Inductively Coupled Argon Plasma Mass Spectrometry Research Articles

CHEMICAL ELEMENTAL COMPOSITION OF DATURA STRAMONIUM L. GROWING IN UZBEKISTAN

Inductively coupled argon plasma mass spectrometry (ICP-MS) was used to study the elemental composition of the underground and aboveground parts of the Datura stramonium growing on the territory of the Republic of Uzbekistan. The obtained data show that 41 elements were found in the composition of the vegetative organs of the D. stramonium, including 6 macroelements (Ca, P, K, Na, S, Mg), 8 essential microelements (Co, Cr, Cu, Fe, Mn, Se, Zn, Mo), and 6 conditionally essential. Moreover, 6 trace elements (B, Si, Ni, V, As, Li), 16 toxic (Pb, Cd, Ge, Sr, Zr, Tl, Bi, Sn, Sb, W, Ag, Ba, Al, Ga, Ti, Be) and 5 little studied elements (Nb, Cs, Ta, Rb, Re) were identified. It was revealed that among the detected elements in D. stramonium, 3 macroelements (Ca, K and Fe) are contained in a concentration of more than 1000 mg/kg, 4 elements (P, S, Mg, Si) are from 100 to 1000 mg/kg, 3 elements (Na, Mn, B), ranging from 10 to 100 mg/kg and the rest were in the range of less than 10 mg/kg. The macroelements were located between each other in the following order: in the roots of the plant Ca (40%)>K (39%)>P (9%)>Mg (6%)>S (4%)>Na (2%), and in the aerial part of the plant Ca (50%)>K (30%)>Mg (9%)>P (7%)>S (3%)>Na (1%). The highest content of essential trace elements in the composition of the roots and aboveground parts of the D. stramonium falls on the share of Fe (n/h 2015.4521 mg/kg, n/h 1516.3041 mg/kg), and among the conditionally essential microelements Si (n/h 397.8607, n/ch 234.4246). It has been established that the higher content of toxic elements in the composition in the underground part of D. stramonium falls on the proportion of A1 (36.92%) and Ti (35.54%), and in the aboveground part of Ga (48.57%) and Al (17.37%), relative to the total content toxic elements. According to the content of salts of heavy metals of the D. stramonium growing in Uzbekistan meets the requirements established by the Global Fund XIV and WHO. Salts of toxic elements Hg were not found. Comparative data showed that in both organs of D. stramonium growing in Uzbekistan, the content of the considered elements is lower than amount of the element of D. stramonium growing in Kazakhstan and South Africa.

Cadmium, manganese, mercury and lead in the general adult population of Kinshasa, DR Congo

Background and Aim. Many metals are of health concern due to their toxic proprieties and health impairments in the human body. To evaluate values for the internal exposure in the general population, the International Federation of Clinical Chemistry and Laboratory Medicine (IFCC) and the International Union of Pure and Applied Chemistry (IUPAC), recommend the use of reference intervals (RIs) of metals as an indicator of the background exposures. This work aimed to derive RIs for Cd, Hg, Mn and Pb in the blood and urine of the adult population living in Kinshasa (n = 396, aged 18–70 years with 210 females). Methods. Levels of metals were measured using Inductively Coupled Argon Plasma - Mass Spectrometry (ICP-MS). Results. In blood, the proposed RIs [P5-P95 (GM)] were 0.089–2.365 µg/L (0.262), 41.41–199.20 µg/L (84.43), 0.100–1.964 µg/L (0.450) and 6.014–15.380 µg/L (9.394) for Cd, Pb, Hg and Mn, respectively. Urinary levels [(P5-P95 (GM)] were 0.142–1.430 µg/L (0.458) for Cd, 1.910–17.840 µg/L (5.424) for Pb, 0.349–2.295 µg/L (0.816) for Hg and 0.063–1.340 µg/L (0.188) for Mn. Conclusion. Except for Pb, levels of all metals were significantly lower than those found in the same city in 2012 and similar to databases involving non-occupationally exposed populations from other countries, probably due to exclusion criteria of metal exposure applying in the present survey (occupationally exposed to the studied metals, smoking habits, amalgam tooth fillings, fish consumption habit more than one time per week, etc.). These background metal exposures will be useful for future occupational and/or environmental surveys as well as undertaking a reliable regulation of chemical exposure in Kinshasa via a national HBM program.

