Human biomonitoring to evaluate exposure to toxic and essential trace elements during pregnancy. Part B: Predictors of exposure.

Maternal exposure to toxic and essential trace elements represents a surrogate of exposure to the unborn child. Variables of exposure as sociodemographic, lifestyles and diet may contribute to different exposure of pregnant women to specific trace elements. Blood, urine and cord blood samples of 53 pregnant women of the HEALS-EXHES cohort, recruited in Reus (Catalonia, Spain) between 2016 and 2017, were analysed for the concentrations of As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Se and Zn. Univariate and multivariate models were built in order to assess associations between element concentrations in each matrix, and variables obtained by questionnaires on mothers' characteristics and dietary habits. Results showed several significant associations between various variables and essential trace and toxic elements. Age was associated with higher levels of Cd and Pb in cord blood samples. Multiparous women showed lower levels of Cd in maternal blood and Pb in both maternal and cord blood than nulliparous women. Hispanic mothers presented higher levels of blood As and lower levels of blood Se compared to mothers of different ethnicity. Higher education level was associated with higher As and Hg concentrations in both maternal and cord blood samples. Higher annual income diminished the level of Pb in maternal blood. Smoking in pregnancy incremented the levels of Cd in mothers' blood. Alcohol consumption may affect the absorption of Cu, Mn and Zn. Supplementations with multivitamins, folic acid and iron showed effects on elements as Cr, Mn, Se and Zn. Regarding food group intake, bluefish incremented Pb levels, while canned fish and seafood affected levels of some elements as As, Hg, Cu and Se. Other elements such as Mn and Pb were influenced by the intake of different kinds of foods. The present results showed that some modifiable lifestyles and food intakes could be the target of interventions to help pregnant women to maintain suitable concentrations of essential elements and lower levels of toxic ones, and to improve consequently neonatal health outcomes.

Human biomonitoring to evaluate exposure to toxic and essential trace elements during pregnancy. Part A. concentrations in maternal blood, urine and cord blood.

Exposures to toxic elements or deficiencies of essential elements during pregnancy may be associated to various birth complications or even diseases in early life. The aim of this paper was to assess the concentrations of selected toxic (As, Cd, Cr, Hg, Ni, Pb) and essential trace elements (Co, Cu, Mn, Se and Zn) in blood and urine samples of delivering women at different periods of gestation and cord blood, as well as to evaluate the placental permeability for these elements. A total of 53 women participating in the HEALS-EXHES study were enrolled. In particular, 48 blood samples from 1st trimester of pregnancy, 40 blood samples at delivery, and 31 cord blood at delivery were collected. Moreover, mothers' urine were sampled at the 1st (53 samples), 2nd (53 samples) and 3rd trimester (49 samples) of pregnancy. Results showed that Hg and Mn levels in cord blood were about 2.0 times higher than in maternal blood, suggesting that these elements may be transferred from mother to fetus. The cord blood levels of As and Pb were lower (ca. the 65%) than those in maternal blood, showing that the placenta modulates the rate of transfer for these elements. Essential elements as Cu and Zn showed significantly lower levels in cord than in maternal blood suggesting that the transplacental transfer of these nutrients was very limited. In addition, correlation between paired maternal and cord blood samples for As, Hg and Pb was statistically significant indicating that the fetal body burden may reflect the maternal exposure. Cadmium, Co, Cr, Ni and Se levels did not show significant correlations between maternal and cord blood. Maternal urinary concentrations of trace elements, including As, Cr, Cu, Hg, Se and Zn decreased along pregnancy, which may cause variations in fetal exposure. The levels of toxic and essential elements in maternal blood and urine, as well as in cord blood, were for most elements at the lower end of the ranges found in the scientific literature not being of special concern for pregnant women and the unborn.

Urinary metabolites of organophosphate and pyrethroid pesticides in children from an Italian cohort (PHIME, Trieste).

