The Impact of Various Types of Cooking on the Fate of Hg and Se in Predatory Fish Species.

This study addresses the effect of various cooking approaches on total Hg (HgT) and total Se (SeT) contents in three predatory fish species. For this purpose, samples of swordfish, dogfish, and tuna from regular French (fish) markets were cooked by boiling, steaming, grilling, and frying, respectively. The levels of HgT and SeT in raw and cooked samples were determined by inductively coupled plasma-mass spectrometry. The data showed a significant increase in HgT and SeT levels between raw and cooked samples (33% of the samples for SeT and 67% for HgT) due to the water loss during the cooking. High intra-species variation related to HgT and SeT levels was found. Considering the level of exposure to HgT through fish consumption and taking also into account the possible protective effect of Se (expressed here via the Se/Hg molar ratio), the safest cooking approach corresponds to grilled swordfish, fried tuna, and steamed dogfish, which show Se/Hg molar ratios of (1.0 ± 0.5), (4.3 ± 4.2), and (1.0 ± 0.6), respectively.

Trace elements and arsenic speciation in Paracentrotus lividus from North-West Mediterranean Sea.

Levels of 14 trace elements (Al, Ti, V, Cr, Mn, Co, Ni, Zn, As, Se, Cd, Sn, Hg, and Pb) and 5 arsenic species (arsenite/As(III), arsenate/As(V), monomethylarsonic acid/MA, dimethylarsinic acid/DMA, and arsenobetaine/AsB) were assessed in the gonads of sea urchin samples (Paracentrotus lividus) from North-West Mediterranean Sea (French coast). The samples were collected from 13 sites characterized by different types and levels of chemical contamination. Trace elements levels were measured by inductively coupled plasma-mass spectrometry (ICP-MS) following microwave (acid) digestion in a closed system, whereas As speciation analysis was carried out by ion-exchange liquid chromatography coupled with ICP-MS after microwave-assisted extraction. High levels of trace elements were found in sea urchins sampled from Corsica whereas the samples from Théoule were found to be the least contaminated. From all the analyzed urchin samples, none showed Cd, Hg, or Pb concentrations above the regulatory levels set by the European Community (EC) No. 1881/2006 for seafood or bivalve mollusks. Regarding arsenic speciation, AsB was confirmed to be the predominant species. Inorganic As (As(III) + As(V)) was mainly constituted by As(III), which was quantified in all samples. Methylated As forms (MA and DMA) represent 9 to 23% of the total As.

Assessment of Differentiated Thyroid Carcinomas in French Polynesia After Atmospheric Nuclear Tests Performed by France.

Importance: Due to the amount of iodine 131 released in nuclear tests and its active uptake by the thyroid, differentiated thyroid carcinoma (DTC) is the most serious health risk for the population living near sites of nuclear tests. Whether low doses to the thyroid from nuclear fallout are associated with increased risk of thyroid cancer remains a controversial issue in medicine and public health, and a misunderstanding of this issue may be associated with overdiagnosis of DTCs. Design, Setting, and Participants: This case-control study was conducted by extending a case-control study published in 2010 that included DTCs diagnosed between 1984 and 2003 by adding DTCs diagnosed between 2004 and 2016 and improving the dose assessment methodology. Data on 41 atmospheric nuclear tests conducted by France between 1966 and 1974 in French Polynesia (FP) were assessed from original internal radiation-protection reports, which the French military declassified in 2013 and which included measurements in soil, air, water, milk, and food in all FP archipelagos. These original reports led to an upward reassessment of the nuclear fallout from the tests and a doubling of estimates of the mean thyroid radiation dose received by inhabitants from 2 mGy to nearly 5 mGy. Included patients were diagnosed from 1984 to 2016 with DTC at age 55 years or younger and were born in and resided in FP at diagnosis; 395 of 457 eligible cases were included, and up to 2 controls per case nearest by birthdate and matched on sex were identified from the FP birth registry. Data were analyzed from March 2019 through October 2021. Exposure: The radiation dose to the thyroid gland was estimated using recently declassified original radiation-protection service reports, meteorological reports, self-reported lifestyle information, and group interviews of key informants and female individuals who had children at the time of these tests. Main Outcomes and Measures: The lifetime risk of DTC based on Biological Effects of Ionizing Radiation (BEIR) VII models was estimated. Results: A total of 395 DTC cases (336 females [85.1%]; mean [SD] age at end of follow-up, 43.6 [12.9] years) and 555 controls (473 females [85.2%]; mean [SD] age at end of follow-up, 42.3 [12.5] years) were included. No association was found between thyroid radiation dose received before age 15 years and risk of DTC (excess relative risk [ERR] per milligray, 0.04; 95% CI, -0.09 to 0.17; P = .27). When excluding unifocal noninvasive microcarcinomas, the dose response was significant (ERR per milligray, 0.09; 95% CI, -0.03 to 0.02; P = .02), but several incoherencies with the results of the initial study reduce the credibility of this result. The lifetime risk for the entire FP population was 29 cases of DTC (95% CI, 8-97 cases), or 2.3% (95% CI, 0.6%-7.7%) of 1524 sporadic DTC cases in this population. Conclusions and Relevance: This case-control study found that French nuclear tests were associated with an increase in lifetime risk of PTC in FP residents of 29 cases of PTC. This finding suggests that the number of thyroid cancer cases and the true order of magnitude of health outcomes associated with these nuclear tests were small, which may reassure populations of this Pacific territory.

