G. Marcotrigiano

Heavy metal residues in tissues of marine turtles

Heavy metal concentrations in the tissues of marine turtles are presented. The most frequently monitored elements are mercury, cadmium and lead; and the tissues mainly analysed in nearly all the stranded individuals are muscle, liver and kidney. The highest mercury and cadmium levels were found in liver and kidney respectively; the majority of the lead burden existed in bones and carapace, while arsenic was present mainly in muscle tissue. Mercury occurred quite completely as methylmercury in muscle, whereas in liver the main form was the inorganic one. Arsenic was exclusively present in the metallorganic form either in muscle tissue or in liver. Metals in the eggs were mainly present in the yolk. Significantly higher concentration of mercury, copper, zinc and iron were found in yolk than albumen, while shell contained highest levels of manganese and copper. The load of trace metals in these animals strictly correlated with the species seems to depend on their different food behaviour.

Heavy metals in the aquatic environment of the Southern Adriatic Sea, Italy: Macroalgae, sediments and benthic species

Samples of sea urchins (Paracentrotus lividus), holothurians (Holothuria polii), green algae (Ulva lactuca. Codium vermilara and Enteromorpha prolifera) and sediments were collected from different coastal zones of the South Adriatic Sea (Italy). The occurrence of metals in macroalgae is poor especially if compared with that reported in other coastal areas affected by human activities, with the exception of Fe that showed high mean values (405 microg g(-1) dry wt.). Likewise, relationships between metal concentrations in holothurians and sediments were found, demonstrating that H. polii could serve as bioindicator for Hg and Cu.

Total and methylmercury residues in cartilaginous fish from Mediterranean Sea.

Concentrations of mercury and methylmercury residues were determined in the muscle tissue of three cartilaginous fishes Chimaera monstrosa (ghostshark), Torpedo nobiliana (electric ray) and Myliobatis aquila (eagle ray) from the Mediterranean Sea. The highest mean levels of total mercury were detected in ghostshark (3.14 mg/kg wet weight), followed by electric ray (2.42 mg/kg wet weight), and eagle ray (0.83 mg/kg wet weight). Such a variability is influenced by quite a number of factors, among which size, fish ecology and feeding habits. The percentages of the methylated form to total mercury ranged from a minimum of 72% in eagle ray to a maximum of 83% in ghostshark. Relationship between specimen size and mercury and methylmercury concentrations were found in ghostshark species.

Piperidine-, thiomorpholine-4- and n-methylpiperazine-4-carbodithioate transition metal complexes

Abstract Piperidinecarbodithioate (Pipdtc), thiomorpholine-4- (Timdtc) and N-methylpiperazine-4- carbodithioate (CH3Pzdtc) complexes of iron(III), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II) have been prepared and characterized by magnetic and spectroscopic techniques. Structures are proposed based upon the spectra of these new dithiocarbamate complexes.

Mercury in fish: Concentration vs . fish size and estimates of mercury intake

Total mercury concentrations were determined in different fish size classes of commercial importance such as, conger eel (Conger conger), starry ray (Raja asterias), forkbeard (Phycis blennoides), frostfish (Lepidopus caudatus), striped mullet (Mullus barbatus), red gurnard (Aspitrigla cuculus) and yellow gurnard (Trigla lucerna) in order to evaluate variations in consumer exposure to mercury as a function of fish consumption of a spectrum of different sizes. The highest mean levels of total mercury were detected in conger eel (0.80 µg g−1) and starry ray (0.75 µg g−1). Forkbeard (0.67 µg g−1), frostfish (0.59 µg g−1) and striped mullet (0.55 µg g−1) showed slightly lower levels, while red gurnard (0.33 µg g−1) and yellow gurnard (0.22 µg g−1) exhibited the lowest concentrations. The results of linear regression analysis showed a significant relationship between mercury concentrations and fish size for all species. Consequently, dietary consumption of larger size specimens leads to an increase in the exposure level for consumers. Understanding by consumers of all factors leading to an increase of exposure to mercury is the first step to enable them to make decisions about eating fish.

Survey of total mercury and methylmercury levels in edible fish from the Adriatic Sea

Total mercury and methylmercury concentrations were measured in the muscle tissue of different fish species from the Adriatic Sea to ascertain whether the concentrations exceeded the maximum level fixed by the European Commission. Large species-dependent variability was observed. The highest total mercury mean concentrations were in benthic (0.20–0.76 μg g−1 wet wt) and demersal fish (0.22–0.73 μg g−1 wet wt), while pelagic species showed the lowest levels (0.09–0.23 μg g−1 wet wt). In 15% of frost fish, in 42% of skate and in 30% of angler fish samples total mercury concentrations exceeded the maximum level fixed by the European Commission (Hg = 1 μg g−1 wet wt); for the species for which the maximum level was set to 0.5 μg g−1 wet wt, concentrations exceeding the prescribed legal limit were observed in 6.4% of bokkem, in 6.6% of pandora, in 20% of megrin, in 12.5% of four-spotted megrim, in 16% of striped mullet, in 5.0% of forkbeard and in 5.3% of picarel samples. In all the different species, mercury was present almost completely in the methylated form, with mean percentages between 70 and 100%. Weekly intake was estimated and compared with the provisional tolerable weekly intake recommended by the FAO/WHO Expert Committee on Food Additives. A high exposure was associated with the consumption of only skates, frost fish and angler fish, thought the consumption of the other species, such as, megrim, four spotted megrim, red fish striped mullet and forkbeard, resulted in a weekly intake slightly below the established provisional tolerable weekly intake.

