Use of potentially harmful skin-lightening products among immigrant women in Rome, Italy: a pilot study.

BACKGROUND: Skin-lightening products are increasingly common in European cities. These products may contain substances that are banned under EU regulations as they can induce adverse effects, including cutaneous and systemic reactions (e.g., mercury, hydroquinone and topical corticosteroids). OBJECTIVES: To assess the knowledge, attitudes and practices of women regarding skin-lightening products and to quantify the potentially harmful substances in the products used. METHODS: We performed a cross-sectional study among 82 non-Italian women visiting an outpatient facility in Rome, Italy. The women completed a questionnaire on product use, side effects and risk awareness. We performed patch tests among a subgroup of 48 women who presented with contact dermatitis. We also quantified the allergenic and toxic substances in the 14 products reported, using dynamic reaction cell inductively coupled plasma mass spectrometry for metals and high-performance liquid chromatography for hydroquinone and topical corticosteroids. RESULTS: Out of the 82 women, 33 used skin-lightening products; about one fourth of these women were aware of potential risks. Three cosmetic creams and two soaps contained high concentrations of metals (Cr, Ni and Pb); hydroquinone was found in three creams and one oil. The only topical corticosteroid detected was dexamethasone, in one product. More than half of the women in the clinical evaluation had irritant contact dermatitis (i.e., negative response to patch test). CONCLUSIONS: Among immigrant women in Rome, the use of skin-lightening products seems to be fairly common, and some of these products contain potentially hazardous substances. Consumers must be informed of the potential risks, and EU regulations must be more strictly enforced.

Method validation for determination of arsenic, cadmium, chromium and lead in milk by means of dynamic reaction cell inductively coupled plasma mass spectrometry.

With Regulation No. 1881/2006 the European Union fixed a maximum level for lead in milk. Consequently, there is the need to determine very low concentration of elements that may be present in milk in trace and ultratrace levels. Quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) combined with dynamic reaction cell (DRC) has been widely employed in order to reach very low concentration, requested for this product. Furthermore, the DRC technology can help in removing polyatomic and argon-based interferences. In the present study, a method for the determination of arsenic, cadmium, chromium and lead in bovine milk was validated according to the EU common standards by means of DRC-ICP-MS. The main parameters evaluated in the validation were: recovery, repeatability and within-laboratory reproducibility, detection and quantification limits, linearity range and measurement uncertainty. Additionally, stability studies of the analyte in solution and ruggedness studies were carried out. The results obtained for limit of detection (LoD) and limit of quantification (LoQ) in microg kg(-1) were respectively: As, 3.1 and 9.5; Cd, 0.08 and 0.24; Cr, 0.229 and 0.693; Pb, 0.5 and 1.5. While for the recovery: As, 91%; Cd 96%; Cr 99%; Pb, 95%. As for the repeatability: As, 7%; Cd, 3%; Cr, 6%; Pb, 4%.

A pilot study on the content and the release of Ni and other allergenic metals from cheap earrings available on the Italian market.

