Anetta Hanć

Application of spectroscopic techniques: ICP-OES, LA-ICP-MS and chemometric methods for studying the relationships between trace elements in clinical samples from patients with atherosclerosis obliterans

AbstractThe study was aimed to evaluate the influence of the vascular disease, atherosclerotic obliterans (AO), on the location and concentration of elements in the arterial wall and serum. Use of a modern method for studying element’s concentration and distribution in samples of clinical material, i.e. laser ablation inductively coupled plasma mass spectrometry, is presented. Elements are not equally distributed between the inner (intima) and the outer (media + adventitia) layer of the arterial wall. Among the studied elements, calcium was found to have an unquestionable role in the calcification of the wall. Increased concentration of calcium found in the inner part of the atherosclerotic arterial wall and in the plaque, as compared to the control arterial wall samples, demonstrates the unquestionable role of this element in the calcification of the wall observed in AO. Applied chemometric methods were useful for demonstrating the differences in the element’s concentration in blood serum and the arterial wall samples between AO and the control group. FigureImage of the ruptured atherosclerotic plaque done while surgery

An analysis of long-distance root to leaf transport of lead in Pisum sativum plants by laser ablation–ICP–MS

Laser ablation (LA) inductively coupled plasma mass spectrometry (LA–ICP–MS) has been applied to determine the nature of lead (Pb) distribution in plant tissues. Plants were cultivated hydroponically in Hoagland medium supplemented with 0.5 mM Pb(NO3)2. After 96 h, parts of root were cut off from Pisum sativum and analysed. The difference in the amount of Pb transported through the vascular tissues was expressed as the level of signal intensity. Mapping in vivo tissues reveals the metal pathway in the plant which may be particularly helpful in understanding of the mechanisms of heavy metal accumulation and transport in the plant.

Toxic elements and bio-metals in Cantharellus mushrooms from Poland and China

Data on multi-trace element composition and content relationships have been obtained for Cantharellus cibarius, C. tubaeformis, and C. minor mushrooms from Poland and China by inductive coupled plasma–dynamic reaction cell–mass spectroscopy. There is no previous data published on As, Li, V, Tl, and U in chanterelles from Poland and on Ba, Co, Cr, Ni, Rb, and Sr in chanterelles from China. The results implied a role of the soil background geochemistry at the collection site with the occurrence of Ag, As, Ba, Cr, Cs, Li, Mn, Pb, Rb, Sr, U, and V in the fruiting bodies. Both geogenic Cd and anthropogenic Cd can contribute in load of this element in chanterelles from the Świetokrzyskie Mts. region in Poland, while geogenic source can be highly dominant in the background areas of Yunnan. An essentiality of Cu and Zn and effort by mushroom to maintain their physiological regulation could be reflected by data for Cantharellus mushrooms from both regions of the world, but its geogenic source (and possibly anthropogenic) can matter also in the region of the Świetokrzyskie Mountains in Poland. The elements Co, Ni, and Tl were at the same order of magnitude in contents in C. cibarius in Poland and Yunnan, China. C. tubaeformis differed from C. cibarius by a lower content of correlated Co, Ni, and Zn. Soil which is polymetallic and highly weathered in Yunnan can be suggested as a natural geogenic source of greater concentrations of As, Ba, Cr, Li, Pb, Sr, U, and V in the chanterelles there while lower of Mn and Rb, when related to chanterelles in Poland. A difference in Cs content between the sites can be attributed as an effect of the 137Cs release from the Chernobyl accident, in which Poland was much more affected than Yunnan, where deposition was negligible.

Simultaneous determination of Cd, Cr, Cu, Ni, Pb and Zn in sewage sludge by slurry introduction ICP-OES method.

In order to evaluate the slurry nebulisation method as an alternative method for analysis of sewage sludge, the metal content of sludge samples of different origins was determined. The concentrations of six elements: Cd, Cr, Cu, Ni, Pb, and Zn were determined by introducing the sludge as a slurry into an inductively coupled plasma optical emission spectrometer (ICP-OES). Calibration was performed by using aqueous standard solutions. For comparison, the sewage sludge was also digested by microwave digestion and introduced into the plasma as an aqueous solution. The accuracy of the method was checked by analysing a sewage sludge certified reference material (CRM 007-040 Sewage Sludge). The Students t-test showed that values obtained using slurry nebulisation were close to the certified values at a 95% confidence level. The values of elements Cd 11.1 ± 0.8; Cr 37.7 ± 3.3; Cu 563.3 ± 38.4; Pb 119.2 ± 10.1; Zn 729 ± 68.2 mg kg−1 obtained using this method were comparable with those obtained using the conventional method. The slurry method can, therefore, be successfully applied to the determination of content of each element in sewage sludge with RSD less than 3%, without the need to predissolve them. This could avoid the use of hazardous chemicals, incomplete dissolution and loss of volatile analytes.

