Isotopic identification of natural vs. anthropogenic lead sources in marine sediments from the inner Ría de Vigo (NW Spain).

San Simón Bay, the inner part of the Ría de Vigo (NW Spain), an area previously identified as highly polluted by Pb, was selected for the application of Pb stable isotope ratios as a fingerprinting tool in subtidal and intertidal sediment cores. Lead isotopic ratios were determined by inductively coupled plasma mass spectrometry on extracts from bulk samples after total acid digestion. Depth-wise profiles of (206)Pb/(207)Pb, (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)Pb and (208)Pb/(207)Pb ratios showed, in general, an upward decrease for both intertidal and subtidal sediments as a consequence of the anthropogenic activities over the last century, or centuries. Waste channel samples from a nearby ceramic factory showed characteristic Pb stable isotope ratios different from those typical of coal and petrol. Natural isotope ratios from non-polluted samples were established for the study area, differentiating sediments from granitic or schist-gneiss sources. A binary mixing model employed on the polluted samples allowed estimating the anthropogenic inputs to the bay. These inputs represented between 25 and 98% of Pb inputs in intertidal samples, and 9-84% in subtidal samples, their contributions varying with time. Anthropogenic sources were apportioned according to a three-source model. Coal combustion-related emissions were the main anthropogenic source Pb to the bay (60-70%) before the establishment of the ceramic factory in the area (in the 1970s) which has since constituted the main source (95-100%), followed by petrol-related emissions. The Pb inputs history for the intertidal area was determined for the 20th century, and, for the subtidal area, the 19th and 20th centuries.

Multiple small volume microwave-assisted digestions using conventional equipment for multielemental analysis of human breast biopsies by inductively coupled plasma optical emission spectrometry.

A multiple microwave-assisted digestion procedure using small PTFE closed vials (6 mL capacity) inserted into conventional microwave digestion vessels has been developed as a fast, efficient and clean methodology for multielemental analysis of human breast biopsies by inductively coupled plasma optical emission spectrometry. This small volume strategy allows drastically diminishing the volume of acid needed for digestion, and in turn, a decrease in sample dilution and an increase in sample throughput is achieved. A 2(IV)(4-1) fractional factorial design was used for screening optimization of four variables that can influence the digestion efficiency: (A) nitric acid volume, (B) pre-digestion step, (C) microwave power, and (D) digestion time. A validation study included linearity, precision, detection and quantification limits. Validation against different biological certified reference materials (CRMs) was also performed. The digestion method is suitable for the determination of Al, Ca, Cu, Fe, K, Mg, Mn, P, S and Zn in small size biological samples such as breast biopsies (<30 mg dry mass). Forty-seven biopsies from 39 women were analyzed: 20 samples from healthy women corresponding to mammoplasties and 27 samples from patients suffering from cancer pathology (19 corresponded to tumour and 8 to adjacent normal tissue). A significant accumulation of Al, Ca, Cu, K, Mg, Mn, P and Zn was found in tumour as compared to healthy tissues. When this comparison is made for tumour and adjacent tissues, a significant accumulation of Al, Mg, P and Zn in tumour tissues was observed. Finally, only Ca significantly accumulates in the adjacent tissues as compared to healthy tissues.

Multielemental determination in breast cancerous and non-cancerous biopsies by inductively coupled plasma-mass spectrometry following small volume microwave-assisted digestion.

