Biological monitoring of Italian soldiers deployed in Iraq. Results of the SIGNUM project.

BACKGROUND: Leukemia/lymphoma cases reported in 2001 among United Nation soldiers or peacekeepers deployed to the Balkans aroused alert on the exposure to depleted uranium. Recent epidemiological studies carried out in different European countries among peacekeepers who served in the Balkans failed to demonstrate a higher than expected risk of all cancers but, mostly due to their limitations in size and follow up time, leave open the debate on health risk of depleted uranium. The aim of SIGNUM (Study of the Genotoxic Impact in Military Units) was to identify potential genotoxic risk associated with the exposure to depleted uranium or other pollutants in the Italian Army military personnel deployed in Iraq. METHODS: Blood and urine samples were collected before and after the deployment from 981 Italian soldiers operating in Iraq in 2004-2005. As, Cd, Mo, Ni, Pb, U, V, W, and Zr were determined in urine and serum. DNA-adducts, 8-hydroxy-2'-deoxyguanine and micronuclei frequency were evaluated in blood lymphocytes. Three different genetic polymorphisms, GSTM1, XRCC1, OGG1 were analyzed. RESULTS: Significant T0-T1 reduction in the total concentration of uranium, increases for Cd, Mo, Ni, Zr, and decreases for As, Pb, W, and V in urine and plasma were observed. Increases in oxidative alterations and in micronuclei frequency, included in the range of values of non-occupationally exposed populations, were observed at the end of the period of employment. CONCLUSIONS: Our results did not detect any toxicologically relevant variation of DNA-damage biomarkers related to the deployment in the operational theater.

Detection and quantification of residues and metabolites of medicinal products in environmental compartments, food commodities and workplaces. A review.

The toxicological assessment of medicinal products (MPs) and their residues and metabolites in the environment have become a challenging task worldwide. The contamination of environmental compartments, biota, workplace, foodstuff and feedstuff by residues and metabolites of these substances poses a risk to human health which is still far from being fully understood. On the other hand, existing analytical methods not always possess sufficient detection power to quantify residues of MPs at very low concentrations. This review sets forth some of the most significant contributions made in this field over the past decade with a special focus on novel fit-for-purpose analytical approaches for the detection, identification and quantification of these pollutants and the assessment of their noxious potential for human beings and the environment.

Exposure of rome city tram drivers to airborne platinum, rhodium, and palladium.

OBJECTIVE: To investigate the exposure of tram drivers of Rome to Pt, Rh, and Pd in total suspended particulate, PM10, and PM2.5 fractions. METHODS: Sampling was performed on a tram running on about 15-km pathway characterized by a medium-high traffic car density. The analytical determination of metals was performed using inductively coupled plasma mass spectrometry. RESULTS: Mean element values (in pg/m) total suspended particulate, PM10, and PM2.5, were Pt, 20.3, 14.1, and 8.86, Rh, 3.99, 2.83, and 1.94, and Pd, 82.1, 58.0, and 15.2, respectively. CONCLUSIONS: Although the Pt, Rh and Pd levels in urban air were found to be still 8 to 11 orders of magnitude below the values thought to cause adverse effects on adult worker health, periodic environmental monitoring would be necessary to detect possible increments which could affect occupational exposure of tram drivers.

Biomonitoring of tram drivers exposed to airborne platinum, rhodium and palladium.

OBJECT: The aim of this study was to evaluate urinary levels of Pt, Rh and Pd in occupationally exposed subjects. METHODS: A total of 122 healthy male subjects of Rome (Italy) were studied; 64 were municipal tram drivers and 58 control subjects. Metal quantification in the urine samples was carried out by sector field inductively coupled plasma mass spectrometry. RESULTS: There were statistically significant differences between urinary Pt and Rh levels of the workers and the control group (Pt median: 1.23 versus 1.03 ng/g creatinine; Rh median: 19.16 versus 11.18 ng/g creatinine), while no difference in Pd levels was observed (Pd median: 11.47 versus 8.75 ng/g creatinine). CONCLUSIONS: Urinary Pt and Rh could be useful biomarkers for monitoring population groups occupationally exposed to these elements. Urinary concentration of Pt and Rh, though still low, could be of some concern in workers heavily exposed to urban car traffic.

Investigation of palladium and platinum levels in food by sector field inductively coupled plasma mass spectrometry.