Urinary metabolites of organophosphate (OP) and pyrethroid (PYR) pesticides from seven years old children of a birth cohort study (n=199; PHIME cohort of Trieste, Italy) have been measured. Six OP and two PYR metabolites have been investigated, 2-diethylamino-6-methylpyrimidin-4-ol (DEAMPY, pirimiphos metabolite) was the one found at higher concentrations, median 3.4 ng/mL specific gravity adjusted (SG adjusted), followed by 4-nitrophenol (PNP, median 1.4 ng/mL SG adjusted) and 3,5,6-trichloro-2-pyridinol (TCPY, median 0.36 ng/mL SG adjusted), parathion and chlorpyriphos metabolites, respectively. TCPY concentrations were low in comparison to other distributions of OP metabolites in children from other studies. Accordingly, the PHIME cohort showed a distinct OP metabolite distribution with high concentrations of pirimiphos and parathion. Another specific characteristic of this cohort was the high concentration of 3-phenoxybenzoic acid (3-BPA, median 0.36 ng/mL SG adjusted), a general metabolite of PYR pesticides. Evaluation of anthropometric and socio-demographic characteristics of children and families only showed a positive association between family educational level and urinary concentrations of DEAMPY metabolite (p<0.05), which could reflect distinct dietary habits depending on the educational level. Estimated daily intakes were evaluated, all studied metabolites were found within safe levels.

Setting up a collaborative European human biological monitoring study on occupational exposure to hexavalent chromium.

The EU human biomonitoring initiative, HBM4EU, aims to co-ordinate and advance human biomonitoring (HBM) across Europe. Within its remit, the project is gathering new, policy relevant, EU-wide data on occupational exposure to relevant priority chemicals and developing new approaches for occupational biomonitoring. In this manuscript, the hexavalent chromium [Cr(VI)] study design is presented as the first example of this HBM4EU approach. This study involves eight European countries and plans to recruit 400 workers performing Cr(VI) surface treatment e.g. electroplating or stainless steel welding activities. The aim is to collect new data on current occupational exposure to Cr(VI) in Europe and to test new methods for Cr biomonitoring, specifically the analysis of Cr(VI) in exhaled breath condensate (EBC) and Cr in red blood cells (RBC) in addition to traditional urinary total Cr analyses. Furthermore, exposure data will be complemented with early biological effects data, including genetic and epigenetic effects. Personal air samples and wipe samples are collected in parallel to help informing the biomonitoring results. We present standard operational procedures (SOPs) to support the harmonized methodologies for the collection of occupational hygiene and HBM samples in different countries.

Neurocognitive impact of metal exposure and social stressors among schoolchildren in Taranto, Italy.

BACKGROUND: Metal exposure is a public health hazard due to neurocognitive effects starting in early life. Poor socio-economic status, adverse home and family environment can enhance the neurodevelopmental toxicity due to chemical exposure. Disadvantaged socio-economic conditions are generally higher in environmentally impacted areas although the combined effect of these two factors has not been sufficiently studied. METHODS: The effect of co-exposure to neurotoxic metals including arsenic, cadmium, manganese, mercury, lead, selenium, and to socio-economic stressors was assessed in a group of 299 children aged 6-12 years, residing at incremental distance from industrial emissions in Taranto, Italy. Exposure was assessed with biological monitoring and the distance between the home address and the exposure point source. Children's cognitive functions were examined using the Wechsler Intelligence Scale for Children (WISC) and the Cambridge Neuropsychological Test Automated Battery (CANTAB). Linear mixed models were chosen to assess the association between metal exposure, socio-economic status and neurocognitive outcomes. RESULTS: Urinary arsenic, cadmium and hair manganese resulted inversely related to the distance from the industrial emission source (ß - 0.04; 95% CI -0.06, - 0.01; ß - 0.02; 95% CI -0.05, - 0.001; ß - 0.02 95% CI -0.05, - 0.003) while the WISC intellectual quotient and its sub-scores (except processing speed index) showed a positive association with distance. Blood lead and urinary cadmium were negatively associated with the IQ total score and all sub-scores, although not reaching the significance level. Hair manganese and blood lead was positively associated with the CANTAB between errors of spatial working memory (ß 2.2; 95% CI 0.3, 3.9) and the reaction time of stop signal task (ß 0.05; 95% CI 0.02, 0.1) respectively. All the other CANTAB neurocognitive tests did not show to be significantly influenced by metal exposure. The highest socio-economic status showed about five points intellectual quotient more than the lowest level on average (ß 4.8; 95% CI 0.3, 9.6); the interaction term between blood lead and the socio-economic status showed a significant negative impact of lead on working memory at the lowest socio-economic status level (ß - 4.0; 95% CI -6.9, - 1.1). CONCLUSIONS: Metal exposure and the distance from industrial emission was associated with negative cognitive impacts in these children. Lead exposure had neurocognitive effect even at very low levels of blood lead concentration when socio-economic status is low, and this should further address the importance and prioritize preventive and regulatory interventions.

