Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma/Mass Spectrometry (ICP-MS) for Trace Element Biomonitoring using Mosses

Two analytical methods - instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS) - were used for the trace element analysis of naturally growing mosses for a heavy metal biomonitoring survey. The techniques were applied to reference mosses to evaluate the feasibility, analytical variability, detection limits and accuracy. These parameters were evaluated using 563 mosses sampled in the 1996 French survey. All the elements of interest in the European program "Atmospheric Heavy Metal Deposition in Europe - estimation based on moss analysis" (As, Cd, Cr, Cu, Fe, Hg, Pb, Ni, V, Zn) were able to be determined by ICP-MS. INAA appeared suitable for the determination of As, Cr, Fe, Hg, V and Zn. The Cd, Cu, Ni and Pb concentrations determined by ICP-MS were preferred to the INAA results, because of increased feasibility or accuracy. The results provided by both methods on the French mosses were statistically compared for 14 elements. Significant linear correlation appeared for: Ba, Ce, Cs, La, Rb, Sm, Th and V. Among these eight elements, Ba, Cs, La and Sm concentrations determined by both methods exhibited a strong statistical similarity. The correlations obtained for As, Eu, Fe and Sb were not as strong and no correlation at all was observed for Co and Cr. These differences were attributed to instrumental factors (e.g. spectral interference occurred for both methods) or due to the sample preparation prior to ICP-MS. The consequences of such results on the regional trend evaluation of atmospheric heavy metal deposition were discussed.     

Multi-element determination in earthworms with instrumental neutron activation analysis and inductively coupled plasma mass spectrometry: A comparison

Earthworms were collected from agricultural fields in Admont, Graz, Piber and Gumpenstein, Austria. Six earthworm samples were investigated with INAA and with ICP-MS in parallel for the element concentrations of As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Pb, Rb, Sb, Se and Zn. With both techniques 14 elements were analysed in a wide concentration range (ng/g to mg/g) GF-AAS and HG-AAS were used for verification of some element concentrations. A comparison of analytical results between INAA and ICP-MS was discussed. In general, good agreement between ICP-MS and INAA was obtained, the relative difference values of most of the elements are within ±20% range, however, a methodical error for the determination of Hg by ICP-MS was found.     

Intercomparison of moss reference material by different multi-element techniques

An intercomparison of data obtained for a moss reference material (Hylocomium splendens) used as biomonitor of atmospheric deposition by different multi-element techniques is presented. In total 43 elements (Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Ag, Sn, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ta, W, Au, Th, U) were determined using inductively coupled plasma-mass spectrometry (ICP-MS), conventional instrumental neutron activation analysis (INAA), epithermal neutron activation analysis (ENAA) and as well as shorttime neutron activation analysis without and with a⁶LiD-converter. Advantages and drawbacks of each method are discussed. The introduction of moss reference materials for atmospheric multi-element deposition studies involving nuclear analytical techniques is strongly recommended.     

Comparison of instrumental neutron activation analysis of geological materials with other multielement techniques

Results obtained for 12 elements in approximately 1600 rocks by instrumental neutron activation analysis (INAA) are compared with those obtained by ICP emission spectrometry (ICP-ES), XRF, and atomic-absorption spectrometry (AAS). Sample duplicates and two controls are used to evaluate the precison of the methods investigated. Application of a method (Maximum Likelihood Functional Relationship) to determine and quantify rotational and translational bias is demonstrated. The elements Na, Fe, Ba, Co, Cr, La, Ni and Rb can be determined in rocks by INAA with sufficient sensitivity and precision, whereas the determination of Ag, Yb, Zn and Zr suffers from inadequate sensitivity. Good agreement is seen in the results for Na (by INAA, ICP-ES and XRF) and AG (INAA and AAS). A significant positive bias (13% or less) is evident in the comparison of results by INAA and ICP-ES or XRF for Cr, Ba, Ni and Fe over a wide range of concentration. A similar trend, though less significant, is observed for the elements Yb, Rb, La and Co; the upper limit of concentration for satisfactory determination is within a decade of the highest detection limit for these elements. Rotational and translational bias is evident for Zn in the comparison of data obtained by INAA and ICP-ES, the results by INAA being appreciably lower above about 400 ppm Zn.     

Pure graphite as a reference material for the determination of trace elements — an interlaboratory collaborative study

Seven synthetic graphite powders of different grade of purity were analyzed by means of INAA, WDXRF, EDXRF, DC-OES directly and using ICP-MS, ICP-OES, ETAAS and FAAS in combination with various sample preparation techniques. On the basis of a statistical evaluation of the results obtained, for the trace elements Al, Ca, Cr, Cu, Fe, Mn and Ni, reference values were established and, for the elements As, Co, Mg, Mo, Pb, Sb, Si, Sr, Ti, V, Zn and Zr, informative values are given. The analyzed reference materials are commercially available.     