PREVENTION OF MICROELEMENTS DEFICIENCY IN THE BODY OF SWIMMERS

Introduction. As you know, trace elements play an important role in the life of every living cell. Deficiency of trace elements or their unbalanced ratio in food can lead to profound metabolic disorders and cause the development of a number of diseases, including "sports anemia". The content of trace elements in the blood depends on the nature of muscle activity, its volume, intensity and fitness of the body. Under the influence of systematic training, in parallel with the growth of muscles and their need for oxygen, the content of iron, copper, and manganese in the blood cells increases. At the same time, the physical performance of athletes also increases. In the practice of sports, there are very few clear recommendations for the consumption of microelements with food for athletes of various qualifications, age and gender. It is possible to say exactly how much alimentary iron (Fe), copper (Cu) and manganese (Mn) is necessary to satisfy the body's need for microelements only after studying the balance of microelements in the body of athletes, which is the most relevant today. The purpose of this study was to study the daily balance of microelements in the body of swimmers of high qualification categories. Research methods. The elemental profile of the organism of the examined contingent was established on the basis of urine analysis (morning, middle portion collected in a special container). The analysis was carried out by inductively coupled argon plasma mass spectrometry (ICP-MS) on a Nexion 300D + NWR213 device (PerkinElmer, USA), as well as the effectiveness of prescribed drugs was assessed by indicators of capillary blood. Hemoglobin and serum iron were determined using the appropriate standard kits, hematocrit and erythrocytes were determined using conventional methods. Statistical processing of the obtained data was carried out using Microsoft Excel XP software packages (MicosoftCorp., USA) and Statistica 6.0 (StatSoft Inc., USA). Results. In our studies, it was found that the total loss of iron in most cases significantly exceeded the intake of iron with food. During the period of active rest, the absorption of iron from food increased. In most cases, his balance was positive. Through the correct selection of foods rich in trace elements, you can try to influence the balance of trace elements in the body. Conclusion. Thus, the complexes we offer to a greater or lesser extent have a positive effect on a number of important indicators, and are recommended for the prevention of anemia and, also, are highly effective and, therefore, very promising products for improving physical performance.

Impacts of Trace Metals Pollution of Water, Food Crops, and Ambient Air on Population Health in Zambia and the DR Congo.

Zambia and the DR Congo are situated in the central African Copperbelt, which is part of the Lufilian geological structure arc stretching over from Kolwezi in Katanga Province in the DRC to Luanshya in Copperbelt Province in Zambia. The area has large copper-cobalt deposits of which the extraction causes severe ecosystem damage due to pollution of water, food crops, and the ambient air negatively impacting population health. Contamination of drinking water for domestic use and foods (cereals, roots and tubers, vegetables, and fruits) was determined by assessing the contents of trace metals including Mn, Ni, Pb, Zn, Co, As, U, Cd, and Cu and through a questionnaire for environmental damage. Food samples were analyzed by inductively coupled argon plasma/optical emission spectroscopy (ICP-OES), while water and urine samples were analyzed by inductively coupled argon plasma mass spectrometry (ICP-MS). Concentrations of Ni, Pb, and Cd were higher in almost all food crops, although Cu was more in samples of Cucurbita maxima and Amaranthus hybridus. Mean contents (μg/L) of Mn, Zn, Cd, Pb, and U were, respectively, 5,454.6, 2552.2, 138.7, 39.7, 2361.1, and 21.4 in the DRC and 108.9, 543.3, 0.3, 0.2, 1.5, and 0.5 in Zambia, being significantly higher and always far above World Health Organization maximum limits in the DRC. Urine samples taken only from the DRC contained trace metals with children's samples being more contaminated than adult ones. Our results conclusively echo the most critical challenges of toxic pollutants causing numerous health issues among the population. Given an outcry among households adjacent to mines about land degradation and food spoilage, and health problems over years, joint efforts are needed from public and private sectors for stringent mining exploitation monitoring for sustainable governance to protect the environment and ensure food and nutrition safety, and population well-being in Zambia and the DR Congo.