[Exposure assessment to air pollutants: dispersion models versus human biomonitoring]. / La valutazione dell'esposizione a contaminanti ambientali: modelli di dispersione e biomonitoraggio umano.

BACKGROUND: the assessment of individual exposure to toxicants in industrially contaminated areas is difficult when multiple productions are actively close to residential areas. Two thermoelectric power plants (one recently converted to coal) and a large harbour have been operating since the Sixties in the area of Civitavecchia (North of Rome, Lazio Region, Central Italy). Detailed exposure assessment of pollutants from industrial sources, heating (biomass combustion), and urban traffic were not available. OBJECTIVES: to assess the individual exposure of residents by using both dispersion models and human biomonitoring. DESIGN: cross-sectional study. SETTING AND PARTICIPANTS: residents in the area of Civitavecchia since 2001 aged 35-69 years were enrolled and their addresses were geocoded. Exposure assessment to power plants emissions (PM10), traffic (NOx), harbour (PM10), and biomass burning (PM10) was performed at individual residential address using Lagrangian dispersion models. The "Ambiente e Biomarcatori a Civitavecchia" study (Environment and biomarkers in Civitavecchia - ABC study) made available urinary concentrations of metals (i.e., Cd, Pt, W, Pd, Hg, Tl, Cr, Pd, Ni, As) in a sample of residents, while information on personal characteristics, lifestyles, work history, clinical history, and use of drugs was collected by interview. MAIN OUTCOME MEASURES: for each metal, a linear regression analysis was implemented to study the association between its log-transformed values (adjusted for urinary creatinine) and the linear terms of the estimated pollutants concentrations, adjusted for age, gender, period, and other risk factors (i.e., educational level, smoking habit, alcohol, BMI). Geometric Mean Ratios (GMR) and the corresponding confidence intervals (95%CI) were computed. RESULTS: in the ABC sample of 1,141 residents (42% male, mean age 53.5 years, SD 9.7), there was a positive association between PM10 from power plants and urinary cadmium (Cd) (GMR: 1.12; 95%CI 1.00-1.25), traffic pollution (NOx) and platinum (Pt) (GMR: 1.17; 95%CI 1.00-1.38), PM10 from biomass burning and Cd (GMR: 1.14; 95%CI 1.05-1.24), and tungsten (W) (GMR: 1.19; 95%CI 1.03-1.37) and palladium (Pd) (GMR: 1.11; 95%CI 1.00-1.23). Other associations observed did not reach statistical significance. CONCLUSIONS: although it may not be said that dispersion models can replace biomonitoring studies, they certainly represent an excellent tool for exposure assessment and, therefore, they may be used for the estimation of the individual exposure of populations living in industrially contaminated areas.

A medical-toxicological view of tattooing.

Long perceived as a form of exotic self-expression in some social fringe groups, tattoos have left their maverick image behind and become mainstream, particularly for young people. Historically, tattoo-related health and safety regulations have focused on rules of hygiene and prevention of infections. Meanwhile, the increasing popularity of tattooing has led to the development of many new colours, allowing tattoos to be more spectacular than ever before. However, little is known about the toxicological risks of the ingredients used. For risk assessment, safe intradermal application of these pigments needs data for toxicity and biokinetics and increased knowledge about the removal of tattoos. Other concerns are the potential for phototoxicity, substance migration, and the possible metabolic conversion of tattoo ink ingredients into toxic substances. Similar considerations apply to cleavage products that are formed during laser-assisted tattoo removal. In this Review, we summarise the issues of concern, putting them into context, and provide perspectives for the assessment of the acute and chronic health effects associated with tattooing.

