Derivation and validation of thresholds of cadmium, chromium, lead, mercury and arsenic for safe rice production in paddy soil.

Cadmium (Cd), chromium (Cr), lead (Pb), mercury (Hg) and arsenic (As) are potent toxicants to human health via dietary intake. It is imperative to establish accurate soil thresholds based on soil-plant transfer models and food safety standards for safe agricultural production. This study takes rice genotypes and soil properties into account to derive soil thresholds for five heavy metal(loid)s using the bioconcentration factors (BCF) and species sensitivity distribution (SSD) based on the food safety standard. The BCF generated from two paddy soils was calculated to investigate the sensitivity of heavy metal accumulation in nine rice cultivars in a greenhouse pot experiment. Then, empirical soil-plant transfer models were developed from a middle-sensitivity rice cultivar (Denong 2000, one selected from nine rice) grown in nineteen paddy soils with various soil properties under a proper exogenously metal(loid)s concentration gradient. After normalization, hazardous concentrations from the fifth percentile (HC5) were calculated from the SSD curves, and the derived soil thresholds were obtained from HC5 prediction models that based on the combination of pH and organic carbon (OC) or cation exchange capacity (CEC). The soil Cd threshold derived based on pH and organic carbon (pH < 7.5, OC ≥ 20 g kg-1) was 1.3-fold of those only considering pH, whereas the Pb threshold (pH > 6, CEC ≥ 20 cmolc kg-1) was 3.1 times lower than the current threshold. The derived thresholds for five elements were validated to be reliable through literature data and field experiments. The results suggested that deriving soil heavy metal(loid)s threshold using SSD method and local food safety standards is feasible and also applicable to other crops as well as other regions with potential health risks of toxic elements contamination in agricultural production.

Development of certified reference materials for the determination of cadmium and acrylamide in cocoa.

Since 1 January 2019 a maximum content of 0.6 mg kg-1 cadmium (Cd) in cocoa powder sold to the final consumer or as an ingredient in sweetened cocoa powder sold to the final consumer (drinking chocolate) is set by the Commission Regulation (EU) No. 488/2014. Monitoring compliance with the specified limit value requires analytical measuring methods and reference materials for quality control. However, suitable certified reference materials intended for quality assurance and quality control purposes are still lacking. Therefore, three cocoa reference materials (ERM®-BD513, ERM®-514 and ERM®-515) were developed according to the requirements of ISO 17034 and the recommendations of ISO Guide 35. The whole process of reference material development, including material preparation, assessment of homogeneity and stability, characterisation and value assignment is presented. The assignment of the certified mass fractions was based upon an interlaboratory comparison study involving 19 expert laboratories for Cd and 12 laboratories for acrylamide. The certified mass fractions and expanded uncertainties (k = 2) of the reference materials were (0.181 ± 0.009) mg kg-1 Cd (ERM®-BD513), (0.541 ± 0.024) mg kg-1 Cd (ERM®-BD514) and (0.690 ± 0.029) mg kg-1 Cd (ERM®-BD515). Acrylamide contents are given for information.

Risks of consuming cadmium-contaminated shellfish under seawater acidification scenario: Estimates of PBPK and benchmark dose.

We aim to assess the risks of renal dysfunction and osteoporosis that is attributed to the seawater acidification caused cadmium (Cd) level increase in human consumed shellfish. A physiology-based pharmacokinetic model was used to estimate Cd concentrations in urine and blood among shellfish-only consumers and among the general population. We used the benchmark dose (BMD) method to determine the threshold limits of Cd in urine for renal dysfunction and in blood for osteoporosis for assessing the human health risk. Our results revealed that seawater acidification could increase the Cd accumulation in shellfish by 10-13% compared to the situations under current pH levels. Under the lower seawater pH level, the daily intake of Cd could increase by 21%-67% among shellfish-only consumers, and by 13%-17% among the general population. Our findings indicated that seawater acidification would lead to a marginal increase in Cd intake among humans in shellfish-only consumers. The results of BMDs of urinary Cd showed that the threshold limits for renal dysfunction at 5% were 3.00 µg g-1 in males and 12.35 µg g-1 in females. For osteoporosis, the estimated BMDs of blood Cd were 7.95 µg L-1 in males and 1.23 µg L-1 in females. These results of the risk of Cd intake showed that the consumption of Cd-contaminated shellfish in the general population is largely unaffected by changes in seawater pH levels. Notably, the potential impact of seawater acidification on renal dysfunction for males in shellfish-only consumers face a 14% increase of risk.

