Vekoslava Stibilj

Iodine in different food articles and standard reference materials

SummaryThe greater part of essential iodine enters living organisms via the food chain. Nevertheless, quantitative data on its concentration in diets, food articles and also in available SRMs are very poor and scarce. This and WHO recommendations on daily allowances of iodine for man via food articles caused an added demand for accurate and reliable determination of iodine in these samples. From this point of view the purpose of the present was to analyse and to establish the concentration levels of total iodine in some food articles, diets, SRMs and candidate reference materials by the use of rapid radiochemical separation, developed in our laboratory. The results were checked by the analysis of SRMs with available certified values for iodine and good agreement is evident.

Selenium Species in Selenium-Enriched and Drought-Exposed Potatoes

The aim of this work was to study selenium (Se) speciation in the potato ( Solanum tuberosum L.) cultivar Desiree, enriched in Se by foliar spraying with a water solution containing 10 mg of Se/L in the form of sodium selenate. Four combinations of treatments were used: well-watered plants with and without Se foliar spraying and drought-exposed plants with and without Se foliar spraying. Water-soluble Se compounds were extracted from potato tubers by water or enzymatic hydrolysis with the enzyme protease XIV, amylase, or a combination of protease XIV and amylase. Extraction was performed using incubation at a constant temperature and stirring (37 degrees C at 200 rpm) or by ultrasound-assisted extraction (300 W), using different extraction times. Separation of soluble Se species (SeCys2, SeMet, SeMeSeCys, selenite, and selenate) was achieved by ion-exchange chromatography, and detection was performed by inductively coupled plasma-mass spectrometry (ICP-MS). Results showed that the concentration of selenate extracted was independent of the enzymatic extraction technique (approximately 98 ng/g for drought-exposed and 308 ng/g for well-watered potato tubers), whereas the extraction yield of SeMet changed with the protocol used (10-36%). Selenate and SeMet were the main soluble Se species (representing 51-68% of total Se) in potato tubers, regardless of the growth conditions.

Speciation of inorganic arsenic in some bottled Slovene mineral waters using HPLC–HGAFS and selective coprecipitation combined with FI-HGAFS

Five bottled mineral waters from the Radenska and the Rogaska springs (Slovenia) were analyzed for their inorganic arsenic species As(III) and As(V) using existing speciation procedures. Both a hyphenated technique (HPLC-HGAFS) and a more conventional technique based on selective coprecipitation of As(III) with dibenzyldithiocarbamate prior to arsenic analysis (FI-HGAFS) were used. The techniques yielded data which were not significantly different on the 5% level, with HPLC-HGAFS to be the least sensitive (DL 1 microgl(-1)) and the selective coprecipitation technique to be suitable for sub pgl(-1) levels (DL 0.05 microgl(-1)). The latter technique showed recoveries of 96.4 +/- 0.4%. In none of the mineral waters As(III) was found whereas the Radenska minerals waters (vrelec Radin vrelec Miral, Kraljevi Vrelec) contained little As(V) (only detectable with the selective coprecipitation technique) and the Rogaska mineral waters (Tempel, Donat Mg) (very) high As(V) concentrations. Rogaska, Donat Mg even had an average As(V) concentration around the permittable level of 50 microgl(-1) for arsenic in minerals waters, viz. 47.8 microg l(-1). Speciation calculations based on pH and Eh and taking into account the ionic strength gave a similar speciation pattern then speciation analysis with additional information about the degree of protonation of As(III) and As(V).

Simultaneous determination of iodine and selenium in biological samples by radiochemical neutron activation analysis

SummaryRegarding the favourably sensitive nuclear characteristics of iodine and of selenium but the very different half lives of their induced nuclides 128I and 75Se, a radiochemical neutron activation analysis method for simultaneous determination of these elements in a single sample was developed. It is based on the double irradiation LICSIR technique — Long Irradiation for Se (40h), Cooling (a week or more), Short Irradiation for iodine (1–15 min) with following Radiochemistry. After the second short irradiation, the sample is ignited in an oxygen flask and iodine and selenium are sequentially and selectively extracted as elemental iodine and 5-nitro-2,1,3 benzoselena diazole chelate. With the described method biological samples were analysed and the reliability of the results was checked by the analyses of different standard reference materials. Good agreement with certified values and high radiochemical purity of the spectra show the applicability of the radiochemical separation developed.

Assessment of pollution level using Mytilus galloprovincialis as a bioindicator species: The case of the Gulf of Trieste

A multidisciplinary approach was used to estimate the pollution level of the marine environment in the North Eastern Adriatic by measurement of the isotopic composition of carbon and nitrogen (δ(13)C, δ(15)N), metal/metalloids analyses (Fe, Cu, Zn, As, Se, Cd and Pb, including As speciation) in the Mytilus galloprovincialis, as well by using metallothioneins (MT) concentrations, micronuclei (MN) in gill cells and biological parameters (condition index and gonadosomatic index). Concentrations of MT were in the range from 44 to 175 μg g(-1) wet matter tissue and were higher at the end of the winter season. The frequency of MN did not indicate an elevated level. Sewage sludge pollution was not confirmed. Elevated As concentrations in mussel are related to salinity and low nutrients concentrations and not to pollution. Elevated concentrations of Cu, Zn and Pb were found in the Bay of Koper in comparison with the Bays of Strunjan and Piran.

Distribution of Se and its species in Myriophyllum spicatum and Ceratophyllum demersum growing in water containing Se (VI).