Trace elements, oxidative status and antioxidant capacity as biomarkers in very low birth weight infants.

Reference data on trace elements, oxidative status and antioxidants in very low birth weight infants (VLBW) are limited and need to be updated for use in clinical settings. Serum and urine of 30 VLBW infants (mean weight, 1167g) at mean age of 23.8 (t0) and 37.8 (t1) days were analyzed. Cadmium (Cd), copper (Cu), iron (Fe), mercury (Hg), manganese (Mn), selenium (Se) and zinc (Zn), nitrate/nitrite (NOx), catalase (CAT), CuZnFeMn-superoxide dismutases (CuZnFeMn-SODs), total antioxidant capacity (SAC: sum of thiols, proteins, bilirubin, uric acid, ß-beta-carotene, ascorbic acid, vitamin E) and total oxidative status (SOS: sum of lipo- and hydroperoxides) were determined. A higher urinary excretion of Cu and Zn was observed at t0 than at t1; while an increase in urine Cd was found at t1 respect to t0. A deficiency in serum levels of Cu and Zn was also found. A lower CAT activity, a higher total oxidants level (SOS) and a reduction of total antioxidant barriers (SAC) were observed in some infants. No Fe and Mn deficiency or Hg overload was found; also CuZnFeMn-SODs and NOx levels did not change. The findings showed that losses of trace elements and incomplete mineral body stores were more pronounced in the earlier life stage (at 23.8th day) than later on; moreover, antioxidant defenses were poor and lipo- and hydroperoxides were higher still at 5 weeks of infants' life.

Human biomonitoring data analysis for metals in an Italian adolescents cohort: An exposome approach.

The first Italian human biomonitoring survey (PROBE - PROgramme for Biomonitoring general population Exposure) considered a reference population of adolescents, aged 13-15 years, living in urban and rural areas and investigated their exposure to metals. The study was expanded up to 453 adolescents living in the same areas of Latium Region (Italy) and blood samples were analyzed for 19 metals (As, Be, Cd, Co, Cr, Hg, Ir, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Sb, Sn, Tl, V, and W) by sector field inductively coupled plasma mass spectrometry. The exposure assessment was contextualized following an exposome approach that considered several determinants related to the subjects, available environmental parameters and geo-coding of residence address. To assess the influence of exposure determinants and modifiers on children biomarkers levels we used two independent methodologies. The first makes use of the so-called Environment-Wide Association Study (EWAS) methodology while the second was based on the application of a Generalized Liner Model (GLM) capturing co-exposures to pairs of key determinants. Based on our analysis, Hg and As were positively associated with dietary pathways (primarily linked to fish and to a lesser extent to milk consumption) while Cr showed a more complex interaction between co-exposure to different dietary pathways (milk and fish) coupled to proximity of residence to industrial activities. In addition to diet, socio-economic status of the mother revealed robust statistical associations with Cd, Ni and W biomonitoring levels in the respective children.

Human biomonitoring of metals in adults living near a waste-to-energy incinerator in ante-operam phase: Focus on reference values and health-based assessments.

The human biomonitoring (HBM) of metals is a part of the ongoing project SPoTT for the longitudinal health surveillance of the population living near a waste-to-energy (WTE) incinerator (Turin, Italy). The HBM of metals in the SPoTT population aimed to evaluate: i) reference values (RVs) before the WTE incinerator started operation; ii) differences in exposure by variables; iii) variations respect to other HBM studies; iv) exposure that exceeds the available health-based benchmarks as the Biomonitoring Equivalents (BEs) for urine Cd and Human Biomonitoring (HBM-I and HBM-II) values for urine Hg, Tl, and blood Pb; v) risk assessment by generating hazard quotients (HQs) for the single metal and hazard index (HI) for the co-occurrence of metals. Eighteen metals in urine and Pb in blood were determined by sector field inductively coupled plasma mass spectrometry. Metal concentrations were comparable with RVs reported in other countries, except for slightly higher As, Be, Ir, Pd, Pt, Rh, and Tl levels. Smoking was associated with Cd; age with Pb; drinking bottled water with As and Cd; consumption of fish with As and Hg; amalgams with Hg and Sn; dental restorations with Pd and Pt; use of jewelry with Co and Rh, and piercing with Ni. While HQs for urine Cd, Hg, Tl and blood Pb suggested that adverse effects were unlikely, the HQ value raised the question of whether additive interactions of these metals could produce health concern. The obtained HBM data can be an early warning for accumulations of metals and identification of subgroups at risk.