Systemic Essential Metal and Metalloid Levels in Patients with Benign Breast Disease and Breast Cancer.

The objective of the present study is evaluation of serum and hair levels of essential metals and metalloids in women with benign breast disease and breast cancer in order to define similar and distinct patterns that may mediate the link between these pathologies. A total of 310 adult women aged 20-80years old were enrolled in the present study. Of those, 103 patients had benign (fibrocystic) breast disease, 107 patients had breast cancer (stage II), and 100 women were healthy and with absence of breast pathology. Trace metal and metalloid levels in hair and serum were evaluated by inductively coupled argon plasma mass-spectrometry (ICP-MS). The data demonstrate that breast cancer patients were characterized by significantly higher hair Cr and V levels, as well as reduced Cu and Mn content as compared to both benign breast disease patients and controls. In contrast, serum Cu levels in women with breast cancer exceeded those in the controls and benign breast disease cases. Patients with both benign and malignant breast tumors were characterized by lower serum Mn levels as compared to the control values. Serum Cu/Zn and especially Cu/Mn were found to be significantly increased in cancer patients. Significantly reduced hair and serum Se levels were noted only in women with fibrocystic disease. Based on the analysis of two biosamples, it is proposed that malignant breast tumor development is associated with the reduction of systemic Mn and Zn levels, and a concomitant elevation of Cu concentrations.

Trace element levels in pleural effusions.

Trace element levels in pleural effusions.

Environmental and take-home lead exposure in children living in the vicinity of a lead battery smelter in Serbia

Blood lead levels (BLLs) have been falling steadily worldwide due to restricted use of lead (Pb) and its compounds. although they remain above preindustrial Pb levels. Elevated BLL can still be found in children living near secondary Pb smelters that represent around 50% of Pb production. There have been no studies on Pb exposure in children living in Serbia ever since the 1980s. The aim of this study was to evaluate the BLLs in children living in two villages in Serbia (Zajača, the location of a secondary lead smelter, and Paskovac, 5 km away), identify the primary determinants of children’s BLLs, and investigate the impact of BLLs on children’s health symptoms and school achievement.The study was conducted in 2011 on 127 children, aged 1–18 years, whose BLLs were measured using inductively coupled argon plasma mass spectrometry (ICP-MS).The median BLL in children was 12 μg/dl, with a significantly higher value of 17.5 μg/dl in Zajača, compared to 7.6 μg/dl in Paskovac. Only 1 out of 75 and 12 out of 52 children from Zajača and Paskovac, respectively, had BLLs below the CDC recommended 5 μg/dl level. Living near the smelter resulted in 19 times, and having a father who works in the plant 4 times higher odds of elevated BLLs. No significant effects of elevated BLLs health symptoms were seen in this study.BLLs of children living near a battery recycling plant in Serbia, an upper-middle income European country, were in the range and even higher than those of children living in developing countries. For the first time, the contribution of environmental and take-home lead exposure was quantified using mixed-effect modeling, and our results indicate a contribution of 25–40% of the take-home lead exposure to the BLLs of children living in the vicinity of a secondary lead smelter.

Long-Term Follow-up of Survival, Complications, Arsenic Retention and Quality of Life in Patients with Newly Diagnosed Acute Promyelocytic Leukemia Treated with All-Trans Retinoic Acid/Arsenic Trioxide Combination Therapy