The uptake of Se (VI) by two aquatic plants, Myriophyllum spicatum L. and Ceratophyllum demersum L., and its effects on their physiological characteristics have been studied. Plants were cultivated outdoors under semi-controlled conditions and in two concentrations of Na selenate solution (20 μg Se L(-1) and 10 mg Se L(-1)). The higher dose of Se reduced the photochemical efficiency of PSII in both species, while the lower dose had no effect on PSII. Addition of Se had no effect on the amounts of chlorophyll a and b. The concentration of Se in plants grown in 10 mg Se L(-1), averaged 212 ± 12 μg Seg(-1) DM in M. spicatum (grown from 8-13 d), and 492 ± 85 μg Se g(-1) DM in C. demersum (grown for 31 d). Both species could take up a large amount of Se. The amount of soluble Se compounds in enzyme extracts ranged from 16% to 26% in control, and in high Se solution from 48% to 36% in M. spicatum and C. demersum, respectively. Se-species were determined using HPLC-ICP-MS. The main soluble species in both plants was selenate (∼37%), while SeMet and SeMeSeCys were detected at trace levels.

The uptake and distribution of selenium in three aquatic plants grown in Se(IV) solution.

The uptake of Se(IV) by Myriophyllum spicatum, Ceratophyllum demersum and Potamogeton perfoliatus, and the effects of Se(IV) on their physiological and biochemical characteristics were studied. Plants were cultivated outdoors under semi-controlled conditions in water solution containing Na selenite (20 μg Se L(-1) and 10 mg Se L(-1)). The higher concentration of Se lowered the photochemical efficiency of PSII in all species studied, while the lower concentration had no effect on any species. The higher concentration of Se lowered respiratory potential in M. spicatum. The response of M. spicatum and C. demersum to Se(IV) regarding chlorophylls was variable, however in the majority of cases, there was a trend of increasing the amount of chlorophylls, while in P. perfoliatus the amount of chlorophyll a decreased. The concentration of Se in plants cultured in 10 mg Se(IV) L(-1) ranged from 436 to 839 μg Se g(-1) DM in M. spicatum, 319 to 988 μg Se g(-1) DM in C. demersum and 310 to 661 μg Se g(-1) DM in P. perfoliatus. The amount of soluble Se compounds in enzyme extracts of high Se treatment was 27% in M. spicatum, 41% in C. demersum and 35% in P. perfoliatus. Se compounds were determined using HPLC-ICP-MS. It was observed that the applied Se(IV) was mainly transformed to insoluble Se.

Effect of arsenic trioxide on metallothionein and its conversion to different arsenic metabolites in hen liver.

The metabolism of arsenic, its affinity to metallothionein (MT), its influence on selenium levels, and its biotransformation to different metabolites in the liver tissue of laying hens exposed to arsenic trioxide (As2O3) was investigated. The experiment was performed with two groups of hens fed for 19 d with either a standard diet or with the same diet enriched in arsenic (30 µg/g). The major findings were as follows:1.After 19 d exposure, about 65% of the total liver As was found in the water-soluble phase (100,000g centrifuged supernatant). In liver supernatant, As binding was found mostly in the range of very low-molecular-weight proteins (Mr<10,000). Although after exposure the amount of MT-like proteins increased, the As bound to it was only in trace amounts. The protein was identified by convential procedures as Zn,Cu-thionein with traces of selenium and arsenic.2.Arsenic exposure resulted in almost unchanged Se levels regarding its tissue concentrations and distribution between supernatant and pellet, where about 10% of total Se was found in the supernatant. On the contrary, As exposure did affect Cd levels. Tissue Cd concentration was slightly diminished, but the percentage of tissue Cd found in the water-soluble phase was increased from 20% to 40%.3.In methanol extracts of tissue and supernatant of the As-exposed group, only two arsenic compounds were detected, As(III) and dimethylarsinic acid (DMA), the latter prevailing.

Applicability of neutron activation analysis (NAA) in quantitative determination of some essential and toxic trace elements in food articles

Accurate and reliable data on microgram and nanogram quantities of some essential and toxic elements in most food articles are very scarce. Neutron activation analysis (NAA), with its essentially blankfree advantage, is a valuable approach in the field of determination of trace elements in different foodstuffs and diets. Accordingly, various radiochemical (RNAA) and instrumental (INAA) approaches have been developed in our laboratory for the elements As, Cd, Co, Cu, Hg, I, Mo, Ni, Sb, Se, Sn, Th, U, V, and others, and verified by the analysis of compositionally appropriate certified reference materials.

Maternal diet and selenium concentration in human milk from an Italian population.

Background Low selenium (Se) status is associated with several diseases. International organizations have proposed intakes of Se for general populations, including infants. Studies of the association of Se concentration in breast milk and maternal diet have yielded inconsistent results. We evaluated the relation between the intake of food items during pregnancy and Se concentration in human milk after delivery and compared infant intake of Se from breast milk with the recommended intakes. Methods This cross-sectional study was part of the baseline assessment of a prospective cohort of Italian mother–child pairs enrolled in 1999–2001. Se concentration was measured in the milk of 100 women included in the cohort and correlated with the intake of food items during pregnancy and lactation as reported in a food frequency questionnaire. Results Among foods consumed in pregnancy, only eggs had a positive, but weak, correlation with Se concentration in milk (r = 0.20, P = 0.04). Fish intake during lactation was also weakly correlated with Se in milk (r = 0.21, P = 0.04). Se content of breast milk in our population was lower than that noted in other international studies; however, very few children who were exclusively breastfed were estimated not to have met the recommended Se intake. Conclusions Future research should aim to verify whether infants in this part of Italy still meet the recommended nutrient intake of Se and to assess the influence of the concurrent diet of lactating mothers on the Se content of their milk.