 2013; ():449-470.
Chicago/Turabian StyleStefan Mandic-Rajcevic; Federico M. Rubino; Claudio Colosio. 2013. "General Approaches and Procedures for Pesticide Legislation." Green Defense Technology , no. : 449-470.
Since Rachel Carson’s passionate warning in the seminal 1962 book ‘Silent Spring’, which is now celebrating 50 years from its publication, concern on the steadily increasing accumulation in the environment of chemically robust, biologically persistent and possibly toxic organochlorine pesticides led to their substitution with less threatening products and finally to stop or limit their production and to severely restrict their use. In particular, the Stockholm Convention on Persistent Organic Pollutants (POPS) signed in 2001 banned or greatly restricted 12 chlorinated organic compounds or classes due to their toxicity and ability to accumulate in the environment and to magnify through the global trophic network. Among them are 11 pesticides namely aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, hexachloro-benzene, kepone, lindane, mirex, toxaphene. These pesticides played a historical role in mitigating the health impact of parasite-borne human pathogens such as malaria parasites and in protecting food crops to allow better feeding of an increasingly raising population especially in sub-tropical and tropical areas. Concern for human and environmental health is mainly due to long-term effects of some substances, in particular through endocrine disruption, interference with reproduction, carcinogenicity, although the actual size of effects of real-life exposure is still an active and debated research topic. Risk assessment and risk-benefit analysis of some key pesticides such as DDT still need a thorough understanding of the toxicity mechanisms and of its relevance to humans in the different life-stages. As a consequence of the Stockholm ban, large stockpiles of unusable pesticides accumulate in some countries and thus present considerable threat to the environment and to human health, also due to unavoidable degradation of the active formulated substances into poorly tractable materials. To avoid environmental damage through contamination of water and agricultural land resources by leaching or improper disposal of repositories, inventories of existing stockpiles are needed to plan and carry adequately safe disposal interventions. Methods for disposal need to tackle the peculiar chemical characteristics of these highly chlorinated aliphatic and aromatic compounds, i.e., very low water solubility and an unusual stability towards acid, basic and oxidizing conditions. Research and technology development in this field is currently exploiting the most advanced ‘green chemistry’ approaches, aimed at an as complete mineralization of organo-chlorine substrates with as negligible production of toxic waste. We will draw a brief historical perspective of the genesis of this pivotal environmental problem, review the use of the ‘dirty dozen’ pesticides and their contribution to the Green Revolution improvement of agricultural food availability, the ecotoxicological and human health concern and the current efforts to front the problems raised by their use.
Ezra J. Mrema; Federico M. Rubino; Claudio Colosio. Obsolete Pesticides – A Threat to Environment, Biodiversity and Human Health. Green Defense Technology 2013, 1 -21.
AMA StyleEzra J. Mrema, Federico M. Rubino, Claudio Colosio. Obsolete Pesticides – A Threat to Environment, Biodiversity and Human Health. Green Defense Technology. 2013; ():1-21.
Chicago/Turabian StyleEzra J. Mrema; Federico M. Rubino; Claudio Colosio. 2013. "Obsolete Pesticides – A Threat to Environment, Biodiversity and Human Health." Green Defense Technology , no. : 1-21.
F M Rubino; S Mandic-Rajcevic; G Vianello; G Brambilla; C Colosio. [Physically-based model of pesticide application for risk assessment of agricultural workers]. Giornale italiano di medicina del lavoro ed ergonomia 2013, 34, 1 .
AMA StyleF M Rubino, S Mandic-Rajcevic, G Vianello, G Brambilla, C Colosio. [Physically-based model of pesticide application for risk assessment of agricultural workers]. Giornale italiano di medicina del lavoro ed ergonomia. 2013; 34 (3):1.
Chicago/Turabian StyleF M Rubino; S Mandic-Rajcevic; G Vianello; G Brambilla; C Colosio. 2013. "[Physically-based model of pesticide application for risk assessment of agricultural workers]." Giornale italiano di medicina del lavoro ed ergonomia 34, no. 3: 1.