Effects of binary metal combinations on zinc, copper, cadmium and lead uptake and distribution in Brassica juncea

The interaction between lead, copper, cadmium and zinc in their binary combinations was investigated in Indian mustard seedlings (Brassica juncea L. var. Malopolska). Fourteen-days-old seedlings were treated with Pb(NO3)2, CuSO4, CdCl2, ZnSO4 at 50μmol of metal ion concentration and at 25μmol of each metal ion in combinations. Metal combinations were generally more inhibiting in terms of biomass production. This inhibiting effect followed an order: Cu+Cd>Cu+Zn, Cd+Pb>Cu+Pb>Zn+Pb, Cu>Cd>Zn>Zn+Cd>Pb. We observed synergistic and antagonistic effects of metal uptake in binary metal treatments, suggesting metal crosstalk at the plant uptake site. Metal content in plant tissues varied among different combinations. The metal concentrations followed an order of Pb>Cu>Zn>Cd in roots, Zn>Cu>Pb>Cd in the stem and Zn>Cu>Cd>Pb in leaves. Presence of metals altered the distribution of micronutrients (Cu, Zn) in plants: Cu concentration was lowered in roots and leaves and increased in stems; Zn content was increased in plants, with stems having up to 4 or 5 times more Zn than in control plants.

Barium Determination in Gastric Contents, Blood and Urine by Inductively Coupled Plasma Mass Spectrometry in the Case of Oral Barium Chloride Poisoning

A serious case of barium intoxication from suicidal ingestion is reported. Oral barium chloride poisoning with hypokalemia, neuromuscular and cardiac toxicity, treated with intravenous potassium supplementation and hemodialysis, was confirmed by the determination of barium concentrations in gastric contents, blood, serum and urine using the inductively coupled plasma mass spectrometry method. Barium concentrations in the analyzed specimens were 20.45 µg/L in serum, 150 µg/L in blood, 10,500 µg/L in urine and 63,500 µg/L in gastric contents. Results were compared with barium levels obtained from a non-intoxicated person.

Multielemental analysis of 18 essential and toxic elements in amniotic fluid samples by ICP-MS: Full procedure validation and estimation of measurement uncertainty

Amniotic fluid is the substantial factor in the development of an embryo and fetus due to the fact that water and solutes contained in it penetrate the fetal membranes in an hydrostatic and osmotic way as well as being swallowed by the fetus. Elemental composition of amniotic fluid influences the growth and health of the fetus, therefore, an analysis of amniotic fluid is important because the results would indicate abnormal levels of minerals or toxic elements. Inductively coupled plasma mass spectroscopy (ICP-MS) is often used for determination of trace and ultra-trace level elements in a wide range of matrices including biological samples because of its unique analytical capabilities. In the case of trace and ultra-trace level analysis detailed characteristics of analytical procedure as well as properties of the analytical result are particularly important. The purpose of this study was to develop a new analytical procedure for multielemental analysis of 18 elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Mg, Mn, Ni, Pb, Sb, Se, Sr, U, V and Zn) in amniotic fluid samples using ICP-MS. Dynamic reaction cell (DRC) with two reaction gases, ammonia and oxygen, was involved in the experiment to eliminate spectral interferences. Detailed validation was conducted using 3 certified reference mterials (CRMs) and real amniotic fluid samples collected from patients. Repeatability for all analyzed analytes was found to range from 0.70% to 8.0% and for intermediate precision results varied from 1.3% to 15%. Trueness expressed as recovery ranged from 80% to 125%. Traceability was assured through the analyses of CRMs. Uncertainty of the results was also evaluated using single-laboratory validation approach. The obtained expanded uncertainty (U) results for CRMs, expressed as a percentage of the concentration of an analyte, were found to be between 8.3% for V and 45% for Cd. Standard uncertainty of the precision was found to have a greater influence on the combined standard uncertainty than on trueness factor.

