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Cd bioaccumulation pattern was investigated in Mediterranean spider crab (Maya squinado, Herbst, 1788) collected from the northern Adriatic Sea. Specimens were caught in the framework of a monitoring plan in order to quantify the Cd distribution into different organs and tissues of crab. For this purpose, Cd level was studied in appendages, cephalothorax, abdomen as well as gonads. Cd concentrations were found largely below the Maximum Level (ML) established at the European Union (EU) level for muscle from crab appendages (found mean 0.011 mg kg(-1)) and approximately amounted to 2% of the EU ML (0.50 mg kg(-1)). The higher Cd concentrations were found in organs and tissues included in crab body such as abdomen, chephalotorax and gonads with respect to appendages. Chephalotorax showed the highest metal concentration (mean value of 1.19 mg kg(-1)). The possible differences in Cd bioaccumulation rate among crab organs and tissues were also investigated applying a parametric linear regression. A major Cd bioaccumulation rate was revealed in chephalotorax with respect to other analyzed organs and tissues. Furthermore, the evaluation of health risk related to human consumption of the Mediterranean spider crab has been studied for median of total population, median and 95th percentile of consumers of Italy. The observed results highlighted that the consumption of organs and tissues included in crab body such as abdomen, gonads and, in particular, chephalotorax substantially increased the Cd intake reaching also alarming Estimated Weekly Intake (EWI) values especially for median and 95th percentile of Italian consumers., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The presence of selected toxic heavy metals, such as cadmium (Cd), lead (Pb) and mercury (Hg), was investigated in fish and seafood products, namely, blue mussel, carpet shell clam, European squid, veined squid, deep-water rose shrimp, red mullet, European seabass, gilthead seabream, Atlantic cod, European hake, Atlantic bluefin tuna and swordfish so as to assess their human exposure through diet. Metals were detected by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) and hydride generation atomic absorption spectrometry (Hg-AAS). Measurements of Cd, Pb and Hg were performed by means of analytical methods validated in compliance with UNI CEI EN ISO/IEC 17025 [2005. General requirements for the competence of testing and calibration laboratories. Milano (Italy): UNI Ente Nazionale Italiano di Unificazione]. The exposure assessment was undertaken matching the levels of Cd, Pb and total Hg with consumption data related to fish and seafood products selected for this purpose. In order to establish human health implications, the estimated weekly intakes (EWIs) for Cd, Pb and Hg were compared with the standard tolerable weekly intakes (TWI) for Cd and provisional tolerable weekly intakes (PTWIs) for Pb and Hg stipulated by the European Food Safety Authority (EFSA) and the Food and Agriculture Organization/World Health Organization (FAO/WHO) Joint Expert Committee on Food Additives (JECFA). The found metal concentrations were largely below the maximum levels (MLs) established at the European Union level with the exception of Cd. This metal exceeded the MLs in squid, red mullet, European hake and Atlantic cod. Squid and blue mussel showed the highest Pb concentrations which accounted for 60% and 10% of the MLs, respectively. Highest Hg levels were found in predatory fish. The concentrations of Hg in swordfish, Atlantic bluefin tuna and red mullet accounted for 50%, 30% and 30% of the MLs, respectively. The EWIs for Cd, Pb and Hg related to the consumption of fish and seafood products by the median of the Italian total population accounted for 20%, 1.5% and 10% of the standard TWI for Cd as well as PTWIs for Pb and Hg, respectively. Furthermore, the EWIs estimated using consumption data concerning Italian consumers did not exceed the standard TWI and PTWIs, except for Cd at 95th percentile.

Seven hundred and twenty-six samples of wheat grains from the majority of Italian agricultural areas were pooled into 141 composite samples, homogeneous with respect to geographical origin and wheat variety. The average arsenic concentration of the pooled samples was 9 ng g(-1), with a range of 2-55 ng g(-1) (dry weight basis). The spread of arsenic concentrations (coefficient of variation of 91%) was related to spatial variability associated with geochemical and environmental factors. Temporal variability was investigated by a 3-year longitudinal study on 7 wheat cultivars grown in 22 areas of central and northern Italy. Average year-to-year variation in arsenic levels was low, and the average of the coefficients of variation was 23%. These results show that mapping of phytoavailable arsenic in agricultural soils can be done by measuring arsenic concentration in representative samples of wheat grains. Arsenic speciation in the grain showed that As(III) and As(V) were the major As compounds, highlighting the importance of wheat as a source of inorganic arsenic in the diet.