Biomonitoring and exposure assessment of people living near or working at an Italian waste incinerator: methodology of the SPoTT study.

Only few studies on the health effect of waste incinerators were focused on human biomonitoring (HBM). Our aim is to describe a protocol for assessing early variation of selected items in a population group living close to a waste incinerator in Turin, Italy. A cohort of 394 subjects was randomly selected, among residents near the incinerator and residents far from it. To achieve this sample size, 765 subjects were contacted. The cohort was monitored before the start-up of the plant and will be followed up 1 and 3 years after, with measurements of respiratory function, selected blood and urine parameters including 19 metals, 17 congeners of PCDDs/Fs, 12 congeners of DL-PCBs, 30 congeners of NDL-PCBs, 11 OH-PAHs, specific hormones (T3, T4, TSH, cortisol and ACTH) and common health parameters. The same protocol is applied for plant workers and breeders living near the plant. Individual exposure to urban pollution and waste incinerator fallout were assessed through the use of mathematical models. Information on individual habits was assessed using a specific questionnaire. SPoTT is the first Italian study that adopts a longitudinal design of appropriate statistical power to assess health impacts of waste incinerator plants' emission. The initial results comparing the baseline to the first follow-up are due at the end of 2016.

Toxic metals contained in cosmetics: a status report.

The persistence of metals in the environment and their natural occurrence in rocks, soil and water cause them to be present in the manufacture of pigments and other raw materials used in the cosmetic industry. Thus, people can be exposed to metals as trace contaminants in cosmetic products they daily use. Cosmetics may have multiple forms, uses and exposure scenarios, and metals contained in them can cause skin local problems but also systemic effects after their absorption via the skin or ingestion. Even this, cosmetics companies are not obliged to report on this kind of impurities and so consumers have no way of knowing about their own risk. This paper reviewed both the concentration of metals in different types of cosmetics manufactured and sold worldwide and the data on metals' dermal penetration and systemic toxicology. The eight metals of concern for this review were antimony (Sb), arsenic (As), cadmium (Cd), chromium (Cr), cobalt (Co), mercury (Hg), nickel (Ni) and lead (Pb). This was because they are banned as intentional ingredients in cosmetics, have draft limits as potential impurities in cosmetics and are known as toxic.

The Environmental Pollutant Cadmium Promotes Influenza Virus Replication in MDCK Cells by Altering Their Redox State.

Cadmium (Cd) is a toxic heavy metal that is considered an environmental contaminant. Several sources of human exposure to Cd, including employment in primary metal industries, production of certain batteries, foods, soil and cigarette smoke, are known. Its inhalation has been related to different respiratory diseases and toxic effects, among which alterations of the physiological redox state in individuals exposed to the metal have been described. Host-cell redox changes characteristic of oxidative stress facilitate the progression of viral infection through different mechanisms. In this paper, we have demonstrated that pre-treatment with CdCl(2) of MDCK cells increased influenza virus replication in a dose-dependent manner. This phenomenon was related to increased viral protein expression (about 40% compared with untreated cells). The concentration of CdCl(2), able to raise the virus titer, also induced oxidative stress. The addition of two antioxidants, a glutathione (GSH) derivative or the GSH precursor, N-acetyl-L-cysteine, to Cd pre-treated and infected cells restored the intracellular redox state and significantly inhibited viral replication. In conclusion, our data demonstrate that Cd-induced oxidative stress directly increases the ability of influenza virus to replicate in the host-cell, thus suggesting that exposure to heavy metals, such as this, could be a risk factor for individuals exposed to a greater extent to the contaminant, resulting in increased severity of virus-induced respiratory diseases.