Metallic elements and metalloids in Boletus luridus, B. magnificus and B. tomentipes mushrooms from polymetallic soils from SW China

Yunnan Province in China is known for its high biodiversity of mushrooms and a diverse geochemistry of soil bedrock and polymetallic soils, but our knowledge of mineral compositions of mushrooms from Yunnan is scarce. The metallic trace elements, Ag, Ba, Co, Cd, Cs, Cu, Cr, Hg, Li, Mn, Ni, Pb, Rb, Sr, V, Tl, U and Zn, and the metalloids, As and Sb, have been investigated using validated methods with a dynamic reactive cell by mass spectroscopy - inductive coupled plasma and cold vapour - atomic absorption spectroscopy on three popular species of Boletus mushrooms from Southwestern China. The trace mineral profiles in caps and stipes of B. luridus (24 individuals), B. magnificus (29 individuals) and B. tomentipes (38 individuals) have been evaluated. The interspecific differences in the content of several trace elements could be attributed to known differences in the geochemistry of soils in Yunnan, but for copper a difference was observed within species. The mean values of concentrations in composite samples of caps for B. luridus, B. magnificus and B. tomentipes from three to four locations were at the ranges (mgkg-1 dry biomass): Ag (1.3-3.7), As (0.79-53), Ba (4.0-12), Co (0.68-1.2), Cd (0.79-2.2), Cs (0.67-55), Cu (37-77), Cr (5.0-7.6), Hg (2.1-5.4), Li (0.15-0.61), Mn (13-28), Ni (0.86-4.6), Pb (0.59-1.8), Rb (90-120), Sb (0.014-0.088), Sr (0.63-1.6), V (1.4-2.2), Tl (0.017-0.054), U (0.029-0.065) and Zn (130-180). Caps of Boletus mushrooms were richer in Ag, Cu, Hg and Zn than stipes, while other elements were distributed roughly equally between both morphological parts. B. luridus, B. magnificus and B. tomentipes grew in certain sites in Yunnan contained Ag, As, Ba, Cr, Hg, Ni, Sr or V at elevated concentration. A specific geochemistry of the soils type (latosols, lateritic red earths, and red and yellow earths in the Circum-Pacific Mercuriferous Belt of Southwestern China) can explain occurrence of some minerals at greater or elevated amount in mushrooms in Yunnan, while number of available research and data on mineral composition of mushrooms due to geochemical anomalies of soil parent material is so far little.

Test of the relationships between the content of heavy metals in sewage sludge and source of their pollution by chemometric methods

The content of various metals (Cd, Cr, Cu, Ni, Pb and Zn) in sewage sludge was analysed by ICP-OES technique. The study was performed on 14 samples from the Wielkopolska region and 4 from the neighbouring provinces. The results were used to perform chemometric analysis. Two chemometric methods were used to test the relationships between the content of heavy metals in sewage sludge and the sources of their pollution. The application of cluster analysis displayed important information about the identification of similar locations of sewage sludge sampling stations. This chemometric method showed that all the monitoring locations are grouped into three main clusters. Separated clusters present similarities between locations of the sewage treatment plants, which have the same kind of industrial plants in their catchment area. Principal component analysis enabled interpretation of the complex relationships between determined elements. Application of principal component analysis to the whole data set helped to distinguish only two sewage sludge stations (Ostrow Wlkp. and Poznan-Kozieglowy) that could be interpreted, each in different principal component thereby suggesting that elements concentration differ considerably. The interpretation of relationships between the rest of the stations was possible by performing PCA for the second time, but on the reduced data set (two above-mentioned stations were excluded). It distinguished two groups: (1) Gniezno, Srem, Kalisz, Inowrocław and Sroda Wlkp, and (2) Gostyn, Gniezno and Kalisz, which differ with regard to elements concentration.

New procedure of quantitative mapping of Ti and Al released from dental implant and Mg, Ca, Fe, Zn, Cu, Mn as physiological elements in oral mucosa by LA-ICP-MS

A new procedure for determination of elements derived from titanium implants and physiological elements in soft tissues by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is presented. The analytical procedure was developed which involved preparation of in-house matrix matched solid standards with analyte addition based on certified reference material (CRM) MODAS-4 Cormorant Tissue. Addition of gelatin, serving as a binding agent, essentially improved physical properties of standards. Performance of the analytical method was assayed and validated by calculating parameters like precision, detection limits, trueness and recovery of analyte addition using additional CRM - ERM-BB184 Bovine Muscle. Analyte addition was additionally confirmed by microwave digestion of solid standards and analysis by solution nebulization ICP-MS. The detection limits are in range 1.8μgg-1 to 450μgg-1 for Mn and Ca respectively. The precision values range from 7.3% to 42% for Al and Zn respectively. The estimated recoveries of analyte addition line within scope of 83%-153% for Mn and Cu respectively. Oral mucosa samples taken from patients treated with titanium dental implants were examined using developed analytical method. Standards and tissue samples were cryocut into 30µm thin sections. LA-ICP-MS allowed to obtain two-dimensional maps of distribution of elements in tested samples which revealed high content of Ti and Al derived from implants. Photographs from optical microscope displayed numerous particles with µm size in oral mucosa samples which suggests that they are residues from implantation procedure.