Over the last two decades, there has been increased concern regarding the impact of some noble metals, such as Pd and Pt, on human health. These elements pollute the environment due to their widespread use as catalytic converters and in medical applications. The risk they pose to human health and the environment is still controversial; however, literature data point to diet as an important source of uptake by the human body. Within this context, the total Pd and Pt content of several Italian food commodities has been investigated. A total of 90 samples, including flour products, vegetables and foodstuffs of animal origin (meat, milk and eggs), were collected and freeze-dried. Samples were analyzed by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) after chopping or crushing followed by freeze-drying and microwave (MW)-assisted acid digestion in a Class-100 clean-room. A mathematical approach was adopted to correct the mass signals for still unresolved interference (mDeltam = 300, 10 000). The lowest and highest concentrations of Pt, i.e. 17 and 93 ng kg(-1) (dry weight, dw), were found in vegetables and flour products, respectively. The lowest Pd level (2830 ng kg(-1) dw) was found in eggs and the highest (47 800 ng kg(-1) dw) in vegetables.

Determination of Cd, Cu, Pb and Zn in neoplastic kidneys and in renal tissue of fetuses, newborns and corpses.

The incidence of kidney tumors in USA and Europe (in particular, Central Europe and Italy) has been dramatically increasing since the 1970s, possibly as a consequence of ongoing environmental pollution. Environmental factors have been considered responsible for at least 80% of the incidence of neoplastic diseases. To shed some light on this issue, the amounts of Cd and Pb were measured in neoplastic tissue and adjacent normal part of kidney excised for carcinoma and compared with those in renal tissues of fetuses, newborns and subjects that died of non-neoplastic diseases. Cd and Pb were determined by Inductively Coupled Plasma Atomic Emission Spectrometry and Atomic Absorption Spectrometry with Electrothermal Atomization. Metallothionein immunoperoxidase staining technique was used to localize the accumulation of Cd and Zn in the nephrons. Content of Cd and Pb in kidneys of fetuses and newborns was extremely low. However, it was significantly increased in adjacent-normal tissues of kidneys with carcinomas, and significantly higher compared to kidneys of individuals that died of non-neoplastic diseases. In tumoral tissues of the excised kidneys, Cd content was very low, while that of Pb significantly elevated. High amounts of Cd and Pb in the adjacent-normal parts of kidneys with carcinomas are suggestive of possible, individual or synergistic, effects of these pollutants on enzymatic systems, priming an oncogenic pathway. Detection of metallothioneins, primary ligands of Cd, exclusively in the cells of proximal tubuli, i.e. wherein renal carcinoma develops in over 80% of cases, strongly supports the assumption that Cd exerts a carcinogenic effect.

Chemical and biological characterisation of biofilms formed on different substrata in Tisza river (Hungary).

Natural biofilms were simultaneously grown on granite, polished granite, andesite, polycarbonate and Plexi-glass substrata for six weeks in the Tisza River. Biofilm production and abundance of algae were influenced by the substratum. Magnitude of the substratum effect was andesite

Evaluation of carboplatin pharmacokinetics in pediatric oncology by means of inductively coupled plasma mass spectrometry.

Carboplatin is widely used in pediatric oncology to treat different tumors. Aim of the present study was to assess the potential of sector field inductively coupled plasma mass spectrometry (SF-ICPMS) in evaluating the area under the plasma platinum concentration vs time curve in pediatric patients presenting solid tumors and treated with carboplatin 349-1000 mg m-2. Seventeen patients were enrolled and 23 courses of chemotherapy were evaluated. Plasma was ultrafiltered and free carboplatin was measured in ultrafiltrates as platinum by SF-ICP-MS. Comparison was made between different equations to obtain a target AUC. Limits of detection and of quantification, intra- and inter-day repeatability of the measurements, recovery of the 'free-carboplatin' confirmed SF-ICP-MS as a reliable technique in the quantification of serum platinum in anticancer carboplatin-based therapies.

Monitoring Pt and Rh in urban aerosols from Buenos Aires, Argentina.