Atmospheric background trace elements deposition in Tierra del Fuego region (Patagonia, Argentina), using transplanted Usnea barbata lichens.

Lichen, Usnea barbata, transplants taken from Tierra del Fuego (south Patagonia, Argentina) were tested as potential biomonitors of atmospheric airborne deposition in an apparently pristine environment. In 2005, lichens were sampled in a reference site (n = 31) and transplanted in the northern Region of Tierra del Fuego. After, respectively, 1 month and 1 year of exposure, we collected them. The aim of the study was to determine the bioaccumulation of 26 elements in order to evaluate the background levels in the selected area. Samples were analyzed by the sector field inductively coupled plasma mass spectrometry. Discriminant analysis on principal component analysis factors was applied in order to explore the relationship among the different elements as far as time and spatial variation in transplants regards. The analysis was tested by Monte Carlo test based on 999 replicates. The most important contamination source resulted to be the atmospheric soil particle deposition. Furthermore, the results were compared with those obtained from the lichens collected in central and southern Tierra del Fuego. This study confirms the ability of U. barbata to reflect the background levels of the 26 elements in that environment. Compared with other background sites in the world, we did confirm that Tierra del Fuego lichens have a low content of the studied elements. Tierra del Fuego turned out not to be a pristine environment as supposed, but it can be considered as a reference basal ecosystem for useful comparisons among different geographical areas. These findings can be very relevant and useful for environmental conservation programs.

[Exploratory biomonitoring study among workers of livestock farms of the Taranto Province]. / Studio esplorativo di biomonitoraggio tra gli allevatori delle masserie della Provincia di Taranto.

OBJECTIVE: to conduct a survey on blood levels of metals and organochlorine compounds (dioxins and PCBs) among workers of livestock farms, and to identify the factors able to explain the magnitude and variability of the measured concentrations. DESIGN: exploratory human biomonitoring study. SETTING AND PARTICIPANTS: a sample of 45 workers from farms (masserie) located in the Province of Taranto was included in the study. The farms, located between 6 and 43 km from the industrial area, are family owned and animals (mainly sheep and goats) are locally reared outdoors. The study subjects have similar eating habits, including food consumption resulting from their production. RESULTS: manganese concentrations and, to a lesser extent, arsenic, cadmium and lead are in the medium-high range of levels observed in the Italian general population. This study does not identify factors able to explain the variability in the blood levels of metals. The amount of dioxins and PCBs, on the other hand, is strongly associated both with subjects age and the distance of farm from the industrial site. CONCLUSION: the results of this survey are suggestive of research hypotheses that need to be confirmed by biomonitoring studies of adequate design and size, in particular the hypothesis that the blood level of dioxins and PCBs decreases with increasing distance from the industrial site. We recommend ad hoc studies to better characterize the exposure of farmers (also associated with agricultural activities), and of the inhabitants of Taranto, to environmental persistent pollutants, also in terms of food matrices locally produced and consumed.

Uncertainty evaluation in the analysis of biological samples by sector field inductively coupled plasma mass spectrometry. Part B: measurements of As, Co, Cr, Mn, Mo, Ni, Sn and V in human serum.

This protocol was developed to estimate the uncertainty of measurements in the sector field inductively coupled plasma mass spectrometry analysis of As, Co, Cr, Mn, Mo, Ni, Sn and V in human serum by utilizing in-house validation data. The approach is outlined in the Eurachem/Citac Guide and other relevant publications. The results generated were the followings: (i) coefficients of regression >0.9995 over two orders of magnitude of metal concentration; (ii) method quantification limits between 0.05 µg/L (Cr, Mn) and 0.49 µg/L (As); (iii) mean trueness checked against a certified reference material between 95.4% (As) and 107.7% (Ni); (iv) repeatability better than 10.2% over the range 0.1-2.0 µg/L; (v) reproducibility better than 12.0% over the range 0.1-2.0 µg/L; and (vi) expanded uncertainty budget comprised between 14.7% (Mn) and 27.9% (Cr) over the range 0.1-2.0 µg/L.