Objective: All-trans retinoic acid (ATRA)/arsenic trioxide (ATO) combination therapy for newly diagnosed acute promyelocytic leukemia (APL) has yielded high efficacy in clinical trials, but there are few studies focusing on the long-term follow-up of survival and complications.Methods: In this study, we followed up 217 patients with newly diagnosed APL treated with ATRA/ATO combination therapy between 2001 and 2010. Health assessment for long-term complications and quality of life was performed for 112 of these patients, meanwhile the arsenic retention in their plasma, urine, hair and nails was detected by inductively coupled argon plasma mass spectrometry (ICP-MS).Results: A total of 199 patients (91.7%) achieved complete remission (CR). The estimated 10-year event-free survival (EFS), overall survival (OS), disease-free survival (DFS) and cumulative incidence of relapse (CIR) were 78.0%, 86.3%, 87.0% and 12.0%, respectively. High white blood cell (WBC) count remained as the only unfavorable prognostic factor for remission duration and led to significant differences between low-to-intermediate and high-risk groups in EFS (82.1% vs. 63.9%, P=0.016), DFS (90.6% vs. 73.1%, P=0.008) and CIR (8.0% vs. 26.9%, P=0.003). For the 112 patients who received health assessment, there were no significant long-term complications associated with ATRA/ATO therapy, except for higher incidence of grade-1 liver dysfunction (15.2%) and hepatic steatosis (42.9%) compared to healthy controls (both P<0.001). The arsenic concentration in patients¡¯ plasma and urine excreted quickly to normal level right after the cessation of ATO, even lower than that of healthy controls (P<0.001 and P=0.009, respectively). However, in patients¡¯ hair and nails it slowly decreased to normal after 6 months off ATO, with no significant difference than the healthy controls. The results revealed no general retention of arsenic in patients during the long-term follow-up. And the quality of life was satisfactory in almost all patients.Conclusion: This study with long-term follow-up clearly demonstrated that ATRA/ATO in newly diagnosed APL patients was associated with long-term survival, particularly for patients with low-to-intermediate risk diseases, as well as few complications, minimal arsenic retention and good quality of life.Table 1Estimated 10-year Survival by Different Risk StratificationEFSOSDFSCIRTotal78.0%86.3%87.0%12.0%Sanz¡¯s risk stratificationLow-risk82.4%89.7%89.6%8.2%Intermediate-risk81.8%88.2%91.0%8.0%High-risk63.9%78.4%73.1%26.9%P value0.048*0.1650.029*0.009**WBC-based stratificationLow-to-intermediate-risk82.1%88.8%90.6%8.0%High-risk63.9%78.4%73.1%26.9%P value0.016*0.0690.008**0.003***P<0.05, **P<0.01Table 2Major Abnormalities in the Assessment of Long-term Complications (patients No.=112)Abnormal FindingsPatients No. (%)Healthy Controls No. (%)P valueLower WBC count1 (0.9)†01.000Cardiovascular eventsElevated myocardial enzymes5 (4.5)#1 (0.9)0.212Long Q-T interval00/T wave change14 (12.5)15 (13.4)0.842Echocardiogram abnormality1 (0.9)ǂ01.000Liver, kidney and GI dysfunctionLiver dysfunction17 (15.2)2 (1.8)<0.001Elevated creatinine00/Albuminuria1 (0.9)ǂ01.000Fecal occult blood test00/Hepatic steatosis48 (42.9)20 (17.9)<0.001Diabetes6 (5.4)5 (4.5)0.757Neurological disorders1 (0.9)¡ì1 (0.9)D1.000Potential secondary tumorElevated serum tumor markers3†ø//Thoracic neoplasm on CXR00/Abdominal neoplasm on BUS00/Skin lesion8 (7.1)ŋ5 (4.5)¦Ë0.391Breast cancer1 (0.9)01.000££No acute myocardial infarction. 2 had histories of heart diseases before APL.†1 patient was later diagnosed as the 3rd relapse of APL.ǂ1 patient had rheumatic heart disease 1 week after initial therapy, who also had albuminuria probably due to diabetes.¡ì1 patient had depression prior to APL and well controlled by Deanxit.D1 had essential tremor.ø3 patients had a mild and transient elevation in NSE, CEA and CA125, respectively, and retests were normal.ŋ2 patients had hyperpigmentation, 1 had hypopigmentation and 5 had hyperkeratosis/hyperplasia.¦Ë2 had hyperpigmentation and 3 had hyperkeratosis. [Display omitted] [Display omitted] [Display omitted] DisclosuresZhao:National Natural Science Foundation of China (81300451): Research Funding. Chen:National High-tech R&D Program (863 Program) (2012AA02A505): Research Funding.

