Bruno Lemos Batista

Evaluation of the use of human hair for biomonitoring the deficiency of essential and exposure to toxic elements

Monitoring the nutritional status of essential elements and assessing exposure of individuals to toxic elements is of great importance for human health. Thus, the appropriate selection and measurement of biomarkers of internal dose is of critical importance. Due to their many advantages, hair samples have been widely used to assess human exposure to different contaminants. However, the validity of this biomarker in evaluating the level of trace elements in the human body is debatable. In the present study, we evaluated the relationship between levels of trace elements in hair and whole blood or plasma in a Brazilian population. Hair, blood and plasma were collected from 280 adult volunteers for metal determination. An ICP-MS was used for sample analysis. Manganese, copper, lead and strontium levels in blood varied from 5.1 to 14.7, from 494.8 to 2383.8, from 5.9 to 330.1 and from 11.6 to 87.3 microg/L, respectively. Corresponding levels in hair varied from 0.05 to 6.71, from 0.02 to 37.59, from 0.02 to 30.63 and from 0.9 to 12.6 microg/g. Trace element levels in plasma varied from 0.07 to 8.62, from 118.2 to 1577.7 and from 2.31 to 34.2 microg/L for Mn, Cu and Sr, respectively. There was a weak correlation (r=0.22, p<0.001) between lead levels in hair and blood. Moreover, copper and strontium levels in blood correlate with those levels in plasma (r=0.64 , p<0.001 for Cu) and (r=0.22, p<0.05 for Sr). However, for Cu, Mn and Sr there was no correlation between levels in hair and blood. Our findings suggest that while the idea of measuring trace elements in hair is attractive, hair is not an appropriate biomarker for evaluating Cu, Mn and Sr deficiency or Pb exposure.

Speciation of arsenic in rice and estimation of daily intake of different arsenic species by Brazilians through rice consumption

Rice is an important source of essential elements. However, rice may also contain toxic elements such as arsenic. Therefore, in the present study, the concentration of total arsenic and five main chemical species of arsenic (As(3+), As(5+), DMA, MMA and AsB) were evaluated in 44 different rice samples (white, parboiled white, brown, parboiled brown, parboiled organic and organic white) from different Brazilian regions using high-performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The mean level of total arsenic was 222.8 ng g(-1) and the daily intake of inorganic arsenic (the most toxic form) from rice consumption was estimated as 10% of the Provisional Tolerable Daily Intake (PTDI) with a daily ingestion of 88 g of rice. Inorganic arsenic (As(3+), As(5+)) and dimethylarsinic acid (DMA) are the predominant forms in all samples. The percentages of species were 38.7; 39.7; 3.7 and 17.8% for DMA, As(3+), MMA and As(5+), respectively. Moreover, rice samples harvested in the state of Rio Grande do Sul presented more fractions of inorganic arsenic than rice in Minas Gerais or Goiás, which could lead to different risks of arsenic exposure.

Simultaneous determination of Cd, Cu, Mn, Ni, Pb and Zn in nail samples by inductively coupled plasma mass spectrometry (ICP-MS) after tetramethylammonium hydroxide solubilization at room temperature: Comparison with ETAAS

A simple method is described for the determination of Cd, Cu, Mn, Ni, Pb and Zn in nails by using inductively coupled plasma mass spectrometry (ICP-MS) or electrothermal atomic absorption spectrometry (ETAAS). Prior to analysis, 10-20 mg of nail samples were accurately weighed into (15 mL) conical tubes. Then, 1 mL of 25% (w/v) tetramethylammonium hydroxide (TMAH) solution was added to the samples, incubated at room temperature overnight and then further diluted to 10 mL with 1% (v/v) HNO(3). After that, samples were directly analyzed. Rhodium was used as internal standard for ICP-MS analysis. Method detection limits (3 s, n=20) were 0.1, 3.0, 1.0, 4.5, 1.5, 5.0 ng g(-1) for Cd, Cu, Mn, Ni, Pb and Zn, respectively for ICP-MS, and 24, 26, 30, 143, 130 and 1000 ng g(-1), respectively for ETAAS. The key issue addressed here is the elimination of the acid digestion prior to analysis. Moreover, with the use of the proposed method there is a considerable improvement in the sample throughput comparing to the traditional methods using microwave-assisted acid sample digestion prior to analysis. For validation purposes, six ordinary nail samples were solubilized and then directly analyzed by ICP-MS and ETAAS, with no statistical difference between the two techniques at 95% level on applying the t-test.