Toxicity of cadmium in musculoskeletal diseases.

Epidemiological studies have reported that exposure to toxic metals like cadmium (Cd) may promote the development of musculoskeletal diseases, such as osteoporosis, rheumatoid arthritis (RA), and osteoarthritis (OA), among others. The objective of this review is to summarize the molecular mechanisms of inflammation and oxidative stress activated by Cd at the bone level, particularly in osteoporosis, RA, and OA. Cadmium can increase bone resorption, affect the activity of osteoclasts and calcium (Ca) absorption, and impair kidney function, which favors the development of osteoporosis. In the case of RA, Cd interferes with the activity of antioxidant proteins, like superoxide dismutase (SOD) and catalase (CAT). It also promotes an inflammatory state, inducing the process of citrullination, which affects the proteins of immune response. On the other hand, accumulation of Cd in the tissues and blood of smokers has been related to the development of some musculoskeletal diseases. Therefore, knowing the negative impact of Cd toxicity at the articular level can help understand the damage mechanisms it produces, leading to the development of such diseases.

Cadmium uptake by onions, lettuce and spinach in New Zealand: Implications for management to meet regulatory limits.

Paired soil and plant samples collected from the main commercial growing areas for onions (Allium cepa), lettuce (Lactuca sativa) and spinach (Spinacia olearacea) in New Zealand were used to assess the influence of plant and soil factors on cadmium (Cd) uptake in these crops. Differences in Cd concentration between eight lettuce sub-types were not consistent across sites, nor were differences in Cd concentrations in three crisphead cultivars assessed at two sites. Similarly, differences in Cd concentrations between four onion cultivars were inconsistent across sites. Mean lettuce Cd concentrations in eight lettuce varieties (range 0.005-0.034 mg∙kg-1 (fresh weight, FW) were markedly lower than those in baby leaf and bunching spinach, (range 0.005-0.19 mg∙kg-1 FW). Significant regional variation was observed in Cd concentrations in one onion cultivar (mean range 0.007-0.05 mg∙kg-1 FW). Soil Cd concentration, pH and region were statistically significant predictors of onion Cd concentration, explaining low (38% for soil Cd and pH) to moderate (50% for all three parameters) percentage of the variation. Soil Cd concentration and exchangeable magnesium or total carbon were statistically significant predictors of Cd concentration in baby leaf and bunching spinach, respectively, explaining a moderate percentage (49% and 42%) of the variation in Cd concentration. Increasing pH and soil carbon may assist in minimising Cd uptake in onion and bunching spinach, respectively. The low to moderate proportion of explained variation is partly attributable to the narrow range in some measured soil properties and indicates factors other than those assessed are influencing plant uptake. This highlights a challenge in using these relationships to develop risk-based soil guideline values to support compliance with food standards. Similarly, the inconsistency in Cd concentrations in different cultivars across sites highlights the need for multi-site assessments to confirm the low Cd accumulation status of different cultivars.

Health Risk Assessment of Dietary Cadmium Intake: Do Current Guidelines Indicate How Much is Safe?

BACKGROUND: Cadmium (Cd), a food-chain contaminant, is a significant health hazard. The kidney is one of the primary sites of injury after chronic Cd exposure. Kidney-based risk assessment establishes the urinary Cd threshold at 5.24 µg/g creatinine, and tolerable dietary intake of Cd at 62 µg/day per 70-kg person. However, cohort studies show that dietary Cd intake below a threshold limit and that tolerable levels may increase the risk of death from cancer, cardiovascular disease, and Alzheimer's disease. OBJECTIVE: We evaluated if the current tolerable dietary Cd intake guideline and urinary Cd threshold limit provide sufficient health protection. DISCUSSION: Staple foods constitute 40-60% of total dietary Cd intake by average consumers. Diets high in shellfish, crustaceans, mollusks, spinach, and offal add to dietary Cd sources. Modeling studies predict the current tolerable dietary intake corresponding to urinary Cd of 0.70-1.85 µg/g creatinine in men and 0.95-3.07 µg/g creatinine in women. Urinary Cd levels of < 1 µg/g creatinine were associated with progressive kidney dysfunction and peripheral vascular disease. A urinary Cd of 0.37 µg/g creatinine was associated with breast cancer, whereas dietary Cd of 16-31.5 µg/day was associated with 25-94% increase in risk of estrogen receptor-positive breast cancer. CONCLUSION: Modeling shows that dietary intake levels for Cd exceed the levels associated with kidney damage and many other adverse outcomes. Thus, the threshold level of urinary Cd should be re-evaluated. A more restrictive dietary intake guideline would afford enhanced health protection from this pervasive toxic metal. Citation: Satarug S, Vesey DA, Gobe GC. 2017. Health risk assessment of dietary cadmium intake: do current guidelines indicate how much is safe? Environ Health Perspect 125:284-288; http://dx.doi.org/10.1289/EHP108.