Temporal Oscillations of Calcium, Magnesium, Potassium, and Sodium Dissolved Contents in an Agroforestry Catchment from the Atlantic Galicia

There is an increasing awareness worldwide of the conveyance of sediment-associated nutrients across eroding soil surfaces into receiving waters. The objective of this study was to analyze the temporal oscillations of concentrations as well as the exportation of calcium (Ca), magnesium (Mg), potassium (K), and sodium (Na) at the outlet of an agroforestry catchment. These macronutrients were measured in the drainage waters of a 36.3-km2 catchment located at the Valiñas River (Coruña, northwest Spain), where 560 samples were taken from 2003 to 2007. The water collection strategy was a stratified point sampling involving more frequent collections when flow was high. Element contents in the water were analyzed by inductively coupled argon plasma–mass spectrometry (ICP-MS). The dissolved content ranges were as follows: Ca between 4.47 and 20.7 mg L–1, Mg between 2.4 and 7.3 mg L–1, K between 1.13 and 8.6 mg L–1, and Na between 8.9 and 27.2 mg L–1. Significant correlations among all the analyzed elements were observed during the entire study period. Mostly, nutrient losses were related to degradation induced by soil erosion on the cultivated land portion of the catchment.

Lead levels in fur of rats treated with inorganic lead measured by inductively coupled argon plasma mass spectrometry.

The aim of this study was to investigate the relationship between continuous lead exposure and the concentration of this metal in fur. The two main questions we wanted to answer were: 1) Are the fur lead concentrations different according to exposure level? 2) Is the kinetics of lead concentration linear in different compartments?For 12 weeks, 6 rats were force-fed with water containing lead acetate in the following quantities: 0.5 and 50 µg/day. Furs were sampled every two weeks. The lead content of the samples was measured by inductively coupled argon plasma mass spectrometry (ICP-MS).There was a statistical difference (p<0.0001) between fur lead concentration and the three groups (control, low level exposure and high level exposure), between fur lead concentration and time exposure (p<0.0001), and between fur lead concentration and each exposure group at different time exposure (p<0.0001). Thus the level exposure factor and the time exposure factor have an effect on fur lead concentration. Since the determination coefficients were weak for the two exposed groups (0.032 and 0.032), a linear correlation cannot be concluded. The kinetic curves of fur lead concentration are similar for all the exposition groups. Two peaks (at 2 and 8 weeks of exposure) were noted for the two exposed groups.This experimental study cannot conclude a linear relationship to exist between fur lead concentration and exposition duration. It highlights the lack of understanding of mechanisms involved in hair incorporation of metals and raises the question of a cyclic accumulation in hair. A better understanding of the kinetic incorporation of lead in body growths is required.

Simultaneous Determination of Cadmium, Mercury, Lead, Arsenic, Copper, and Zinc in Human Breast Milk by ICP‐MS/Microwave Digestion

An analytical method using microwave digestion and inductively coupled argon plasma-mass spectrometry (ICP‐MS) analysis was developed for the measurement of Cd, Hg, Pb, As, Cu, and Zn in human breast milk. We applied external calibration, internal calibration, and standard addition for reference material and pooled milk analysis. Method performances were defined in terms of detection limits, accuracy, and precision. Accuracy varied between 93% and 105% and precision between 3% and 8%. External calibration and background interferences were checked through a calibrator addition procedure. Our method has shown high accuracy, precision, and sensitivity, as well as linearity within a wide range of values. Our methodology, developed by treatment of reference material and pooled milk samples, was applied for determination of Cu, Zn, As, Cd, Hg, and Pb in 120 human breast milk samples.