Levels and congener pattern of polychlorinated biphenyls in the blubber of the Mediterranean bottlenose dolphins Tursiops truncatus.

Isomer specific concentrations of individual polychlorinated biphenyls (PCBs) including toxic non-ortho (IUPAC 77, 126, 169) and mono-ortho (105, 118, 156) coplanar congeners were determined in the blubber of nine bottlenose dolphins (Tursiops truncatus) stranded along the Eastern Italian coast. The total PCB concentrations ranged from 3534 to 24375 ng/g wet wt. The PCB profile was dominated by congeners 138 and 153 collectively accounting for 55% of the total PCB concentrations. Among the most toxic congeners the order of abundance was 126>169>77. The mean total 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalent of six coplanar PCBs in the blubber of bottlenose dolphins was 45596 pg/g. Non-ortho congeners contributed greater to the 2,3,7,8-TCDD toxic equivalents than mono-ortho members. Particularly, PCB 126 was the major contributor to the estimated toxic potency of PCBs in dolphins.

Polychlorinated biphenyls, hexachlorobenzene, hexachlorocyclohexane isomers, and pesticide organochlorine residues in cod-liver oil dietary supplements.

Levels of polychlorinated biphenyls (PCBs), hexachlorobenzene, hexachlorocyclohexane isomers (alpha, beta, gamma), and chlorinated pesticides (DDTs) in cod-liver oil used as a dietary supplement were determined. Total PCB and DDT concentrations varied from 25 to 201 ng g(-1) lipid weight basis and from 25 to 133 ng g(-1) lipid weight basis, respectively. Hexachlorobenzene contributed very little to the overall contaminant burden of dietary supplement oils, whereas hexachlorocyclohexane isomers were below the instrumental detection limits in all samples. The daily intake of PCBs and DDTs derived by the consumption of cod-liver oil at manufacturer-recommended doses varied from 0.004 to 2.01 microg/day and from 0.004 to 1.24 microg/day, respectively. Relative to some dioxin-like PCB congeners (mono-ortho PCB 105, 118, and 156; non-ortho PCB 77, 126, and 169), the intakes calculated varied from less than 0.001 to 0.74 pg of toxic equivalency values (TEQ) per kg of body weight per day. These values, although below the range of 1 to 4 pg of TEQ per kg of body weight per day set by the World Health Organization, emphasize the need for strict and continuous monitoring of fish oil contamination to reduce, as much as possible, the risks to human health.

Cadmium and mercury in cephalopod molluscs: Estimated weekly intake

Cadmium and mercury concentrations were measured in the flesh and hepatopancreas of different species of cephalopod molluscs (European squid, common octopus, curled octopus, horned octopus, pink cuttlefish, common cuttlefish) in order to establish whether the concentrations exceeded the maximum levels fixed by the European Commission. In hepatopancreas, the levels of cadmium were substantially higher than those in flesh (flesh 0.11–0.87 µg g−1 wet weight, hepatopancreas 2.16–9.39 µg g−1 wet weight), whilst the levels of mercury (flesh 0.13–0.55 µg g−1 wet weight, hepatopancreas 0.23–0.79 µg g−1) were approximately double those in flesh. Concentrations exceeding the maximum permitted limit of cadmium were found in 39.8 and 41.0% of common octopus and pink cuttlefish flesh, respectively. For mercury, concentrations above the limit were found only in octopuses, and precisely in 36.8, 50.0 and 20.0% of flesh samples of common, curled and horned octopus, respectively. In the hepatopancreas, concentrations of cadmium and mercury were above the proposed limits in all the samples examined. The estimated weekly intake of between 0.09 and 0.49 µg kg−1 body weight for cadmium and between 0.05 and 0.24 µg kg−1 body weight for mercury made only a small contribution to the provisional tolerable weekly intake (cadmium 1.3–7.0%, mercury 1.0–4.8%) set by the WHO.

Adducts of Piperidine, Piperazine, Methylpiperazine, and Morpholine with Bis(β-Ketoenolates) of Nickel(II)

The bis(β-ketoenolates)nickel(II) adducts of piperidine, piperazine, methylpiperazine, and morpholine are isolated in the solid state and investigated by magnetic measurements and electronic and i.r. spectra. Magnetic measurements and electronic spectra give evidence of trans-octahedral configuration while i.r. spectra show that the amines are coordinated to the nickel atom towards the nitrogen atom. The new band found in the range 385–300 cm−1 for all complexes can be assigned to Ni—N vibration. In the Ni(DBM)2•4B (B = methylpiperazine and morpholine) the two additional bases are not coordinated to the metal atom.