Spectrum reconstruction method based on the detector response model calibrated by x-ray fluorescence.

Accurate estimation of distortion-free spectra is important but difficult in various applications, especially for spectral computed tomography. Two key problems must be solved to reconstruct the incident spectrum. One is the acquisition of the detector energy response. It can be calculated by Monte Carlo simulation, which requires detailed modeling of the detector system and a high computational power. It can also be acquired by establishing a parametric response model and be calibrated using monochromatic x-ray sources, such as synchrotron sources or radioactive isotopes. However, these monochromatic sources are difficult to obtain. Inspired by x-ray fluorescence (XRF) spectrum modeling, we propose a feasible method to obtain the detector energy response based on an optimized parametric model for CdZnTe or CdTe detectors. The other key problem is the reconstruction of the incident spectrum with the detector response. Directly obtaining an accurate solution from noisy data is difficult because the reconstruction problem is severely ill-posed. Different from the existing spectrum stripping method, a maximum likelihood-expectation maximization iterative algorithm is developed based on the Poisson noise model of the system. Simulation and experiment results show that our method is effective for spectrum reconstruction and markedly increases the accuracy of XRF spectra compared with the spectrum stripping method. The applicability of the proposed method is discussed, and promising results are presented.

Temporal variability of blood lead, mercury, and cadmium levels in elderly panel study (2008-2014).

BACKGROUND: Biological measurements have been employed as useful biomarkers for exposure. Because of its property of reflecting toxicokinetic differences, however, within-subject variability leads to biased results in epidemiologic studies. METHOD: We examined the variability of lead (Pb), mercury (Hg), and cadmium (Cd) levels in blood samples from 1429 participants among 1677 elderly individuals aged over 60 years who lived in an urban area from August 2008 to April 2015. RESULTS: The geometric means of blood Pb, Hg, Cd were 1.92µg/dL, 2.48µg/L, and 1.33µg/L, and the intra-class correlations (ICCs) were 0.81, 0.71, and 0.83, respectively. The mean values of Pb and Hg levels in this study were lower than the results from single spot samples in other national biomonitoring surveys in Korea, with the exception of Cd was higher than those in other studies. Moreover, the predicted exceedances over the guidance levels for Pb, Hg, and Cd were 1.9%, 4.2%, and 0.3%, respectively. CONCLUSION: Korean elderly were exposed to high levels of Pb, Hg and Cd. Especially, those who had high levels of Cd were continuously exposed to Cd during study period with the 6 collection intervals. Therefore, factors affecting environmental Cd exposure should be further studied in the future.

Associated factors for higher lead and cadmium blood levels, and reference values derived from general population of São Paulo, Brazil.

Human activities are associated with emissions of various metals into the environment, among which the heavy metals lead and cadmium stand out, as they pose a risk to human life even at low concentrations. Thus, accurate knowledge of the levels of these metals exhibited by the overall population, including children, is important. The aim of this study was to estimate the concentrations of lead and cadmium in the blood of adults, adolescents and children residing in the city of São Paulo, assess factors associated with higher lead and cadmium blood levels, and to establish reference values for this population. The study sample consisted of 669 adults over 20 years old, 264 adolescents aged 12 to 19 years old and 391 children under 11 years old from both genders. The samples were collected at the end of 2007 and during 2008 in different city zones. Higher blood lead concentration was significantly associated with gender, smoking, offal intake, area of residence and age. The blood cadmium concentration was significantly associated with gender, smoking, consumption of distilled beverages and age. The reference values of lead and cadmium established for adults above 20 years old were 33 µg/L and 0.6 µg/L, respectively, for adolescents (12 to 19 years old) were 31 µg/L and 0.6 µg/L, respectively and for children under 11 years old were 29 µg/L and 0.2 µg/L, respectively. The results of this study indicate that the exposure levels of the investigated population to lead and cadmium are low.

Content of Cadmium and Lead in Vegetables and Fruits Grown in the Campania Region of Italy.

Illegal practices of waste combustion and their burial in some land devoted to agricultural crops caused a severe economic crisis of the agriculture and food sector in the Campania region of Italy. To assess the levels of contamination by lead and cadmium, the only metals subject to European Union legislation, a system of monitoring of plant foods in the whole territory of the region has been promoted, with the goal of certifying productions and consumer protection. In fact, products that comply with European Union standards are assigned a Quick Response Code, which guarantees the traceability of the product (manufacturer and location). The code also ensures the safety of the product, as it allows the consumer to see the results of the analysis performed on the specific chain of production. The content of lead and cadmium was determined in 750 vegetable samples by using the atomic absorption spectrophotometry after microwave mineralization. These levels were below the maximum limits in all but three samples; two samples of tomatoes exceeded the maximum level of cadmium, and one sample of valerian contained an excess of lead.

Dietary intake of trace elements by the population of Catalonia (Spain): results from a total diet study.

This study aimed to analyse the concentrations of Al, Ba, Bi, Cu, Cr, Ge, Mn, Mo, Ni, Sb, Se, Sr and Zn in food samples collected in 2008 in Catalonia (Spain). The dietary intake of these 13 trace elements was subsequently estimated by different age-gender groups of the population: children, adolescents, adults and seniors. In general terms, fish and shellfish, cereals, and pulses were the food groups showing the highest levels for most elements. Higher dietary intakes were associated with male groups (adolescents, adults and seniors). However, none exceeded the tolerable levels. When exposure was estimated based on body weight, children were the group with the highest dietary intake. Notwithstanding, only the weekly intake of Al by children exceeded the recommendations of the European Food Safety Authority (EFSA). It is a consequence of the higher intake of cereals in relation to their respective body weights. In addition to the periodical food surveillance of toxic metals (As, Cd, Hg and Pb), it is also important to determine the levels of other trace elements in order to ensure that the dietary exposure by the Catalan population is under control.

The heavy metals cadmium, lead and mercury in raw materials of animal origin: evaluation of data from practice.

Raw materials from animal origin are widely used in homoeopathy. Due to the lack of dedicated limits, the quality requirements for herbal drugs of the European Pharmacopoeia (Ph. Eur.) and/or the German Homoeopathic Pharmacopoeia (Homöopathisches Arzneibuch, HAB), including limits for heavy metals such as cadmium, lead and mercury, have been applied. A recent database evaluation shows that for some raw materials of animal origin the Ph. Eur. limits for herbal drugs cannot be met in practice. For this reason proposals for new limits for cadmium, lead and mercury are made based on recent experiences from the companies' daily practice. These specific limits are suggested to be included in the individual monographs of the Ph. Eur. or at least the German HAB, respectively, for Ambra grisea, Euspongia officinalis, Formica rufa and Sepia officinalis.

Certification of a reference material of metal content in atmospheric particles deposited on filters.

Air quality is one of the areas in Europe where a series of EU Directives have been published with the aim of achieving improved long-term and harmonised air quality objectives across the European Union. This paper describes the production of a certified reference material, aiming to support QA/QC programmes of analytical laboratories in the framework of the air quality monitoring activities. The certified values are the As, Cd, Ni and Pb masses in PM10 particles deposited on quartz filters (CRM SL-MR-2-PSF-01). All the steps of the certification, i.e. the material characterisation, homogeneity and stability evaluation and uncertainty calculation, were performed according to the ISO guide 35 guidelines. The certification was conducted using the characterisation by a single method approach based on isotope dilution for cadmium, nickel, and lead and gravimetric standard addition calibration for arsenic associated with inductively coupled mass spectrometry (ICP-MS). The amounts of the four elements are in the range of the target values regulated by EU Directives.

Cadmium background concentrations to establish reference quality values for soils of São Paulo State, Brazil.

Proper assessment of soil cadmium (Cd) concentrations is essential to establish legislative limits. The present study aimed to assess background Cd concentrations in soils from the state of São Paulo, Brazil, and to correlate such concentrations with several soil attributes. The topsoil samples (n = 191) were assessed for total Cd contents and for other metals using the USEPA 3051A method. The background concentration was determined according to the third quartile (75th). Principal component analysis, Spearman correlation, and multiple regressions between Cd contents and other soil attributes (pH, cation exchange capacity (CEC), clay content, sum of bases, organic matter, and total Fe, Al, Zn, and Pb levels) were performed. The mean Cd concentration of all 191 samples was 0.4 mg kg(-1), and the background concentration was 0.5 mg kg(-1). After the samples were grouped by parent material (rock origin) and soil type, the background Cd content varied, i.e., soils from igneous, metamorphic, and sedimentary rocks harbored 1.5, 0.4, and 0.2 mg kg(-1) of Cd, respectively. The background Cd content in Oxisols (0.8 mg kg(-1)) was higher than in Ultisols (0.3 mg kg(-1)). Multiple regression demonstrated that Fe was primarily attributed to the natural Cd contents in the soils (R (2) = 0.79). Instead of a single Cd background concentration value representing all São Paulo soils, we propose that the concentrations should be specific for at least Oxisols and Ultisols, which are the primary soil types.

Highly sensitive detection of urinary cadmium to assess personal exposure.

A series of Boron-Doped Diamond (BDD) ultramicroelectrode arrays were fabricated and investigated for their performance as electrochemical sensors to detect trace level metals such as cadmium. The steady-state diffusion behavior of these sensors was validated using cyclic voltammetry followed by electrochemical detection of cadmium in water and in human urine to demonstrate high sensitivity (>200 µA ppb(-1) cm(-2)) and low background current (<4 nA). When an array of ultramicroelectrodes was positioned with optimal spacing, these BDD sensors showed a sigmoidal diffusion behavior. They also demonstrated high accuracy with linear dose dependence for quantification of cadmium in a certified reference river water sample from the U.S. National Institute of Standards and Technology (NIST) as well as in a human urine sample spiked with 0.25-1 ppb cadmium.

Recognizing and overcoming analytical error in the use of ICP-MS for the determination of cadmium in breakfast cereal and dietary supplements.

The potential effect of spectral interference on the accurate measurement of the cadmium (Cd) mass fraction in fortified breakfast cereal and a variety of dietary supplement materials using inductively coupled plasma quadrupole mass spectrometry was studied. The materials were two new standard reference materials (SRMs)--SRM 3233 Fortified Breakfast Cereal and SRM 3532 Calcium Dietary Supplement--as well as several existing materials--SRM 3258 Bitter Orange Fruit, SRM 3259 Bitter Orange Extract, SRM 3260 Bitter Orange-containing Solid Oral Dosage Form, and SRM 3280 Multivitamin/Multielement Tablets. Samples were prepared for analysis using the method of isotope dilution and measured using various operating and sample introduction configurations including standard mode, collision cell with kinetic energy discrimination mode, and standard mode with sample introduction via a desolvating nebulizer system. Three isotope pairs, (112)Cd/(111)Cd, (113)Cd/(111)Cd, and (114)Cd/(111)Cd, were measured. Cadmium mass fraction results for the unseparated samples of each material, measured using the three instrument configurations and isotope pairs, were compared to the results obtained after the matrix was removed via chemical separation using anion exchange chromatography. In four of the six materials studied, measurements using the standard mode with sample introduction via the desolvating nebulizer gave results for the unseparated samples quantified with the (112)Cd/(111)Cd isotope pair that showed a positive bias relative to the matrix-separated samples, which indicated a persistent inference at m/z112 with this configuration. Use of the standard mode, without the desolvating nebulizer, also gave results that showed a positive bias for the unseparated samples quantified with the (112)Cd/(111)Cd isotope pair in three of the materials studied. Collision cell/kinetic energy discrimination mode, however, was very effective for reducing spectral interference for Cd in all of the materials and isotope pairs studied, except in the multivitamin/multielement matrix (SRM 3280) where the large corrections for known isobaric interferences or unidentified interferences compromised the accuracy. For SRM 3280, matrix separation provided the best method to achieve accurate measurement of Cd.

Assessment of homogeneity and minimum sample mass for cadmium analysis in powdered certified reference materials and real rice samples by solid sampling electrothermal vaporization atomic fluorescence spectrometry.