Preferential organ distribution of methylselenol source Se-methylselenocysteine relative to methylseleninic acid

It has been proposed that Se-methylselenocysteine (MeSeCys) and methylseleninic acid (MSA IV) are efficiently transformed through the β-lyase and reduction reactions, respectively, into methylselenol, the assumed biologically active selenometabolite responsive for the anti-carcinogenicity and anti-oxidant actions of selenium. The bioavailability and distribution of the two selenium sources in major organs/tissues were compared under exactly identical conditions. Namely, labeled selenium sources 76Se-MeSeCys and 77Se-MSA IV, at a single oral dose of 10 μg Se/kg body weight each, were administered simultaneously to rats that had been depleted of natural abundance selenium with a single isotope 78Se. The same dose of 82Se-selenite was also administered as a reference selenium source. The distributions of the three labeled selenium isotopes were determined 3 h after the administration in 13 organs/tissues/blood. MeSeCys was taken up more efficiently by most organs, especially the pancreas and duodenum, than MSA IV and selenite, the latter two sources being taken up similarly to each other except for in the kidney, liver, and spleen, where the three labeled isotopes were detected at comparable concentrations. The labeled selenium in the liver supernatant was speciated by HPLC inductively coupled argon plasma-mass spectrometry (ICP-MS), and it was suggested that MeSeCys was delivered in its intact form to organs, and then transformed into methylselenol. In addition to the known properties of that MeSeCys is chemically more stable than MSA IV and is a naturally occurring edible product, and that MeSeCys produces methylselenol much more efficiently than a homologous selenoamino acid selenomethionine, the present study revealed that MeSeCys is more efficiently distributed than MSA IV in its intact form, and then produces methylselenol, suggesting that MeSeCys is the best methylselenol source in most organs/tissues.

Tin accumulation in spermatozoa of the rats exposed to tributyltin chloride by synchrotron radiation X-ray fluorescence (SR-XRF) analysis with microprobe

Organotin compounds are widely used in industry and its environmental contamination by these compounds has recently become a concern. It is known that they act as endocrine disruptors but details of the dynamics of Sn in reproductive organs are still unknown. In the present study, we attempted to determine Sn distribution in the testis of rats exposed to tributyltin chloride (TBTC) by inductively coupled argon plasma-mass spectrometry (ICP-MS) for microdissectioned seminiferous tubules and cell-selective metal determination of synchrotron radiation X-ray florescence (SR-XRF) analysis.TBTC was orally administered to rats at a dose of 45μmol/kg per day for 3 days. One day later, Sn was detected in the microdissectioned seminiferous tubules at a level approximately equivalent to that in the testis. Significant stage-specificity of Sn accumulation was not observed in the experimental model. Sn was also detected in spermatozoa at the stage VIII seminiferous tubule, which are the final step of spermatogenesis in the testis. These data indicate that Sn accumulates in germ cells as well as in spermatozoa in a short period of TBTC exposure.

LOBE-SPECIFIC CHANGES IN ZINC LEVELS IN THE PROSTATE OF RATS EXPOSED TO TRIBUTYLTIN CHLORIDE

The prostate is an accessory sex organ that secretes essential components of semen. High levels of Zn are found both in the prostate and its secretion. In the present study, the effects of environmental stress on zinc levels in the prostate were examined in Wistar male rats exposed to tributyltin chloride (TBTC), an environmental toxicant, by inductively coupled argon plasma–mass spectrometry (ICP-MS) for determination of Zn concentration in lobe-dissectioned specimens and micro-PIXE analysis for determination of site-specific distribution of Zn in prostatic sections. A single oral administration of TBTC to rats at a dose of 90 μmol/kg resulted 14 days later in a decrease in the Zn level in the dorsolateral prostate but not the ventral prostate. The TBTC did not affect the weight of the prostate tissue. Micro-PIXE imaging found Zn both in the lumen and the epithelium of the lateral prostatic tubules. PIXE spot analysis revealed that the epithelium of the control rat contained levels of Zn 4–fold higher than in the lumen and that Zn in the epithelium decreased selectively after TBTC exposure.

The Dof domain, a zinc finger DNA-binding domain conserved only in higher plants, truly functions as a Cys2/Cys2 Zn finger domain.