A microwave-assisted digestion method amenable to analysis of small size biological samples (<30 mg dry mass) has been optimized for determining twelve elements (Ag, As, Cd, Co, Cu, Cr, Mn, Mo, Ni, Pb, Se and Zn) by inductively coupled plasma-mass spectrometry (ICP-MS) in breast cancerous and non-cancerous biopsies. The use of three small volume PTFE closed vials (6-mL capacity) placed inside a conventional microwave vessel allows to drastically diminishing the volume of acid needed for digestion. A Plackett-Burman experimental design was used to evaluate the robustness of the digestion procedure. Effects of nitric acid volume, need for predigestion step, microwave power and digestion time were assessed. No significant effects were found, the digestion method being robust enough to be recommended for a routine practice. The method was successfully validated against CRM BCR 185 (bovine liver), CRM NRCC TORT-2 (lobster hepatopancreas), CRM NRCC DORM-2 (dogfish muscle) and CRM NRCC DOLT-2 (dogfish liver). Procedural detection limits ranged from 0.54 to 40 ng g(-1). Within-batch precision values were less than 3%, whereas between-batch precision values were in the range 2-11%. Forty-seven biopsies from thirty-nine women were analyzed: 20 samples corresponding to mammoplasties from healthy women and 27 samples from patients suffering from cancer pathology, 19 of which corresponded to tumour and 8 to adjacent normal tissue. After applying parametric and non-parametric statistical tests, a significant accumulation of Cu, Mn, Zn and Se in cancerous tissues was demonstrated.

Development of an ultrasound-assisted extraction method for biomonitoring of vanadium and nickel in the coastal environment under the influence of the Prestige fuel spill (North east Atlantic Ocean).

As a consequence of the Prestige shipwreck occurred in the Northeast Atlantic Ocean in November 2002, the need for establishing the environmental impact caused by metals has been of primary concern. Among the different metals contained in the fuel spill, V and Ni are particularly of interest since they appear at relatively high concentration in the original fuel. Biomonitoring of V and Ni using wild mussels (Mytilus edulis) collected along the Galician Coast (NW Iberian Peninsula) has been performed. Ultrasound-assisted extraction of V and Ni from dried mussel tissues using probe sonication allowed a fast solid-liquid extraction thus facilitating sample preparation from large sample batches used for biomonitoring. V and Ni were determined in shellfish caught in the Galician littoral and tar balls from the Prestige spill by electrothermal-atomic absorption spectrometry and inductively coupled plasma-optical emission spectrometry, respectively. A Plackett-Burman saturated design was applied for screening optimization of variables influencing the ultrasound-assisted extraction of V and Ni from shellfish. Efficient extraction of both metals was obtained from slurries prepared in 2 mL capacity sample vials (10 mg sample with a particle size less than 100 microm) using a 3% (v/v) HNO3 diluent and subjected to probe sonication (3 min; 30% vibrational amplitude of the probe). The method was successfully validated by means of three certified reference materials: NRCC-TORT-2 Lobster hepatopancreas, NIST-SRM 1566b Oyster tissue and NIST-SRM 2977 Mussel tissue. The detection limit (LOD) of V and Ni in the marine biological tissues, calculated according to the 3sigma criterion, were 0.24 microg g(-1) and 0.15 microg g(-1) for V and Ni, respectively. V and Ni concentrations in M. edulis were in the range 1.7-4.8 and 0.8-2.8 microg g(-1), respectively. Whilst no significant variations in Ni contents were observed in regard to reference values, an important increase in V concentration is observed at some sampling points, thereby indicating bioaccumulation.

Selenio y carcinogénesis mamaria / Selenium and breast carcinogenesis

La relación entre el selenio (Se) y el cáncer comenzó a plantearse en 1943 y desde entonces, aunque algunos estudios epidemiológicos han mostrado un incremento del riego del cáncer de mama ante estados deficitarios de Se, otra proporción similar de trabajos no han encontrado tal asociación. En estu dios experimentales el Se se mostró muy eficaz para inhibir la carcinogénesis mamaria inducida por diferentes noxas en diversos modelos animales. Se cuestiona la utilidad del Se sérico en las enfermas de cáncer de mama como un marcador tumoral.De acuerdo con los datos de la bibliografía revisada y de los hallazgos de nuestro grupo, la disminución del Se sérico en las enfermas con cáncer de mama estaría relacionada con la actividad biológica del tumor, siendo un fenómeno posterior a la aparición del cáncer. También se apuntan nuevas líneas de investigación. (AU)