Zinc-protoporphyrin determination by HPLC with fluorescence detection as a biomarker of lead effect in artisanal pottery workers.

Lead (Pb) exposure compromises heme synthesis by inhibiting ferrochelatase, forming zinc-protoporphyrin (ZnPP). This study aims to validate a method for the determination of ZnPP by HPLC with fluorescence detection and apply this method to evaluate the extent of Pb exposure of artisanal pottery workers. Extraction procedures were tested using both nonacid and acid liquid-liquid extraction. The former presented a better chromatogram and recovery results. The validated method yielded a good resolution of ZnPP and its free form peaks with acceptable precision and accuracy. Total run time was 15 min and ZnPP peak retention time was 5.6 min. We applied this method to evaluate 39 potters (90% male), mean age 40 years (9-80). The medians (ranges) of blood lead, ZnPP and hemoglobin were 16.0 µg/dl (2.2-71.5), 12.6 µg/dl (4.6-279.8) and 15.1 g/dl (11.0-17.8), respectively. Significant differences were observed for blood lead according to gender, age range (>40 years), direct handling of lead oxide and years of occupation. Significantly higher levels of ZnPP were observed in male potters involved with lead glazing activity. The validated method was shown to be simple with one-step nonacid extraction, good sensitivity, reproducibility and accuracy. Our data shows that these laborers are dangerously exposed to Pb, reflecting the effect on the heme synthesis.

Manganese exposure and association with hormone imbalance in children living near a ferro-manganese alloy plant.

It has been suggested that manganese (Mn) plays a fundamental role in the reproductive system through interference with the regulation of the secretion of hormones related to puberty. The objective of this study was to evaluate the environmental exposure to Mn and its effects on the endocrine regulation of hormones related to puberty in school-aged children living near a ferro-manganese alloy plant. Toenails, occipital hair, and blood samples were collected from 225 children, between 7 and 12 years of age, in four elementary schools in Simões Filho, Bahia, Brazil, who were exposed to different Mn levels owing to different Mn dust deposition rates. The Mn content was determined in the toenails (MnTn), hair (MnH), and blood (MnB), in addition to blood lead levels (PbB), by using graphite furnace atomic absorption spectrometry. Luteinizing hormone (LH), prolactin (PRL), estradiol (E2), testosterone (T), and thyroid stimulating hormone (TSH) levels were determined by using a chemiluminescence method. Of the total participants, 50.2% were boys, with an average age of 9 years. PRL values were higher in children attending the school with a higher Mn deposition rate (p < 0.004). We observed that MnTn was positively correlated with PRL levels and exhibited a non-linear association with LH levels. None of the tested Mn biomarkers were associated with E2, T, or TSH levels. To date, despite several animal studies that have focused on the correlation between Mn exposure and the endocrine regulation of hormones and pubertal development, very few studies have reported a similar relationship between environmental Mn effects and the human endocrine system. Our findings support the hypothesis that elevated exposure to Mn in children may be associated with hormonal imbalances that might trigger the early onset of puberty.

Environmental Co-Exposure to Lead and Manganese and Intellectual Deficit in School-Aged Children.

Studies have demonstrated that, for urban children, dust represents the main exposure to sources of metals like lead (Pb) and manganese (Mn). We aimed to investigate the exposure to these metals and their association with intellectual deficit in children living in an industrial region. This cross-sectional study recruited volunteers from four elementary schools in the town of Simões Filho, Brazil. We evaluated 225 school-aged children (7⁻12 years) for blood lead (PbB) and manganese hair (MnH) and toenails (MnTn) by graphite furnace atomic absorption spectrometry. Child and maternal IQs were estimated using the Wechsler Abbreviated Scale for Intelligence (WASI). Median and range PbB were 1.2 (0.3⁻15.6) µg/dL. MnH and MnTn medians (ranges) were 0.74 (0.16⁻8.79) µg/g and 0.85 (0.15⁻13.30) µg/g, respectively. After adjusting for maternal IQ, age and Mn exposure, child IQ drops by 8.6 points for a 10-fold increase in PbB levels. Moreover, an effect modification of Mn co-exposure was observed. In children with low MnTn, association between Pb and child IQ was not significant (ß = -6.780, p = 0.172). However, in those with high MnTn, the association was increased by 27.9% (ß = -8.70, p = 0.036). Low Pb exposure is associated with intellectual deficit in children, especially in those with high MnTn.

Noninvasive biomarkers of manganese exposure and neuropsychological effects in environmentally exposed adults in Brazil.

Manganese (Mn), an essential element to humans, in excess can cause neurotoxic damage. So far, Mn exposure assessment has no ideal biomarker. This study aims to investigate the association between Mn exposure, using noninvasive biomarkers, and neuropsychological effects in environmentally exposed adults. The residents of two communities near to a ferromanganese refinery in Bahia, Brazil were evaluated. Volunteers aged 15-55 of both sexes provided scalp hair, axillary hair, fingernail and saliva specimens for Mn determination by electrothermal absorption spectrometry. Several neuropsychological tests were used to evaluate cognitive, attention, memory, motor and executive functions. Significant correlations were observed between Mn in hair (MnH, median 8.95 µg/g), axillary hair (MnAxH,18.49 µg/g) and fingernail (MnFN, 6.91 µg/g) with the performances in several neuropsychological tests. No association was observed between manganese levels in saliva (MnSal, 4.2 µg/L) and any neuropsychological function. Multiple regression analysis detected an inverse association between Log MnH and IQ (ß=-4.76 [CI 95% -9.17 to -0.36]) and between Log MnFN and visual working memory (ß=-3.33 [CI 95% -6.15 to -0.52]). Direct association was observed between Log MnFN and time of completion in the cognitive flexibility task (ß=56.29 [CI 95% 2.41-110.18]). The Mn biomonitoring using noninvasive biomarkers was able to detect high exposure levels, which were associated with detrimental neuropsychological effects in adults exposed to industrial emissions.