Arsenic (As) speciation in muscle tissues of freshwater fish was investigated with special emphasis on extraction yields and mass balances. For the quantification of water-soluble As compounds, samples were extracted using a 1:1 (v/v) methanol/water mixture. Various extraction parameters, such as extraction volume, number of additional extractions, intermediate and final volume in sample preconcentration were optimized so as to improve the extraction efficiency. Arsenic compounds were determined by HPLC with online ICP-MS, using both cation and anion exchange separation. The species studied were eel (Anguilla anguilla L.), flathead grey mullet (Mugil cephalus L.), chub (Leuciscus cephalus L.), and carp (Cyprinus carpio L.). Mean total As concentrations ranged from 354 microg kg(-1) dry weight (carp) to 1804 microg kg(-1) dry weight (mullet). Under optimized conditions, the percentage of total As extracted ranged from 64% for carp, to 82%, 84%, and 89% for grey mullet, eel and chub, respectively. Extraction of lipid-rich eel with n-hexane recovered some additional 3% of total As. The sizeable effect of sample matrix on HPLC retention time of some organoarsenicals in gradient elution cation exchange chromatography was exploited to achieve separation of coeluting compounds by analysing the same sample at different dilutions. The recovery of As from chromatographic columns was 101%, 102%, 103% and 104% for carp, chub, mullet and eel, respectively, indicating that no As was retained during chromatography. Arsenobetaine (AB) was the dominating As compound, but several other arsenicals, including arsenous acid (Asiii), arsenic acid (Asv), methylarsonic acid (MMA), dimethylarsinic acid (DMA), trimethylarsine oxide (TMAO), arsenocholine ion (AC), tetramethylarsonium ion (TETRA), oxo-arsenosugar-glycerol (AS1), oxo-arsenosugar-phosphate (AS2), oxo-arsenosugar-sulfate (AS4), thio-arsenosugar-phosphate (ThioAS2), and three unknown As compounds, were found. Arsenic speciation in carp was different compared to the other fish species, and a lower proportion of AB along with a high contribution of AS2 and ThioAS2 was found. DMA and TMAO were noteworthy minor compounds in eel and carp, respectively. Arsenic speciation and the chemical composition of fish muscle both appeared to affect the extraction yield., ((c) 2009 Elsevier B.V. All rights reserved.)

Wheat (Triticum aestivum) collected in the Nawanshahr-Hoshiarpur Region (Punjab, India) showed the highest selenium concentrations ever recorded in cereal grains (29-185 microg g(-1)). There was a strong positive relationship between the selenium content in shoots and that in kernels, showing that grain selenium concentration can be predicted from that in the vegetative tissues of the plant. The identity and content of the selenocompounds in the grain samples and in wheat-based reference materials were investigated by HPLC-ICP-dynamic reaction cell-MS. Reversed-phase, cation exchange, and anion exchange HPLC were used to separate the selenium species after ultrasound-assisted enzymatic extraction with an ultrasonic probe. Selenomethionine and selenate accounted for 72-85% and 2-6% of the sum of the selenium species, respectively. The proportion of organic Se species varied with increasing Se content; namely, SeMet showed a relative reduction whereas the other organoselenium compounds increased up to 18-22% of the total chromatographed selenium. Se-methyl-selenocysteine was detected as a minor compound (0.2-0.5%) in high-Se wheat by both reversed-phase and cation exchange HPLC using retention time matching with the standard substance spiked to the sample extracts. Regular consumption of locally produced wheat-based food items may lead the population of the study area to an excessive intake of selenium. On the other hand, the large predominance of selenomethionine shows that local wheat can be a promising raw material for naturally enriched products to be used to supplement human and animal diets in low selenium areas.

The distribution and potential bioaccumulation of dietary arsenic, cadmium, lead, mercury, and selenium in organs and tissues of rainbow trout (Oncorhyncus mykiss Walbaum, 1792), a major aquaculture species, was studied in relation to fish growth over a period of >3 years. Fish were reared under normal farming conditions, that is, fed a standard fish food and exposed to negligible levels of waterborne trace elements. The age-related variations in the content of each trace element in gills, kidney, liver, muscle, and skin were studied through nonparametric regression analysis. A buildup of all elements in all tissues and organs was observed, but due to dilution with growth, the concentrations did not increase, except in a few cases such as cadmium and mercury in liver and kidney. In muscle tissue, the concentrations of mercury, lead, and selenium did not alter significantly with growth, whereas cadmium increased but remained at exceedingly low levels. The concentration of arsenic in muscle tissue peaked at 14 months and then decreased in adult specimens. Arsenic speciation by high-performance liquid chromatography--inductively coupled plasma mass spectrometry revealed that arsenic in muscle was almost exclusively present in the form of nontoxic arsenobetaine. Application of a mercury mass balance model gave predicted concentrations in agreement with measured ones and showed that in farmed rainbow trout the ratio of mercury concentrations in feed and in fish is about 1:1. Therefore, rainbow trout does not approach the limits established for human consumption even when reared with feed at the maximum permitted levels. These findings highlight the low bioaccumulation potential of toxic trace elements such as cadmium, lead, and mercury in rainbow trout following dietary exposure. On the other hand, selenium concentrations in muscle (about 0.2 microg g (-1) of fresh weight) show that rainbow trout may be a good source of this essential element.

The preparation of a new candidate certified reference material (CRM) for trace elements based on the antarctic bivalve Adamussium colbecki(IRMM 813) was carried out by the Istituto Superiore di Sanità(ISS, Rome, Italy) in cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission (EC-JRC-IRMM), in the frame of the Italian National Programme of Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). Samples were collected at Terra Nova Bay (Ross Sea) during the 2000-2001 expedition in Antarctica. The preparation of a material suitable for certification was performed by the EC-JRC-IRMM. Measurements for homogeneity and short-term stability tests were carried out by ISS. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. For the above-mentioned tests, the determination of the elements of interest was performed on samples mineralised by microwave-assisted acid digestion. The analytical techniques employed to this end were inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry (ICP-DRC-Q-MS). The candidate material was shown to be fit for purpose with regard to homogeneity and short-term stability, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign.