Pablo Olmedo

Determination of toxic elements (mercury, cadmium, lead, tin and arsenic) in fish and shellfish samples. Risk assessment for the consumers

Although fish intake has potential health benefits, the presence of metal contamination in seafood has raised public health concerns. In this study, levels of mercury, cadmium, lead, tin and arsenic have been determined in fresh, canned and frozen fish and shellfish products and compared with the maximum levels currently in force. In a further step, potential human health risks for the consumers were assessed. A total of 485 samples of the 43 most frequently consumed fish and shellfish species in Andalusia (Southern Spain) were analyzed for their toxic elements content. High mercury concentrations were found in some predatory species (blue shark, cat shark, swordfish and tuna), although they were below the regulatory maximum levels. In the case of cadmium, bivalve mollusks such as canned clams and mussels presented higher concentrations than fish, but almost none of the samples analyzed exceeded the maximum levels. Lead concentrations were almost negligible with the exception of frozen common sole, which showed median levels above the legal limit. Tin levels in canned products were far below the maximum regulatory limit, indicating that no significant tin was transferred from the can. Arsenic concentrations were higher in crustaceans such as fresh and frozen shrimps. The risk assessment performed indicated that fish and shellfish products were safe for the average consumer, although a potential risk cannot be dismissed for regular or excessive consumers of particular fish species, such as tuna, swordfish, blue shark and cat shark (for mercury) and common sole (for lead).

Biomonitorization of cadmium, chromium, manganese, nickel and lead in whole blood, urine, axillary hair and saliva in an occupationally exposed population

Heavy metal contamination from occupational origin is a cause for concern because of its potential accumulation in the environment and in living organisms leading to long term toxic effects. This study was aimed to assess Cd, Cr, Mn, Ni and Pb levels in whole blood, urine, axillary hair and saliva from 178 individuals with occupational exposure to heavy metals. Levels of metal compounds were determined by atomic absorption spectrometry. We collected information on occupation, lifestyle habits and food intake by questionnaire. Multiple linear regression analyses for metal ion concentration in whole blood, urine, axillary hair and saliva were adjusted for age, gender, smoking and alcohol consumption, lifetime workplace exposure, residence area and food habits. Overall, blood and urine median concentrations found for the five metals analyzed do not exceed biological exposure indexes, so that they are very similar to a non-occupationally exposed population. Toxicokinetic differences may account for the lack of correlations found for metal levels in hair and saliva with those in blood or urine. For those heavy metals showing higher median levels in blood with respect to hair (Cd, Mn and Pb) indicating lesser hair incorporation from blood, the lifetime working experience was inversely correlated with their hair levels. The longer the lifetime working experience in industrial environments, the higher the Mn and Ni concentration in saliva. Axillary hair and saliva may be used as additional and/or alternative samples to blood or urine for biomonitoring hair Mn, and saliva Ni in subjects with occupational exposure.

Validation of a method to quantify chromium, cadmium, manganese, nickel and lead in human whole blood, urine, saliva and hair samples by electrothermal atomic absorption spectrometry.

For biological monitoring of heavy metal exposure in occupational toxicology, usually whole blood and urine samples are the most widely used and accepted matrix to assess internal xenobiotic exposure. Hair samples and saliva are also of interest in occupational and environmental health surveys but procedures for the determination of metals in saliva and hair are very scarce and to our knowledge there is no validation of a method to quantify Cr, Cd, Mn, Ni and Pb in four different human biological materials (whole blood, urine, saliva and axilary hair) by electrothermal atomization atomic absorption spectrometry (ETAAS). In the present study, quantification methods for the determination of Cr, Cd, Mn, Ni and Pb in whole blood, urine, saliva and axilary hair were validated according to the EU common standards. Pyrolisis and atomization temperatures have been determined. The main parameters evaluated were: detection and quantification limits, linearity range, repeatability, reproducibility, recovery and uncertainty. Accuracy of the methods was tested with the whole blood, urine and hair certified reference materials and recoveries of the spiked samples were acceptable ranged from 96.3 to 107.8%.