To optimize analytical quality controls of solid sampling electrothermal vaporization atomic fluorescence spectrometry (SS-ETV-AFS), the homogeneity (H(E)) of rice samples and their minimum sample mass (M) for cadmium analysis were evaluated using three certified reference materials (CRMs) and real rice samples. The effects of different grinding degrees (particle sizes <0.85, <0.25, <0.15, and >1 mm) on H(E) and M of real rice samples were also investigated. The calculated M values of three CRMs by the Pauwels equation were 2.19, 19.76, and 3.79 mg. The well-ground real rice samples (particle size <0.25 mm) demonstrated good homogeneity, and the M values were 3.48-4.27 mg. On the basis of these results, the Cd concentrations measured by the proposed method were compared with the results by microwave digestion graphite furnace atomic absorption spectrometry with a 0.5 g sample mass. There was no significant difference between these two methods, which meant that SS-ETV-AFS could be used to accurately detect Cd in rice with several milligrams of samples instead of the certified value (200 mg) or the recommended mass (200-500 mg) of the methods of the Association of Official Analytical Chemists.

A baseline study of levels of mercury, arsenic, cadmium and lead in Northeast Arctic cod (Gadus morhua) from different parts of the Barents Sea.

This study is one of several baseline studies that will provide basic and reliable information about the content of undesirable substances in important species of fish caught in Norwegian waters. Concentrations of metals in the muscle and liver of more than 800 Northeast Arctic cod caught at 32 sites in the Barents Sea are reported. The highest concentration of both mercury in the muscle and cadmium in the liver was found in cod caught in the western part of the Barents Sea, while the highest concentration of total arsenic was found in cod from the eastern part. The arsenic concentrations varied greatly among individual fish, ranging from 0.3 to 170 mg kg(-1) wet weight in the muscle. Such high levels of total arsenic have never previously been reported in any fish, and the primary factor for these high concentrations is likely to be the shrimp in the cod diet.

Development of a certified reference material (NMIJ CRM 7531-a) for the determination of trace cadmium and other elements in brown rice flour.

A certified reference material (CRM) for trace cadmium and other elements in brown rice flour was developed at the National Metrology Institute of Japan (NMIJ). The CRM was provided as a dry powder after drying and frozen pulverization of fresh brown rice obtained from a Japanese domestic market. Characterization of the property value for each element was carried out exclusively by NMIJ with at least two independent analytical methods, including inductively coupled plasma mass spectrometry (ICP-MS), ICP high-resolution mass spectrometry, isotope-dilution ICP-MS, ICP optical emission spectrometry, and graphite-furnace atomic-absorption spectrometry. Property values were provided for six elements (Mn, Fe, Cu, Zn, As, and Cd). The concentration range of the property values was from 0.280 mg kg(-1) of As to 31.8 mg kg(-1) of Zn. The combined relative standard uncertainties of the property values were estimated by considering the uncertainties of the homogeneity, characterization, difference among analytical methods, dry-mass correction factor, and calibration standard. The range of the relative combined standard uncertainties was from 1.1% of Zn to 1.6% of As.

Validation of an analytical method for the determination of cadmium (Cd) in fish by atomic absorption spectrometry with electrothermal atomisation.

The validation of an analytical method was carried out for the determination of cadmium (Cd) in fish. The method was based on sample digestion in a microwave oven and subsequent reading using an atomic absorption spectrometer with a graphite furnace. The factorial design of experiments was applied to assess method ruggedness using the methodology of Box et al. [Box GEP, Hunter WG, Hunter JS. 1978. Statistics for experiments: an introduction to design, data analysis and model building. New York (NY): Wiley], studying the influence of sample mass, volume and concentration of acid used for sample digestion and the volume of modifier used. To study the possible matrix effect in the determination of Cd, the standard addition method was also performed. The results were treated using the OLS method. For the normality test a homoskedastic distribution was observed for the developed method and the results were adjusted to the statistical model proposed. F-tests and Student's t-tests indicated that there was no matrix effect on the calibration curve between the concentration range 1.0-10.0 µg Cd l(-1). Parameters such as selectivity, precision, decision limit, detection capability and limit of quantification were established by the method of standard addition to blank samples. The limit of quantification was 6.8 µg kg(-1). Accuracy, which was evaluated by using a certified reference material, was 107.0%. The recovery of the spiked analyte was 93.69% for the concentration of 50 µg kg(-1). Precision was defined by the coefficient of variation observed (Horrat value), estimated in terms of repeatability and reproducibility, and the values were below the limit, which is 2.0. The validation procedure confirmed the suitability of the method.