Development and validation of a single run method based on species specific isotope dilution and HPLC-ICP-MS for simultaneous species interconversion correction and speciation analysis of Cr(III)/Cr(VI) in meat and dairy products.

This study presents the development, validation and application of a new analytical approach for the simultaneous speciation analysis of Cr(III) and Cr(VI) in meat and dairy products by high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) and double spike species specific-isotope dilution (SS-ID). The species extraction was achieved by sequential complexation of Cr(III) with ethylenediaminetetraacetic acid (EDTA) and of Cr(VI) with 1,5-diphenylcarbazide (DPC) in the same analytical run. The HPLC separation of complexed species was carried out using a short (5 cm) microbore anion-exchange HPLC column and a mobile phase consisting of 0.01 mol L-1 HNO3 + 2.5% (v/v) MeOH + 0.30 mol L-1 EDTA (pH = 2) in isocratic elution mode with excellent baseline separation achieved in less than 3 min. The method was validated by means of the accuracy profile approach by carrying out 6 measurement series in duplicate on (six) different days over a timespan of two months. The quantification limit was 0.013 µg kg-1 for Cr(III) and 0.049 µg kg-1 for Cr(VI), respectively. The measurement bias corresponding to the validity domain ranged from 0.01 to 0.11%, whereas the coefficient of variation in terms of repeatability (CVr) varied from 2.9 to 11.6% (depending on the analyte level) for Cr(III) and from 6.7 to 11.8% for Cr(VI). Similarly, the coefficient of variation in terms of intermediate reproducibility (CVR) ranged from 6.8 to 13% for Cr(III) and from 6.8 to 25.9% for Cr(VI), respectively. The method was successfully applied to the analysis of a selection of food samples such as baby and semi-skimmed milk and steak beef samples. Cr(VI) was not quantified in any of these samples while Cr(III) levels ranged between 2.7 and 4.7 µg kg-1, which were comparable with the levels of total chromium analysed in the same samples by ICP-MS (accredited method). The method presented here with combined use of species specific isotope dilution and sequential species complexation is a powerful analytical tool for accurate and precise quantification of Cr(III) and Cr(VI) at trace levels and allows for correction of any species interconversion during sample preparation.