The Dof (DNA-binding with one finger) proteins are plant transcription factors that have a highly conserved DNA-binding domain, called the Dof domain. The Dof domain, which is composed of 52 amino acid residues, is similar to the Cys2/Cys2 zinc finger DNA-binding domain of GATA1 and steroid hormone receptors, but has a longer putative loop than that in the case of these zinc finger domains. The DNA-binding function of ascorbate oxidase gene binding protein (AOBP), a Dof protein, was investigated by gel retardation analysis. When Cys was replaced by His, the Dof domain could not function as a Cys3/His- or a Cys2/His2-type zinc finger. The characteristic longer loop was essential for DNA-binding activity. Furthermore, heavy metals such as Co(II), Ni(II), Cd(II), Cu(II), Hg(II), Fe(II), and Fe(III) inhibited the DNA-binding activity of the Dof domain. Manganese ion as well as zinc ion was coordinated by the Dof domain in vitro. On the other hand, the analysis using inductively coupled argon plasma mass spectrometry (ICP-MS) showed that the Dof domain contained zinc ion but not manganese ion. Thus, the Dof domain was proved to function as a Cys2/Cys2 zinc finger domain.

Stage-specific and age-dependent profiles of zinc, copper, manganese, and selenium in rat seminiferous tubules

Stage-specific and age-dependent profiles of zinc, copper, manganese, and selenium in testis were examined in Wistar rats by both inductively coupled argon plasma-mass spectrometry (ICP-MS) with a microdissection technique and in situ elemental imaging of micro-PIXE analysis. The young adult animals (10 weeks old) contained higher levels of zinc and manganese in the seminiferous tubules at stages VII-VIII than stages XI through VI and IX-X and the levels were higher than those of the immature and old animals. Copper and selenium levels at stages VII-VIII of the young adult animals were also higher than those of the immature and old animals. In stages VII and VIII, zinc was higher in the central area of the seminiferous epithelium, where spermatozoa were localized, demonstrating a cell-specific property.

Elemental imaging of rat epididymis by micro-PIXE analysis

The epididymis, a male reproductive organ, which is a highly convoluted duct, plays an important role in transportation of spermatozoa, their maturation, and their storage. Although major elements, such as P, S and K, as well as trace elements, such as Mn, Cu, Zn, Se, are known to be essential for spermatogenesis, detailed distributions of the elements in the epididymis are only poorly understood. In the present study, Mn, Cu, Zn and Se levels in the epididymis were examined in male Wistar rats by inductively coupled argon plasma-mass spectrometry (ICP-MS) analysis and in situ multi-elemental distributions of epididymal sections were determined by micro-PIXE (particle induced X-ray emission) analysis. The Zn, Cu and Se concentrations in the epididymis of the young adult rats were around 30 μg/g wet weight, 2 μg/g wet weight and 1 μg/g wet weight, respectively, and their Mn were less than 0.5 μg/g wet weight. PIXE imaging of P and K exhibited that P and K were higher in the epididymal epithelium. In contrast, more S was detected in the lumen, which is composed of spermatozoa and a fluid. Elemental imagings of the trace elements were unclear compared with the major elements, but information about zinc localization in the epididymis was obtained.

Biological significance of non-acetylated metallothionein

The biological significance of non-acetylated metallothionein (MT) was investigated from the viewpoint of N α -acetylation after induction of MT synthesis by metallic and non-metallic inducers, by partial hepatectomy and under physiological conditions. N α -Acetylated and non-acetylated forms of MT-2 in liver supernatants and plasma were detected by the tandem size-exclusion and anion-exchange HPLC columns with in-line detection by mass spectrometry. The non-acetylated isoform of MT-2 (MT-2′) was present at a comparable level to the N α -acetylated form of MT-2 (MT-2) at an early stage after induction by not only zinc but also cadmium, and by partial hepatectomy in the livers of rats. Plasma MT-2 in neonatal rats was similar to liver MT-2 in the composition of N α -acetylated and non-acetylated forms, suggesting that there are no differences in the roles of N α -acetylation of MT in the extracellular trafficking of MT. The column switching HPLC method with in-line detection by inductively coupled argon plasma mass spectrometry (ICP-MS) was shown to be a sensitive and powerful method to detect MT proteins at not only isoform level but also at acetylated and non-acetylated form levels.