Arsenic, cadmium, chromium and nickel in cancerous and healthy tissues from patients with head and neck cancer

Chronic exposure to heavy metals has long been recognized as being capable to increase head and neck cancer incidence among exposed human populations. Head and neck cancer is a significant public health issue in Tunisia. The aim of the present study was to evaluate the concentrations of As, Cd, Cr and Ni in healthy and tumor tissues of head and neck cancer patients. Metal concentrations were determined in tumor and healthy tissues of 101 head and neck cancer patients, using Atomic Absorption Spectrometry. The As, Cd, Cr, and Ni levels in tumor tissues were 3.4, 2.5, 1.3 and 1.5 times higher than those of healthy tissues (p<0.05), respectively. Tumor tissue metal levels were higher in men than in women. As and Cd levels in tumor and healthy tissue samples of patients smokers are significantly higher than those of non-smokers (p<0.05). A strong effect of cumulative smoking as expressed in the number of pack per year, and tumor tissue Cd levels were positively associated with three groups of age (<40, 51-60 and >60 years) in both never-smokers and ever-smokers (<20 and ≥20 pack per year). Healthy tissue Cd levels were negatively associated with age in those three groups of smokers. The highest Cd and Cr concentrations among both workers and non-workers were observed in tumor tissues. The Cd and Cr in tissues of farmers, bricklayers and painters were all significantly higher among the workers as compared with the non-workers group. Tissue metal levels have increased due to smoking and occupational exposure. Heavy metal exposure via tobacco smoking and occupational exposures may increase the risk of head and neck in the Tunisian population.

Determination of essential elements (copper, manganese, selenium and zinc) in fish and shellfish samples. Risk and nutritional assessment and mercury-selenium balance.

Fish and shellfish are an important source not only of toxic heavy metals, but also of essential elements in the diet. In this study, levels of Cu, Mn, Se and Zn have been determined in fresh, canned and frozen fish and shellfish products. A total of 485 samples of the 43 most frequently consumed fish and shellfish species in Andalusia (Southern Spain) were analyzed for essential elements content. The potential human health risks for the consumers and the nutritional value of the products analyzed were assessed. Furthermore, the mercury-selenium ratios and the selenium health benefit value (Se-HBVs) were calculated. The highest concentrations of Cu were found in crustaceans species (shrimp and prawn) as they have hemocyanin (a copper-containing protein) that functions as an oxygen-transport molecule. Mn levels were higher in canned bivalve molluscs, such as cockle and clam, and in fresh common sole. Concerning Se, two fresh predatory fish species (tuna and swordfish) presented the most remarkable concentrations of this element. The highest concentration of the essential metals analysed was found for Zn, especially in fresh and canned mussels. All the species analyzed showed beneficial Hg:Se ratios and Se-HBVs, except for the shark species (blue shark and cat shark) and gilt-head bream because of their high Hg levels and low Se content, respectively. Nevertheless, the biomagnification usually observed in hazardous metals such as Hg would not occur for the essential elements measured in predatory species. The estimated daily intakes of the elements studied represented very low percentages of their reference values, ranging from 0.1% (Se) to 3.9% (Cu) for person weighting 60 kg, so the intake of these elements through fish and shellfish would not pose any risk for the average consumer. Moreover, the contribution of fish and shellfish products to the recommended daily allowances and adequate intakes of these mineral elements ranges from 2.5% (Mn) to 25.4% (Se).

E-cigarettes as a source of toxic and potentially carcinogenic metals

Background and aims The popularity of electronic cigarette devices is growing worldwide. The health impact of e‐cigarette use, however, remains unclear. E‐cigarettes are marketed as a safer alternative to cigarettes. The aim of this research was the characterization and quantification of toxic metal concentrations in five, nationally popular brands of cig‐a‐like e‐cigarettes. Methods We analyzed the cartomizer liquid in 10 cartomizer refills for each of five brands by Inductively Coupled Plasma Mass Spectrometry (ICP‐MS). Results All of the tested metals (cadmium, chromium, lead, manganese and nickel) were found in the e‐liquids analyzed. Across all analyzed brands, mean (SD) concentrations ranged from 4.89 (0.893) to 1970 (1540) &mgr;g/L for lead, 53.9 (6.95) to 2110 (5220) &mgr;g/L for chromium and 58.7 (22.4) to 22,600 (24,400) &mgr;g/L for nickel. Manganese concentrations ranged from 28.7 (9.79) to 6910.2 (12,200) &mgr;g/L. We found marked variability in nickel and chromium concentration within and between brands, which may come from heating elements. Conclusion Additional research is needed to evaluate whether e‐cigarettes represent a relevant exposure pathway for toxic metals in users. HighlightsCertain brands of cig‐a‐like e‐cigarettes contain high levels of nickel and chromium.Cig‐a‐likes contain low levels of cadmium, compared to tobacco cigarettes.Nickel and chromium in the e‐liquid of cig‐a‐likes may come from nichrome heating coils.