Non-Essential Trace Elements Dietary Exposure in French Polynesia: Intake Assessment, Nail Bio Monitoring and Thyroid Cancer Risk

Background: In French Polynesia, thyroid cancer mortality and incidence is reported to be the highest in the world. Excessive levels of non-essential trace elements (nETE) in the body are associated with several types of cancer. Objective: The present study aims to provide quantitative information on food contamination by mercury (Hg), lead (Pb), arsenic (As) and cadmium (Cd) in French Polynesia and its potential correlation with measurements performed in fingernails of Polynesians, and then to investigate the potential association between these nETE and different thyroid cancer risks. Methods: The study population included 229 interviewed cases and 373 interviewed controls We performed a descriptive analysis of Polynesian food and examined the association between thyroid cancer risk and daily intake levels of nETE and with fingernail nETE levels. Results: Hg contamination was mainly present in sea products, Pb contamination was present in almost all samples, Cd was detectable in starchy food and As was detectable in all sea products. No patient exceeded dietary contamination WHO limits for Pb, 2 participants exceeded it for Hg and 3 individuals (0.5%) for cadmium. In fingernail clippings, the most detectable pollutant was Pb (553 participants), then Hg (543 participants) then Cd (only in 130 participants). Thyroid cancer risk was increased more than 4 times by Pb daily intake in patients with a history of cancer in first-degree relatives than in ones without (p for interaction =0.01), and 2 times more in women with more than 3 pregnancies than in those with none or less (p for interaction =0.005); it was also increased following As intake by more than 30% in patients with a history of cancer in first-degree relatives than in ones without (p for interaction =0.05). Conclusion: Locally produced foods are not a source of nETE exposure in French Polynesia. Dieatry nETE exposure and fingernail nETE concentration are not associated to differentiated thyroid cancer risk. No correlation found between nETE dietary exposure and fingernail nETE concentration.

FOXE1 Polymorphism Interacts with Dietary Iodine Intake in Differentiated Thyroid Cancer Risk in the Cuban Population.

BACKGROUND: The incidence of differentiated thyroid cancer (DTC) is low in Cuba, and the contribution of dietary factors to DTC in this population has not been investigated so far. The aim of this study was to evaluate the relationship between dietary iodine intake and DTC with regard to the interaction with environmental factors or some common single nucleotide polymorphisms (SNPs), based on a case-control study carried out in Cuba. METHODS: A total of 203 cases and 212 controls from the general population were interviewed face-to-face using the dietary intake questionnaire and the photo booklet from the E3N cohort. A specific food composition table was constructed for this study. For each parameter studied, the odds ratio (OR) was stratified on age group and sex, and further adjusted for dietary energy, smoking status, ethnic group, level of education, number of pregnancies, and body surface area. RESULTS: The risk of DTC was significantly reduced with increasing consumption of fish (p = 0.04), but no association between total dietary iodine intake and DTC risk was evident (p = 0.7). This lack of significant association was true whatever the age, the smoking status, the dietary selenium intake, and the ethnicity (p > 0.05). DTC risk was positively and strongly associated with the number of copies in the minor allele (A) for SNP rs965513 near FOXE1 among people who consumed less iodine than the median (p = 0.005). CONCLUSION: Overall, the majority of the studied population had an optimal dietary iodine intake. DTC risk was inversely associated with high fish consumption. Furthermore, DTC risk was positively associated with the number of copies in the minor allele (A) of rs965513 among people who consumed less iodine than the median. Because these findings are based on post-diagnostic measures, studies with pre-diagnostic dietary iodine are needed for confirmation.

Determination of total iodine in French Polynesian foods: method validation and occurrence data.

Pacific Island populations show some of the highest incidences of thyroid cancer in the world, and iodine deficiency is suspected to play a role. Iodine content was determined in 124 different French Polynesian food samples using inductively coupled plasma-mass spectrometry after alkaline digestion. For samples containing starch, the method was optimised by including an additional enzymatic treatment step. This analytical method was validated with an accuracy profile approach, using certified reference materials with iodine contents ranging from 0.027 to 4.95mgiodinekg(-1) dry weight. The trueness bias ranged from -5.8% to 22.4% and the highest observed intermediate precision coefficient of variation CVR was 11% in starchy materials. Tested Polynesian foods showed large variation in iodine content, with values of 0.014-0.032mgkg(-1) for fruits, 0.014-0.081mgkg(-1) for starchy samples, 0.027-1.85mgkg(-1) for green vegetables, 0.222-5.19mgkg(-1) for fish, 6.51-85.6mgkg(-1) for shellfish, and 0.004-1.39mgkg(-1) for beverages.