Vehicular traffic is the main source of platinum group elements (PGEs) in highly populated urban areas like Buenos Aires where a traffic density of 1,500,000 vehicles day(-1) (corresponding to 7,500 vehicles km(-2)) is estimated. Since there is no information on the levels of PGEs in Buenos Aires, a pilot study was undertaken to ascertain the amount of two major PGEs, namely Pt and Rh, in the atmosphere of this city. To this end, 49 samples of PM-10 particulate matter were collected during 7 days in seven representative sampling sites located downtown Buenos Aires and spread over an area of about 30 km(2). The collection of particulate matter was performed on ash-free glass-fiber filters using high volume samplers with PM-10 sampling heads. Filters loaded with the particulate matter were subjected to microwave (MW)-assisted acid digestion using a combination of HNO(3), HF and HClO(4). The resulting solutions were evaporated and then diluted with 0.1 mol l(-1) HCl. Analyses were performed by sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) and special attention was paid to the control of mass interferences. Statistical analysis was performed on the experimental data obtained for the element concentrations taking also into account local meteorological data for the monitored period. The highest concentrations of Pt and Rh were detected at two sites (Hospital Alemán and Casa Rapallini) located in streets with traffic consisting mostly of passenger cars. The Pt content (in pg m(-3)) in airborne particulate matter was found to vary from 2.3 to 47.7, with a mean value of 12.9+/-7, and that of Rh from 0.3 to 16.8, with a mean value of 3.9+/-2.8. These concentrations are by far below the levels for which adverse health effects might be expected to occur, i.e., around 100 ng m(-3). On the other hand, monitoring of PGEs should be carried out in a systematic fashion to detect possible dramatic increases from today's levels.

[Reference materials for quality control of water analysis]. / Materiali di riferimento per il controllo di qualità nelle analisi delle acque.

The ability to carry out analytical determinations meeting the needs which have prompted them is the first priority of a laboratory independent of its specific area of competence. In this framework the key concepts inspiring the quality management of a laboratory are discussed with particular emphasis on the quantification of analytes in water, the availability to this end of certified and work reference materials, their use for the quality control of measurements and the participation in proficiency testing for quality assurance and sampling procedures. A laboratory managed in conformity with such criteria allows analytical methods to be validated and generates valid, defensible and comparable experimental information on the qualitative and quantitative presence of organic and inorganic substances in water.

Identification and quantification of major species of arsenic in rice.

A study was undertaken to develop a method for the chemical speciation of As in rice on the basis of current knowledge in this field for use in preparing a certified reference material (CRM). Samples of the Arborio rice variety were ground to a fine powder, which was extracted under sonication with a water-methanol mixture (1 + 1, v/v). The resulting solutions were injected into a high-performance liquid chromatograph combined on-line with a quadrupole inductively coupled plasma-mass spectrometer. This hyphenated system allowed for the quantification of As species in one analytical step. Four forms of As were detected: inorganic As (III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and inorganic As (V) at concentrations of 88.2 +/- 7.1, 50.8 +/- 5.0, 15.2 +/- 1.7, and 51.2 +/- 3.5 ng/g, respectively. The concentration of total As was 211 +/- 7 ng/g. The limits of detection (3sigma criterion) and the quantitation (10sigma criterion) were, respectively, as follows (in ng/g): As (III), 0.095 and 0.320; As (V), 0.082 and 0.273; MMA, 0.110 and 0.367; and DMA, 0.145 and 0.480. Ten hours were needed for the extraction procedure, 6 h for the evaporation, and 30 min for quantification of the analytes. This investigation was performed in the frame of a European Commission Project on the feasibility of CRMs for As and Se species.

Platinum, palladium and rhodium content in road dust, tunnel dust and common grass in Bialystok area (Poland): a pilot study.

Automobile traffic is the main source of Pt, Pd and Rh, i.e. platinum-group elements (PGEs), contamination in urban areas and there is growing concern about the effects of these emerging contaminants for people living in these areas. PGE contents were determined in samples of road dust, tunnel dust and common grass as well as pine needles collected from the residential areas of Bialystok, northeast Poland. High resolution (HR) and quadrupole inductively coupled plasma mass spectrometry (ICP-MS) were compared for their adequacy in the environmental analysis of Pt and Rh. Palladium was determined by total X-ray fluorescence (TXRF) and HR-ICP-MS after matrix separation by reductive co-precipitation with Hg. The highest PGEs concentration was found in road dust samples. Platinum content in road dust varied from 34.2 to 110.9 ng g(-1), while that of Rh from 6.0 to 19.7 ng g(-1). The mean concentration of Pd in this matrix was 32.8 ng g(-1) as determined by TXRF analysis and 42.2 ng g(-1) by HR-ICP-MS. The highest Pt concentration in tunnel dust was found in the size fraction below 75 microm (22.3-23.3 ng g(-1)). The mean concentrations of PGEs in grass were 8.63 ng g(-1) for Pt, 0.65 ng g(-1) for Rh and 3.2 ng g(-1) for Pd. The concentration of PGEs in pine needles was below the limits of detection of the methods used.