Trace Elements in Pleural Effusions

When the secretion of pleural fluids exceeds their resorption, liquid (pleural effusion ) will accumulate between the visceral and parietal pleura. Pleural effusions derived from the liquid components of blood are expected to contain trace elements and may, as a sink for trace elements, deprive the body of needed essential elements upon their removal by medical intervention. Consequently, patients may be at risk of drifting into trace-element deficiencies. Because the literature is almost devoid of data about trace elements in effusions, the concentrations of 14 trace elements (Ba, Ca, Cd, Co, Cs, Cu, Mg, Mn, Mo, Pb, Rb, Sn, Sr, Zn) were determined simultaneously by inductively-coupled argon-plasma mass spectrometry (ICP-MS) in effusions from 17 patients. The median values for the concentrations of Rb (209 microgram/kg, range 104-334 microgram/kg) and Cs (1.5 micrograms/kg, range 0.8-2.4 microgram/kg) in the effusions were almost the same as in the sera. The concentrations of Mg (range 15-22 mg/kg), Ca range 52-91 mg/kg), Sr (range 12-37 micrograms/kg), and Ba (range 1.4-18.2 micrograms/kg) were consistently lower in the effusions than in the sera by 18% for Mg, 26% Ca 14% for Sr, and 88% for Ba (percentages based on median in serum as 100%). The concentrations of the essential trace elements Co (range 0.16-0.5 microgram/kg), Cu (130-902 micrograms/kg), Mn (0.2-2.2 micrograms/kg), Mo (0.4-1.5 micrograms/kg), Sn (0.4-1.2 micrograms/kg), and Zn (27-1931 micrograms/kg) in the effusions are generally lower (25-55% based on median) than in the corresponding sera, although a few effusions have higher concentrations of Co, Mn Mo, or Zn than in the sera. The concentrations of Cd (range 0.2-0.5 microgram/kg) in the effusions were approximately the same as in the sera for three patients, considerably lower than in the sera for four patients, and considerably higher for three patients. The concentrations for lead (range 0.6-45 micrograms/kg) in the effusions were generally much higher than in the sera. The effusions were not significantly contaminated with lead-rich erythrocytes. The concentrations of Ca, Cu, and Zn in the effusions correlated positively with the protein concentrations in the effusions. One kilogram of the effusions contain from 10-30% of the trace elements present in the entire volume of serum in circulation.

Simultaneous speciation of endogenous and exogenous elements by HPLC/ICP-MS with enriched stable isotopes.

High performance liquid chromatography (HPLC)/ inductively coupled argon plasma-mass spectrometry (ICP-MS) was introduced to investigate the distributions of selenium (Se) in biological fluids. The method was to determine both the natural abundance of Se and an enriched stable isotope of Se used as a tracer. The distributions of Se in plasma and in urine specimens were determined in Wistar rats on various Se diets with and without an intravenous injection of 82Se-selenite. Although the distribution of natural abundance Se (endogenous Se) in the plasma was affected little by the nutritional status of Se, that in the urine gave a Se peak depending on the nutritional status of Se, and the peak was identified as methylselenol. When 82Se-selenite was injected in excess into rats given three different Se diets (Se-deficient, Se-adequate, Se-excessive), three Se peaks occurred in the HPLC chromatogram of the urine samples, corresponding to selenite, methylselenol and trimethylselenonium ion in the order of elution, and the intensities of the tracer peaks reflected the nutritional status. These results indicate that the HPLC/ICP-MS method is a powerful analytical tool for specifying Se-containing biological constituents, both natural abundance and enriched stable isotopes. Methylselenol in urine is proposed to be a sensitive and Se-specific biological indicator for diagnosing the nutritional status of Se. Furthermore, it was shown that an enriched stable isotope such as 82Se-selenite was shown to be used for the same purpose, and that 82Se-methylselenol and 82Se-trimethylselenonium ion in urine were more sensitive indicators of the Se status of the rats.