The capability of alloys used in cheap jewellery to release metal ions on contact with the skin causing allergic contact dermatitis (ACD) is generally acknowledged. To reduce the diffusion of the Ni-induced ACD the Council Directive 94/27/EC [Council Directive 94/27/EC of 30 June 1994. Official Journal L 188, 22/07/1994, 1.] limited the total Ni content in alloys and its release rate in artificial sweat. In this work, three different aspects were explored: i) the frequency of skin sensitization to Ni-containing earrings in patients before and after the introduction of the Directive's limit; ii) metal composition of alloys by X-ray analysis; iii) metal leaching in artificial sweat followed by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS) quantification. Well-known allergenic metals, as Ni, Cr and Co, and possible emergent allergens, as Al, Ag, Au, Cd, Cu, Fe, Ir, Mn, Pb, Pd, Pt, Rh, Sn, V and Zn, were studied. Results showed that the frequency of allergy due to earrings did not decrease after the introduction of the Ni limit: in 1994 and in 2005 patients positive to Ni patch tests were 54.3% and 53.5%, respectively. The earring components analyzed were Fe-based or alloys of Cu/Zn or Fe/Cr/Ni, plated with a thin film of precious metal (Ag, Au) which, in several cases, was combined with a Ni layer beneath. Five out of 10 items were not in compliance with the Ni Directive 94/27/EC having a total Ni content >0.05%. In three cases the release of Ni concentrations was higher than the safe sensitizing limit given by the above mentioned Regulation (i.e., <0.5 microg/cm(2)/week). The release of Cu and Zn was very variable among the different pieces (Cu: 0.134-30.9 microg/cm(2)/week; Zn: 0.141-160 microg/cm(2)/week); two objects released high amounts of Fe (358 and 586 microg/cm(2)/week) and one released considerable Mn (21 microg/cm(2)/week). Lead was released from 70% of the objects, while Ag, Al, Cd, Co, Cr and Sn from ca. 30% of the items and concentrations of these elements were well below 0.5 microg/cm(2)/week. Vanadium was released by only one item whereas Au, Ir, Pd, Pt and Rh were never leached.

Determination of depleted uranium in fish: validation of a confirmatory method by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS).

Depleted uranium (DU) is a by-product of the uranium enrichment process for nuclear fuel. According to the Commission Decision 2002/657/EC, a confirmatory method for the quantification of DU in freeze-dried fish was developed by isotope ratio dynamic reaction cell inductively coupled plasma-mass spectrometry (IR-DRC-ICP-MS). A preliminary study was performed to determine the following parameters: instrumental detection limit (IDL), isotopic ratio measurement limit (IRML), percentage of DU (P(DU)) in presence of natural uranium (NU) and limit of quantification (LoQ(DU)). The analyses were carried out by means of IR-DRC-ICP-MS. Ammonia was the reaction gas used for the dynamic reaction cell. In addition, a sector field inductively coupled plasma mass spectrometer (SF-ICP-MS) was employed to calculate the within-laboratory reproducibility. For the confirmatory method the following parameters were determined: (a) trueness; (b) precision; (c) critical concentrations alpha and beta (CC(alpha), CC(beta)); (d) specificity; (e) stability. Trueness was assessed by using the recovery tests. The recovery and within-laboratory reproducibility were determined by fortifying the blank digested solution of dogfish tissue: six aliquots were fortified at 1, 1.5 and 2 times the LOQ(DU) with 25.0, 37.5 and 50.0 ng L(-1) or 4.16, 6.24, 8.32 microg kg(-1) with a recovery of -8.2, +9.5 and +9.6%, respectively and a within-laboratory reproducibility (three analytical run) of 15.5, 8.0 and 11.0%, respectively. The results for the decision limit and the detection capability were: CC(alpha) = 11.69 ng L(-1) and CC(beta) = 19.8 ng L(-1). The digested solutions resulted to be stable during testing time (60 days) and the method can be considered highly specific as well.

Metal changes in CSF and peripheral compartments of parkinsonian patients.

BACKGROUND: Involvement of metals in the risk of developing Parkinson's disease (PD) has been suggested. In the present study, concentration of metals in cerebrospinal fluid (CSF), blood, serum, urine and hair of 91 PD patients and 18 controls were compared. METHODS: Blood and hair were microwave digested, while CSF, serum and urine were water-diluted. Elements quantification was achieved by Inductively Coupled Plasma Atomic Emission Spectrometry and Sector Field Inductively Coupled Plasma Mass Spectrometry. RESULTS: Some metal imbalances in PD were observed: i), in CSF, lower Fe and Si; ii), in blood, higher Ca, Cu, Fe, Mg and Zn; iii), in serum, lower Al and Cu; iv), in urine, lower Al and Mn, higher Ca and Fe; and v), in hair, lower Fe. The ROC analysis suggested that blood Ca, Fe, Mg and Zn were the best discriminators between PD and controls. In addition, hair Ca and Mg were at least 1.5 times higher in females than in males of patients and controls. A decrement with age of patients in hair and urine Ca and, with less extent, in urine Si was observed. Magnesium concentration in CSF decreased with the duration and severity of the disease. Elements were not influenced by the type of antiparkinsonian therapy. CONCLUSIONS: Variation in elements with the disease do not exclude their involvement in the neurodegeneration of PD.