Traffic-related platinum and rhodium concentrations in the atmosphere of Rome.

Platinum and Rh content in the atmosphere of Rome as released by car catalytic converters was monitored from 1998 to 2000 in six urban sites with different traffic intensities and in one rural area. Samples collected with medium-volume PM10 samplers were analyzed by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS). The Pt content varied from 2.4 to 60.1 pg m(-3) (mean value 17.8 pg m(-3)) at the urban locations whilst that of Rh spanned the range 0.8-9.4 pg m(-3) (average value 4.0 pg m(-3)). The rural area showed metal levels mostly below the limits of detection, pointing to automobile traffic as the main source of those elements in the urban atmosphere. The highest mean concentrations of Pt and Rh, ie. 22.2 and 5.0 pg m(-3), were detected along the ring road where the traffic density is high (>100,000 vehicles per day) and the driving speed between 100 and 120 km h(-1). The lowest Pt and Rh mean concentrations, i.e. 11.4 and 3.4 pg m(-3), were measured downtown, where traffic density is lower (20,000 vehicles per day) and the driving speed is limited (50 km h(-1)). Significant concentrations of Pt and Rh were found in the vicinity of traffic signals, indicating that the "stop-and-go" conditions might also affect their release. The measured Pt/Rh ratio spanned the range 3.3-5.9 in accordance with that present in the more commonly used gasoline car catalytic converters. Seasonal variations between wintertime (with Pt and Rh mean concentrations of 23.8 and 5.1 pg m(-3), respectively) and summertime (with Pt and Rh mean concentrations of 14.1 and 3.3 pg m(-3), respectively) were also observed.

[The network of community and national reference laboratories for residues]. / La rete dei laboratori comunitari e nazionali di riferimento per i residui.

The European Union established in the early 1990's a network of Community reference laboratories (CRL) for residues in living animals and their products. This field is regulated at present by the Council Directive 96/23/CE of 26 April 1996, adopted at the national level through the Decree DL.vo no. 336 of 4 August 1999. The four CRL are based in France, Germany, Italy and The Netherlands, respectively, each of them being responsible for different categories of residues. The CRL provides technical support to the European Commission in this matter as well as to the National reference laboratories (NRL) for residues in the member states. The four CRL bear responsibility also as regards the adoption of quality systems by NRL. In this respect, the revised principles of good laboratory practice recently issued by OECD demand that procedures be developed to inform and assist the NRL to implement them.

Biomonitoring of a worker population exposed to low antimony trioxide levels.

Antimony trioxide (Sb2O3) is used as a flame retardant in the textile industry. We carried out a study in a factory for the evaluation of antimony (Sb) occupational exposure and urinary levels in workers exposed to Sb2O3. Urinary levels and airborne Sb2O3 personal exposure values were very low when compared to international occupational standards (500 microg/m3, as Sb). The range of forty-two personal exposures was 0.01-0.55 microg Sb/m3, while twenty-four area samplings ranged from < 0.01 microg Sb/m3 to 1.45 microg Sb/m3. The mean urinary Sb levels at the beginning (n = 39) and end of the shift (n = 39) were 0.31 +/- 0.25 microg/L and 0.35 +/- 0.29 microg/L respectively, without any significant statistical difference. When the workers were divided into two subgroups according to "higher" and 'lower" exposure levels, a statistical difference (P < 0.001) was observed between the mean Sb urinary levels of the two subgroups during the workweek, both at the beginning and end of the shift. A statistical difference was also observed between the above mentioned subgroups and the controls (n = 15). No correlation was found between personal Sb2O3 exposure and the difference in urinary Sb levels at the beginning and end of the workshift on the day the flame retardant was utilized. This lack of correlation could be due to low airborne Sb2O3 levels and Sb dietary intake, estimated as 3 microg/day in UK, but not yet fully investigated in Italy. Any accidental occupational Sb per os exposure however low, could further enhance the lack of correlation.