Determination of trace elements in biological samples by inductively coupled plasma mass spectrometry with tetramethylammonium hydroxide solubilization at room temperature

A simple method for sample preparation of biological samples for trace elements determination by inductively coupled plasma mass spectrometry (ICP-MS) is described. Prior to analysis, 75 mg of the biological samples were accurately weighed into (15 mL) conical tubes. Then, 1 mL of 50% (v/v) tetramethylammonium hydroxide (TMAH) solution was added to the samples, incubated at room temperature for 12 h and the volume made up to 10 mL with a solution containing 0.5% (v/v) HNO(3), 0.01% (v/v) Triton X-100 and 10 microg L(-1) of Rh. After preparation samples may be stored at -20 degrees C during 3 days until the analysis by ICP-MS. With these conditions, the use of the dynamic reaction cell was only mandatory for chromium determination. Method detection limits were 0.2145, 0.0020, 0.0051, 0.0017, 0.0027, 0.0189, 0.02, 0.5, 0.1, 0.0030, 0.0043, 0.0066, 0.0009, 0.020, 0.0043, 0.1794, 0.1 microg(-1) for Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Pb, Sb, Se, Sr, V and Zn, respectively. Validation data are provided based on the analysis of six certified reference materials (CRMs) purchased from the National Institute of Standards and Technology (NIST) and National Research Council Canada (NRCC). Additional validation was provided by the analysis of brain, kidney, liver and heart samples collected from rats and analyzed by the proposed method and by using microwave digestion.

Identification and quantification of phytochelatins in roots of rice to long-term exposure: evidence of individual role on arsenic accumulation and translocation

Summary Six varieties of rice were exposed to low and high levels of arsenic in the same soil. Their individual responses of expressing phytochelatins have been correlated to inorganic arsenic uptake, transport, and accumulation in the rice grain.

A Simple Method Based on ICP-MS for Estimation of Background Levels of Arsenic, Cadmium, Copper, Manganese, Nickel, Lead, and Selenium in Blood of the Brazilian Population

Throughout the world, biomonitoring has become the standard for assessing exposure of individuals to toxic elements as well as for responding to serious environmental public health problems. However, extensive biomonitoring surveys require rapid and simple analytical methods. Thus, a simple and high-throughput method is proposed for the determination of arsenic (As), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se) in blood samples by using inductively coupled plasma–mass spectrometry (ICP-MS). Prior to analysis, 200 μl of blood samples was mixed with 500 μl of 10% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 10 min, and subsequently diluted to 10 ml with a solution containing 0.05% w/v ethylenediamine tetraacetic acid (EDTA) + 0.005% v/v Triton X-100. After that, samples were directly analyzed by ICP-MS (ELAN DRC II). Rhodium was selected as an internal standard with matrix-matching calibration. Method detection limits were 0.08, 0.04, 0.5, 0.09, 0.12, 0.04, and 0.1 μg//L for As, Cd, Cu, Mn, Ni, Pb, and Se, respectively. Validation data are provided based on the analysis of blood samples from the trace elements inter-\comparison program operated by the Institut National de Santé Publique du Quebec, Canada. Additional validation was provided by the analysis of human blood samples by the proposed method and by using electrothermal atomic absorption spectrometry (ETAAS). The method was subsequently applied for the estimation of background metal blood values in the Brazilian population. In general, the mean concentrations of As, Cd, Cu, Mn, Ni, Pb, and Se in blood were 1.1, 0.4, 890, 9.6, 2.1, 65.4, and 89.3 μg/L, respectively, and are in agreement with other global populations. Influences of age, gender, smoking habits, alcohol consumption, and geographical variation on the values were also considered. Smoking habits influenced the levels of Cd in blood. The levels of Cu, Mn, and Pb were significantly correlated with gender, whereas Cu and Pb were significantly correlated with age. There were also interesting differences in Mn and Se levels in the population living in the north of Brazil compared to the south.

Mercury speciation in seafood samples by LC-ICP-MS with a rapid ultrasound-assisted extraction procedure: Application to the determination of mercury in Brazilian seafood samples.