Determination of trace elements in serum by dynamic reaction cell inductively coupled plasma mass spectrometry: developing of a method with a desolvating system nebulizer.

An inductively coupled plasma mass spectrometer (ICP-MS), equipped with a dynamic reaction cell (DRC) and coupled with a desolvating nebulizing system (Apex-ACM) to reduce the oxide formation, was used in the determination of Al, Co, Cr, Mn, Ni and Se in serum samples. The effect of the operating conditions of the DRC system was studied to get the best signal-to-background (S/B) ratio. The potentially interfering molecular ions at the masses m/z27Al, 59Co, 52Cr, 55Mn, 60Ni and 78Se, were significantly reduced in intensity by using NH3 and H2, as the reaction cell gases in the DRC, while a proper Dynamic Bandpass Tuning parameter q (RPq) value was optimized. The detection limits for 27Al, 59Co, 52Cr, 55Mn, 60Ni and 78Se, estimated with 3-sigma method, resulted to be 0.14, 0.003, 0.002, 0.01, 0.01 and 1.8 microg L(-1), respectively. This analytical method was developed on both a human serum certified reference material and a lyophilized animal serum produced and proposed in an intercomparison study. The results obtained for the reference samples agreed satisfactorily with the certified values. Precision (expressed as CV%) between sample replicates was better than 10% for elements determination, with the only exception of aluminium (14%).

Simultaneous quantification of 17 trace elements in blood by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) equipped with a high-efficiency sample introduction system.

A quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) equipped with a dynamic reaction cell (DRC) and coupled with a desolvating nebulization system (APEX-IR) was employed to determine 17 elements (Al, As, Ba, Cd, Co, Cr, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, V, and Zr) in blood samples. Ammonia (for Al, Cr, Mn, and V) and O2 (for As and Se) were used as reacting gases. Selection of the best flow rate of the gases and optimization of the quadrupole dynamic bandpass tuning parameter (RPq) were carried out, using digested blood diluted 1+9 with deionized water and spiked with 1 microg L(-1) of Al, Cr, Mn, V and 5 microgL(-1) of As and Se. Detection limits were determined in digested blood using the 3sigma criterion. The desolvating system allowed a sufficient sensitivity to be achieved to determine elements at levels of ng L(-1) without detriment of signal stability. The accuracy of the method was tested with the whole blood certified reference material (CRM), certified for Al, As, Cd, Co, Cr, Mn, Mo, Ni, Pb, Sb, Se, and V, and with indicative values for Ba, Li, Sn, Sr, and Zr. The addition calibration approach was chosen for analysis. In order to confirm the DRC data, samples were also analyzed by means of sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), operating in medium (m/Deltam=4000) and high (m/Deltam=10,000) resolution mode and achieving a good agreement between the two techniques.

Assessment of workers' exposure to palladium in a catalyst production plant.

Airborne particulate matter was collected and biomonitoring of workers was performed by sampling blood, urine and hair of 84 exposed subjects, 17 occasionally exposed employees, 21 controls from administrative offices and 25 unexposed people (external controls). Determination of Pd was performed using Quadrupole and High Resolution Inductively Coupled Plasma Mass Spectrometry. The Production of Catalysts Department and the Refining Service presented the highest levels of Pd in airborne matter collected by means of an area sampler. The highest level of soluble Pd (1.66 microg m(-3)) was found in the Production of Catalysts Department. The highest concentration of Pd in airborne matter, collected by means of personal devices (7.90 microg m(-3)) was found in the Refining Service. Hair showed a clear distribution pattern among departments, with values ranging from 0.60 to 5.54 microg g(-1). Administrative workers presented blood levels of Pd between 2 and 500 times higher than external controls. Only urine levels correlated with the measurements of airborne Pd collected with personal devices. A very strong association between airborne Pd collected by personal devices and Pd levels in hair (r(2)= 0.569, with p< or = 0.01) and urine (r(2)= 0.684, with p< or = 0.01) was found. On the basis of these findings: (i) blood results appear to be an unsuitable biological marker for occupational exposure to Pd; (ii) urine could be considered as a satisfactorily responsive bio-marker for occupational monitoring; and (iii) hair cannot be considered a good index of time-related exposure.