Use of a continuous leaching method to assess the oral bioaccessibility of trace elements in seafood.

A continuous leaching method, coupled online with inductively coupled plasma mass spectrometry (ICP-MS) was used on seafood samples to assess the maximum bioaccessibility of several trace elements. The method indeed involves continuous leaching of the food sample by artificial saliva and gastric juice, successively, where this exposition of the food to fresh reagent drives the dissolution equilibrium to the right. Leaching with intestinal juice had to be omitted because it resulted in clogging problems. The experimental apparatus includes a mini-column of powdered sample, which is directly connected to the nebulizer of an ICP-MS instrument. The on-line approach allows a quick assessment of the maximum bioaccessibility of elements of interest by monitoring the real-time release of elements by a given reagent. The method was applied to determine the bioaccessibility of four toxic elements (Al, Cd, Hg, and Pb) and of four essential elements (V, Mn, Cu, and Zn) in certified reference materials and in actual seafood samples. In all cases, mass balance was verified by carrying out the total digestion of the remaining residue from the mini-column and the relationship between total concentration and bioaccessibility was examined.

Bioaccessibility of total arsenic and arsenic species in seafood as determined by a continuous online leaching method.

A continuous leaching method coupled online with inductively coupled plasma mass spectrometry (ICP-MS) detection was used to assess the maximum bioaccessibility of arsenic (As) in seafood samples. The method simulates continuous-flow digestion by successively pumping artificial saliva, gastric and intestinal juices through a mini-column of powdered sample directly connected to the nebuliser of an ICP-MS instrument. The method allows the real-time measurement of As being released by a given reagent. Because the analyte is continuously removed from the system, in contrast to batch methods, the dissolution equilibrium is driven to the right, hence quickly providing information about the worst-case scenario. Following consecutive leaching by the digestive reagents, the leachates were subject to speciation analysis by ion-exchange chromatography with ICP-MS detection to determine the arsenic species released. Finally, the remaining residue from the mini-column was fully digested to verify mass balance. The method was used to determine the bioaccessibility of total As and As species in four certified reference materials and in several real seafood samples. The mass balance was verified in each case. Generally speaking, the non-toxic form was easily released whereas the inorganic forms were poorly bioaccessible.

Determination of seven arsenic species in seafood by ion exchange chromatography coupled to inductively coupled plasma-mass spectrometry following microwave assisted extraction: method validation and occurrence data.

The determination of seven arsenic species in seafood was performed using ion exchange chromatography on an IonPac AS7 column with inductively coupled plasma mass spectrometry detection after microwave assisted extraction. The effect of five parameters on arsenic extraction recoveries was evaluated in certified reference materials. The recoveries of total arsenic and of arsenic species with the two best extraction media (100% H(2)O and 80% aqueous MeOH) were generally similar in the five seafood certified reference materials considered. However, because MeOH co-elutes with arsenite, which would result in a positively biased arsenite concentration, the 100% H(2)O extraction conditions were selected for validation of the method. Figures of merit (linearity, LOQs (0.019-0.075 mg As kg(-1)), specificity, trueness (with recoveries between 82% (As(III)) and 104% (As(V) based on spikes or certified concentrations), repeatability (3-14%), and intermediate precision reproducibility (9-16%) of the proposed method were satisfactory for the determination of arsenite, monomethylarsonic acid, dimethylarsinic acid, arsenate, arsenobetaine and arsenocholine in fish and shellfish. The performance criteria for trimethylarsine oxide, however, were less satisfactory. The method was then applied to 65 different seafood samples. Arsenobetaine was the main species in all samples. The percentage of inorganic arsenic varied between 0.4-15.8% in shellfish and 0.5-1.9% at the utmost in fish. The main advantage of this method that uses only H(2)O as an extractant and nitric acid as gradient eluent is its great compatibility with the long-term stability of both IEC separation and ICP-MS detection.