Placental concentrations of heavy metals in a mother–child cohort

Heavy metals are environmental contaminants with properties known to be toxic for wildlife and humans. Despite strong concerns about their harmful effects, little information is available on intrauterine exposure in humans. The aim of this study was to evaluate prenatal exposure to As, Cd, Cr, Hg, Mn, and Pb and its association with maternal factors in a population-based mother-child cohort in Southern Spain. Between 2000 and 2002, 700 pregnant women were recruited and 137 placentas from the cohort were randomly selected and analyzed for the selected metals by atomic absorption. Maternal sociodemographic and lifestyle factors were obtained by questionnaire after delivery. Bivariate analysis and multivariate linear regression were performed. Cd and Mn concentrations were detected in all placentas, while Cr, Pb, and Hg were found in 98.5%, 35.0%, and 30.7% of samples, respectively. The highest concentrations were observed for Pb (mean: 94.80 ng/g wet weight of placenta), followed by Mn (63.80 ng/g), Cr (63.70 ng/g), Cd (3.45 ng/g), and Hg (0.024 ng/g). Arsenic was not detected in any sample. Gestational age and smoking during pregnancy were associated with placental Cd concentrations, while no factor appeared to influence concentrations of Cr, Hg, Mn, or Pb. In comparison to results of European studies, these concentrations are in a low-intermediate position. Studies are required to investigate the factors contributing to early exposure to heavy metals and to determine how placental transfer of these toxic compounds may affect childrens health.

A direct method for e-cigarette aerosol sample collection.

E-cigarette use is increasing in populations around the world. Recent evidence has shown that the aerosol produced by e-cigarettes can contain a variety of toxicants. Published studies characterizing toxicants in e-cigarette aerosol have relied on filters, impingers or sorbent tubes, which are methods that require diluting or extracting the sample in a solution during collection. We have developed a collection system that directly condenses e-cigarette aerosol samples for chemical and toxicological analyses. The collection system consists of several cut pipette tips connected with short pieces of tubing. The pipette tip-based collection system can be connected to a peristaltic pump, a vacuum pump, or directly to an e-cigarette user for the e-cigarette aerosol to flow through the system. The pipette tip-based system condenses the aerosol produced by the e-cigarette and collects a liquid sample that is ready for analysis without the need of intermediate extraction solutions. We tested a total of 20 e-cigarettes from 5 different brands commercially available in Maryland. The pipette tip-based collection system condensed between 0.23 and 0.53mL of post-vaped e-liquid after 150 puffs. The proposed method is highly adaptable, can be used during field work and in experimental settings, and allows collecting aerosol samples from a wide variety of e-cigarette devices, yielding a condensate of the likely exact substance that is being delivered to the lungs.

Trace metal quantification in bladder biopsies from tumoral lesions of Tunisian cancer and controls subjects

The incidence of bladder tumors has been dramatically increasing since the 1970s, possibly as a consequence of ongoing environmental pollution. Previous studies have provided some evidence of an association between cancer and exposure to carcinogenic metals. In order to examine the association between levels of toxic metals in patients with bladder tumors and controls, the amounts of arsenic, cadmium, chromium, and nickel were measured in tumoral lesions and adjacent normal part of the bladder mucosa excised for carcinoma and compared with those in the bladder mucosa of volunteer subjects operated for non-neoplastic diseases. The quantification of metals in tissue was assessed by atomic absorption spectroscopy. In tumoral tissues of the excised bladder mucosa, content of Cr and Ni was significantly low compared to that of adjacent normal tissues and control tissues while that of As and Cd in normal tissues adjacent to the tumor were significantly elevated compared to controls. Though the sample size was small, the present study shows that concentrations of metals such as Cd, Cr, As, and Ni in bladder tissue may be used as a biomarker of exposure. On the basis of the results obtained in this study, high amounts of As and Cd in adjacent normal parts of the bladders with carcinomas compared to controls would strongly suggest possible, individual or synergistic, effects of these pollutants on enzymatic systems, priming an oncogenic pathway.

Dietary determinants of cadmium exposure in the Strong Heart Family Study

Urinary cadmium (Cd) concentrations in the Strong Heart Family Study (SHFS) participants are higher than in the general US population. This difference is unlikely to be related to tobacco smoking. We evaluated the association of consumption of processed meats and other dietary products with urinary Cd concentrations in the SHFS, a family-based study conducted in American Indian communities. We included 1725 participants with urine Cd concentrations (standardized to urine creatinine) and food frequency questionnaire data grouped in 24 categories, including processed meat. Median (IQR) urinary Cd concentrations were 0.42 (0.20-0.85) μg/g creatinine. The age, sex, smoking, education, center, body mass index, and total kcal adjusted geometric mean ratio (GMR) (95%CI) of urinary cadmium concentrations per IQR increase in each dietary category was 1.16 (1.04-1.29) for processed meat, 1.10 (1.00-1.21) for fries and chips, 0.87 (0.80-0.95) for dairy products, and 0.89 (0.82-0.97) for fruit juices. The results remained similar after further adjustment for the dietary categories associated with urinary Cd in the previous model except for fries and chips, which was no longer statistically significant. These findings revealed the potential importance of processed meat products as a dietary source of cadmium.