Biomonitoring of a worker population exposed to platinum dust in a catalyst production plant.

AIMS: To evaluate the occupational exposure to platinum in an industrial plant engaged in the production, recovery, and recycling of catalytic converters for the automotive traction and chemical industries. METHODS: Pt was determined in airborne particulate matter, and blood, urine, and hair of 106 exposed workers, 21 controls from the plant's administrative offices, and 25 unexposed subjects. RESULTS: The highest air Pt level was found in the department of the plant in which supports are coated with acid metal solutions, where values of 2.39 and 4.83 microg/m3 respectively were found in environmental airborne particulate matter and in air collected using personal sampler devices. The percentage of soluble Pt was also highest in this area, varying from 24% to 44% of the total. The biological data confirmed this trend, with mean concentrations in this site being higher than in other working areas: 1.86 microg/l (urine), 0.38 microg/l (blood), and 2.26 microg/kg (hair). The workers employed in the administrative sector, who were not directly exposed to Pt, had levels of contaminant lower than those of other workers, albeit 2-20 times higher than those of external controls. High correlations were obtained between Pt levels detected in airborne samples using personal devices and those found in urine and hair, but not in blood. CONCLUSIONS: The background level of Pt in all areas of the factory implies widespread exposure for the workers. The most reliable biomarker was urine. Hair cannot be considered a good index of time related exposure, at least until more reliable methods of washing can be found that are able to remove exogenous Pt completely.

Trace and major elements in whole blood, serum, cerebrospinal fluid and urine of patients with Parkinson's disease.

Quantifications of Al, Ca, Cu, Fe, Mg, Mn, Si and Zn were performed in urine, serum, blood and cerebrospinal fluid (CSF) of 26 patients affected by Parkinson's disease (PD) and 13 age-matched controls to ascertain the potential role of biological fluids as markers for this pathology. Analyses were performed by Inductively Coupled Plasma Atomic Emission Spectrometry and Sector Field Inductively Coupled Plasma Mass Spectrometry. The serum oxidant status (SOS) and anti-oxidant capacity (SAC) were also determined. Results showed a decreasing trend for Al in all the fluids of PD patients, with the strongest evidence in serum. Calcium levels in urine, serum and blood of PD patients were significantly higher than in controls. Copper and Mg concentrations were significantly lower in serum of PD patients. Levels of Fe in urine, blood and CSF of patients and controls were dissimilar, with an increase in the first two matrices and a decrease in CSF. No significant difference was found in levels of Mn between patients and controls. Urinary excretion of Si was significantly higher in PD subjects than in controls. No clear difference between Zn levels in the two groups was found for serum, urine or CSF, but an increase in Zn levels in the blood of PD patients was observed. The SOS level in PD was significantly higher while the corresponding SAC was found to be lower in patients than in controls, in line with the hypothesis that oxidative damage is a key factor in the pathogenesis of PD. The results on the whole indicate the involvement of Fe and Zn (increased concentration in blood) as well as of Cu (decreased serum level) in PD. The augmented levels of Ca and Mg in the fluids and of Si in urine of patients may suggest an involuntary intake of these elements during therapy.

High-throughput microwave-digestion procedures to monitor neurotoxic elements in body fluids by means of inductively coupled plasma mass spectrometry.