The effects of iridium on the renal function of female Wistar rats.

Despite the widespread use of iridium (Ir) in catalytic converters for improved capacity for reducing carbon monoxide (CO), hydrocarbon (HC) and nitrogen oxide (NO(x)) emissions, there is a lack of studies that have assessed possible toxicological hazards of exposure to Ir. The present investigation indicates that female Wistar rats exposed to Ir in the drinking water for 90 days displayed renal toxicity based on the elevated urinary retinol binding protein (RBP) and albumin. The RBP was more sensitive to albumin, showing significant increases at 0.01 mg/L.

The effects of the exposure to neurotoxic elements on Italian schoolchildren behavior.

Neurodevelopmental disorders are constantly increasing on a global scale. Some elements like heavy metals are known to be neurotoxic. In this cross-sectional study we assessed the neurobehavioral effect of the exposure to trace elements including lead, mercury, cadmium, manganese, arsenic and selenium and their interactions among 299 schoolchildren residing in the heavily polluted Taranto area in Italy. Whole blood, urine and hair were collected for metal analyses, while the Child Behavior Checklist and the Social Responsiveness Scale, administered to the main teacher and the mothers were considered to identify behavioral problems in children. Blood lead mainly influenced social problems, aggressive behavior, externalizing and total problems. Urinary arsenic showed an impact on anxiety and depression, somatic problems, attention problems and rule breaking behavior. A significant interaction between lead and arsenic was observed, with a synergistic effect of the two metals increasing the risk of attention problems, aggressive behavior, externalizing problems and total problems. Overall, we were able to test that higher blood lead, urinary arsenic concentrations and their interaction increase the risk of neurobehavioral problems. This is in line with the U.S. Environmental Protection Agency's priority list of hazardous substances where arsenic and lead are ranked as first and second respectively.

Uncertainty evaluation in the analysis of biological samples by sector field inductively coupled plasma mass spectrometry. Part A: Measurements of Be, Cd, Hg, Ir, Pb, Pd, Pt, Rh, Sb, U, Tl and W in human serum.

A protocol that utilises data (trueness/recovery, precision and robustness) from validation tests to calculate measurement uncertainty was described and applied to a sector field inductively coupled plasma mass spectrometry (SF-ICP-MS)-based method for the determination of Be, Cd, Hg, Ir, Pb, Pd, Pt, Rh, Sb, U, Tl and W in human serum. The method was validated according to criteria issued by international bodies such as AOAC, Eurachem and ISO and the uncertainty in the analytical measurements was estimated following the Eurachem/Citac guide. The methodology was based on dilution of human serum with water and analysis by serum-matched standard calibration. The method quantification limits ranged 0.02 microg/L (Tl, Ir) to 0.26 microg/L (Hg). The coefficients of regression were greater than 0.9991 over a range of two orders of magnitude of concentration. The mean trueness was 101% and the mean recovery on three levels of fortification (1-, 1.5-, and 2-times the baseline serum level) ranged between 93.3% and 106%. The maximum relative standard deviation values for repeatability and within-laboratory reproducibility were 12.8% and 13.5%. The method was robust to slight variations of some critical factors relevant to the sample preparation and SF-ICP-MS instrumentation. The relative expanded uncertainty over three levels of concentration ranged from 11.6% (Hg) to 27.6% (Pt), and the uncertainty on the within-laboratory reproducibility, which included factors such as time, analyst and calibration, represented the main contribution to the overall uncertainty.

Iridium, platinum and rhodium baseline concentration in lichens from Tierra del Fuego (South Patagonia, Argentina).

Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, <0.010-1.011 ng g⁻¹; Pt, 0.016-2.734 ng g⁻¹; and Rh, 0.063-1.298 ng g⁻¹. Data on 7 areas were similar suggesting that no specific source, for example traffic or anthropogenic activity, influenced directly the metal concentrations in Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.