This paper describes a simple method for mercury speciation in seafood samples by LC-ICP-MS with a fast sample preparation procedure. Prior to analysis, mercury species were extracted from food samples with a solution containing mercaptoethanol, l-cysteine and HCl and sonication for 15min. Separation of mercury species was accomplished in less than 5min on a C8 reverse phase column with a mobile phase containing 0.05%-v/v mercaptoethanol, 0.4%m/v l-cysteine and 0.06molL(-1) ammonium acetate. The method detection limits were found to be 0.25, 0.20 and 0.1ngg(-1) for inorganic mercury, ethylmercury and methylmercury, respectively. Method accuracy is traceable to Certified Reference Materials (DOLT-3 and DORM-3) from the National Research Council Canada (NRCC). With the proposed method there is a considerable reduction of the time of sample preparation. Finally, the method was applied for the speciation of mercury in seafood samples purchased from the Brazilian market.

Determination of total and inorganic mercury in whole blood by cold vapor inductively coupled plasma mass spectrometry (CV ICP-MS) with alkaline sample preparation

A simple method with a fast sample preparation procedure for total and inorganic mercury determinations in blood samples is proposed based on flow injection cold vapor inductively coupled plasma mass spectrometry (FI-CV ICP-MS). Aliquots of whole blood (500 µL) are diluted 1 + 1 v/v with 10.0% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 3 h at room temperature and then further diluted 1 + 4 v/v with 2.0% v/v HCl. The inorganic Hg was released by on-line addition of L-cysteine and then reduced to elemental Hg by SnCl2. On the other hand, total mercury was determined by on-line addition of KMnO4 and then reduced to elemental Hg by NaBH4. Samples were calibrated against matrix-matching. The method detection limit was found to be 0.80 µg L−1 and 0.08 µg L−1 for inorganic and total mercury, respectively. Sample throughput is 20 samples h−1. The method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from the National Institute of Standards and Technology (NIST). For additional validation purposes, human whole blood samples were analyzed by the proposed method and by an established CV AAS method, with no statistical difference between the two techniques at 95% confidence level on applying the t-test.

A fast method for the determination of 16 elements in hair samples by inductively coupled plasma mass spectrometry (ICP-MS) with tetramethylammonium hydroxide solubilization at room temperature

This paper describes a simple and fast method for the determination of Se, Pb, Cd, Mn, Co, Zn, Cu, Pt, U, Tl, As, Mg, Cr, Be, Ag and Ni in hair by using inductively coupled plasma spectrometry (ICP-MS). Prior to analysis, 50–100 mg of hair samples were accurately weighed into (15 mL) conical tubes. Then, 1 mL of 25% m/v tetramethylammonium hydroxide (TMAH) solution was added to the samples, incubated at room temperature overnigh and then further diluted to 10 mL with 1% v/v HNO3. After that, samples were directly analyzed by ICP-MS (ELAN DRC II). Rhodium was used as internal standard. Calibration was performed with standards containing 1.0 mg mL−1 of L-cysteine. The method detection limits were 4.0; 0.8; 0.06; 0.8; 0.02; 3.5; 2.3; 0.005; 0.03; 0.02; 0.4; 0.03; 0.09; 0.07; 0.09; 2.0 ng g−1 for Se, Pb, Cd, Mn, Co, Zn, Cu, Pt, U, Tl, As, Mg, Cr, Be, Ag and Ni, respectively. Method accuracy is traceable to Certified Reference Materials (CRMs) 85 and 86 human hair from the International Atomic Energy Agency (IAEA). Additional validation data are provided based on the analysis of hair samples from the trace elements intercomparison program operated by the Institut National de Sante Publique du Quebec, Canada. With the proposed method at least 500 hair samples can be solubilized and analyzed in 3–4 days.

Survey of 13 trace elements of toxic and nutritional significance in rice from Brazil and exposure assessment

Twenty-seven rice samples from Brazil, four parboiled brown, seventeen white and six parboiled white were analysed by ICP-MS for trace element determination. Concentrations of arsenic varied from 58.8 to 216.9 ng g−1, for cadmium from 6.0 to 20.2 ng g−1, for antimony from 0.12 to 1.28 ng g−1, and for uranium from 0.025 to 1.28 ng g−1. The estimated daily intake through rice consumption was 9.5 µg for As, 2.4 µg for Cd, 0.029 µg for Sb, 0.013 µg for U, 3.1 µg for Co, 0.2 µg for Cu, 85.6 mg for Mg, 1.9 mg for Mn, 333 mg for P, 3.0 µg for Se, 1.6 mg for Zn, 0.9 mg for Rb, and 0.3 µg for V. Found values represent a considerable percentage of the dietary reference intakes and provisional tolerable daily intake for essential and toxic elements, respectively.