Microwave (MW) digestion procedures with high sample throughput (simultaneous digestion of 36 or 80 samples) and procedural simplicity (disposable plastic tubes, or re-usable liners with screw-cap) were investigated for their efficiency in routine analyses of biological samples. Different digestion vessel materials were tested for metal leaching/adsorption and thermal resistance: quartz, glass, polyethylene (PE) and polystyrene (PS). For the instrumental quantification of Al, Bi, Cd, Co, Cr, Hg, Mn, Mo, Ni, Pb, Sb, and Tl at ultra-trace levels in urine, serum, and whole blood, sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) was used. The different pretreatment conditions and vessels were evaluated in terms of contamination risk, effective power of detection, accuracy, and precision. Results of analyses of serum, urine and whole blood certified reference materials (CRMs) were fully satisfactory for almost all the analytes. In the case of Hg, Mo, and Tl in serum digested in plastic containers the results were just below the lower limit of uncertainty of the certified range. On the basis of the present data the following MW procedures can be suggested: 1. for urine, digestion with nitric acid at atmospheric pressure in plastic vials; 2. for serum, digestion with nitric acid at atmospheric pressure in glass vessels; and 3. for whole blood, digestion under pressure in quartz tubes. Because of the levels of the procedural blanks, Bi was not measurable at the concentrations expected in human fluids, and Al was accurately detectable in whole blood only.

Assessment of reference values for elements in human hair of urban schoolboys.

Hair samples of youngsters (3-15 years of age) from several urban areas of Rome were analyzed to determine the content of 19 minor and trace elements with the aim of assessing Reference Values (RVs). Thirteen essential elements were taken into account, Ca, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Se, V and Zn. On the other hand, Al, As, Cd, Pb, Sr and Ti were also evaluated on the basis of their potential toxicity. Procedures were developed for the collection, storage and pre-analytical treatment of samples. Measurements were performed by inductively coupled plasma atomic emission spectrometry. Subgroups were formed according to age and sex. Significant differences were found for certain elements depending on age and sex. This was the case, e.g., for Ca which showed a mean value of 336 mg/kg for males and of 537 mg/kg for females. The sex-dependent pattern for this element was also apparent when the three age subgroups of 3-6, 7-10 and 11-15 years were compared. The overall RVs obtained (mg/kg) are as follows Al, 10.2; As, 0.09; Ca, 450; Cd, 0.23; Co, 0.67; Cr, 0.99; Cu, 22.1; Fe, 19.0; Mg, 28.0; Mn, 0.35; Mo, 0.43; Ni, 1.49; P, 195; Pb, 7.11; Se, 0.77; Sr, 1.20; Ti, 0.79; V, 1.22; and Zn 150.

Iron overload in patients with chronic viral hepatitis: how common is it?

OBJECTIVES: To establish the prevalence of increased hepatic iron content in patients with hepatitis C virus-related chronic hepatitis and to assess the accuracy of serum iron and ferritin in detecting tissue iron overload. METHODS: Serum iron, serum ferritin, and hepatic iron content were determined in 81 consecutive patients undergoing liver biopsy for chronic ALT elevation and hepatitis C virus infection. Moreover, in a subgroup of 28 patients, outcome of a 6-month course of interferon (IFN) treatment (6 million U of recombinant IFN, three times weekly) was determined after a mean follow-up of 24 +/- 6 months and the outcome was compared with the pretreatment values of hepatic iron content. RESULTS: Elevated serum iron or ferritin levels were detected in approximately 40% of patients, but elevated hepatic iron content was observed in only eight patients (10%). One of these patients had a hepatic iron index > 1.9, indicating hemochromatosis. Liver iron content and serum iron levels were not correlated. No differences in hepatic iron content were observed among patients with a sustained response to IFN (seven patients), short-term responders (seven patients), or nonresponders (14 patients). CONCLUSIONS: Ten percent of patients with chronic hepatitis C have elevated hepatic iron content. These patients cannot be identified using serum markers of iron status. The relationship between liver iron and response to IFN treatment requires further prospective investigations.

[Handling of biological material before trace element determination]. / Alcuni aspetti del trattamento di materiale biologico prima della determinazione di elementi in traccia.

The various steps of the analytical process are taken into account with particular reference to problems arising in sampling biological materials, their storage, pretreatment, digestion (when necessary) and determination. Emphasis is laid on the fact that the availability of analytical equipment with exceptional detection power is not always flanked by an equivalent ability to control phenomena of contamination and/or loss of analytes as well as to check and guarantee the accuracy of experimental data. In this context, proper use of the most popular analytical techniques for the determination of trace elements and the adoption of strict procedural conditions for data reliability are briefly discussed.

On-line speciation of arsenical compounds in fish and mussel extracts by HPLC-ICP-MS.

The separation and determination of sub-µmol/l levels of six environmentally significant As compounds was accomplished by means of high performance liquid chromatography (HPLC) combined online with inductively coupled plasma mass spectrometry (ICP-MS). The species of interest (arsenite and arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine and arsenocholine) were quantified in fish and mussel extracts after separation on a Dionex AS7 column equipped with an on-guard AG7 column using a bicarbonate buffer as the mobile phase in a gradient mode. The species thus eluted were directly forwarded to the ICP-MS detector. The detection power of the overall system allows each As form to be determined at concentrations as low a 0.0013-0.0027 µmol 1(-1).

Outline of the ISS code for the classification of chemical substances for use in compiling a national inventory.

A coding system for categorizing all types of compounds was developed specifically as part of the National Inventory of Chemical Substances to be applied by the Istituto Superiore di Sanità (ISS) in order to comply with the EEC present legal provisions on chemicals in trade. A number of applications were also described to illustrate the coverage and the adaptability of the code.

Present possibilities for the determination of inorganic arsenic and organoarsenical compounds in biological fluids.

A survey is presented of the applicability of atomic spectrometry and other techniques for the quantitation of both inorganic and organic arsenic in biological fluids. Pretreatment of samples and speciation of the different As forms are particularly emphasized. The potential of inductively-coupled plasma spectrometry combined with high performance liquid chromatography separations is also highlighted.

Reference values for elements of toxicological, clinical and environmental interest in hair of urban subjects.

A monitoring campaign has been undertaken to ascertain the reference concentration ranges for a number of minor and trace elements in hair of healthy urban subjects under age 15. An outline of criteria and methods lying at the root of a sound and reliable experimental approach are presented with special regard to such crucial steps as study planning, sampling, storing, pretreatment, analysis and evaluation of results. Determinations were carried out mainly by inductively-coupled plasma atomic emission spectrometry (ICP-AES) given the wide investigative potential and inherently multielemental character of this technique. The results obtained so far regard 100 youngsters allowing reference intervals for Al, As, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Pb, Se, Ti, V and Zn to be established for the population group tested. Finally, further developments of this activity are highlighted, particularly emphasizing the diagnostic capabilities of hair analysis.

Recent developments in the assay of ferritin containing drugs.

The advent of new stationary phases for gel permeation liquid chromatography (GPLC) capable of withstanding the high pressures of high performance liquid chromatography (HPLC) has opened new avenues for the analysis of large molecules such as ferritin. The exploitation of inductively-coupled plasma atomic emission spectrometry (ICP-AES) as a technique for detection in HPLC has evolved into a significant approach to element analysis and speciation. In general, while the on-line coupling still requires careful optimization, it expediently allows the identification of proteins and the quantification of Fe in ferritin products to be achieved.

[49 XXXXY syndrome. Description of 2 clinical cases]. / La sindrome 49 XXXXY. Descrizione di due casi clinici.

Two children with the 49, XXXXY syndrome were described. The main symptoms were the cranio-facial abnormalities (for exp. upward slant to palpebral fissures), hypogonadism with a small penis, skeletal abnormalities (especially radioulnar synostosis) and severe mental deficiency. The diagnosis, suggested by the clinical picture, was confirmed by the karyotypic analysis.