Chemical analysis of dairy cattle feed from Brazil

The bovine dairy cattle demand diets of high nutritional value being essential to know chemical composition of feed supplied to cows to achieve high levels of quality, safety and productivity of milk. Different roughages and concentrates from Minas Gerais and Rio Grande do Sul states, Brazil, were analyzed by instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS). Concentrate and roughage samples were differentiated by mass fractions of As, Ba, Mg, P, Rb and Sr. Samples of concentrate from both origins were differentiated by mass fractions of As, Cd, Co, Cr, Cs, Ni and Rb.     

Pure graphite as a reference material for the determination of trace elements — an interlaboratory collaborative study

 Seven synthetic graphite powders of different grade of purity were analyzed by means of INAA, WDXRF, EDXRF, DC-OES directly and using ICP-MS, ICP-OES, ETAAS and FAAS in combination with various sample preparation techniques. On the basis of a statistical evaluation of the results obtained, for the trace elements Al, Ca, Cr, Cu, Fe, Mn and Ni, reference values were established and, for the elements As, Co, Mg, Mo, Pb, Sb, Si, Sr, Ti, V, Zn and Zr, informative values are given. The analyzed reference materials are commercially available. Received: 12 February 1996/Revised:27 March 1996/Accepted:2 April 1996     

Trace Elements in Pleurotus Ostreatus,P. Eryngii,and P. Nebrodensis Mushrooms Cultivated on Various Agricultural By-Products

Abstract

Mushrooms are efficient accumulators of essential and toxic elements. Although oyster (Pleurotus spp.) mushrooms are widely commercialized and consumed, few data exist regarding trace elements content and bioaccumulation in cultivated P. ostreatus and P. eryngii, while no data are available for P. nebrodensis. The contents of Al, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, K, Mn, Na, Ni, Pb, Rb, Sr, V, and Zn were monitored using inductively coupled plasma-mass spectrometry (ICP-MS) and atomic emission spectrometry (AES) in P. ostreatus, P. eryngii, and P. nebrodensis mushrooms and their cultivation substrates that include wheat straw (WHS), grape marc (GMC), olive leaves (OLV), and two-phase olive mill wastes (OMW), separately or in mixtures. Bioaccumulation factors (BAFs) less than 0.3 were obtained for Al, Ba, Co, Cr, Fe, Mn, Ni, Pb, Sr, and V; BAFs exceeding 1 for K?>?Zn?>?Cd?>?Cr?>?Rb?>?As, while the BAFs for Na were less 0.7. Mushrooms grown on OLV and OMW presented lower BAFs than those grown on WHS and GMC for all elements except for K, Cd, and Cu. P. ostreatus was an effective accumulator for Cr, Fe, and Zn; P. eryngii for Al, Cs, Ni, and V; and P. nebrodensis for As and Cd. The estimated daily intakes (μg kg^?1 body weight) from mushroom consumption were less than 0.010 for As, Cd, Co, Cs, Pb, and V, 0.010–0.10 for Ba, Cr, Ni, and Sr, 0.10–5.0 for Al, Cu, Fe, Mn, Rb, and Zn, 65–83 for Na, and 858–1030 for K. Overall, the mushrooms studied provide significant amounts of K, adequate amounts of Mn and Zn and low amounts of Na and toxic elements.     

Determination of trace elements by inductively coupled plasma mass spectrometry of biomass and fuel oil reference materials using milligram sample sizes

Most of the analytical techniques used to quantify elements associated with solid samples suffer from high detection limits and cannot be used for trace elements in biomass samples, particularly when only 20 mg are available for analysis. Inductively coupled plasma mass spectrometry (ICP-MS) can achieve detection limits of parts-per-trillion with liquid sample introduction by solution nebulisation. This technique was therefore tested with two standard biomass reference materials: oriental tobacco leaves and cabbage leaves. Two preparations successfully used on coal standards were used to digest the solid samples: a total digestion method (wet ashing digestion) and a partial leaching (microwave extraction). The concentrations of up to seventeen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn) were measured after the two preparations. The accuracy and sensitivity of the measurements improved when the dilution factor decreased from 5000 to 1000 and to 500. Since the proportion of mineral matter in biomass samples is small (5%), the microwave digestion extracted elements that are generally not completely extracted from coal samples (e.g. Sb). However, some trace element concentrations were below the limit of quantification after microwave extraction, even with a reduced dilution factor (As, Se and Mo) and could not be quantified. A fuel oil was also digested. The trace element concentrations were very low (between 28 and 0.1 microgram g(-1)) but acceptable results were obtained by applying a dilution factor of 100. Only six elements in the fuel oil (As, Ba, Co, Ni, Se and V) had certified or indicated values. Factors affecting the accuracy and sensitivity of the analyses are discussed. The reproducibility of analysis of the tobacco leaf standard was checked over a period of nine months by both digestion methods. The wet ashing method gave acceptable reproducibility for Ba, Cd, Co, Cu, Ga, Mn, Mo, Ni, Pb, V and Zn but poor precision for Cr, Se and Sn and showed evidence of residual chloride interference for As. The microwave extraction gave good reproducibility for As, Ba, Cd, Co, Cr, Cu, Mo, Ni and Zn but poor precision for Se and low recoveries for Ga, Mn, Sn and V. In spite of the small quantities of material analysed, it proved possible to determine the trace elements at levels down to 0.1 microgram g(-1) in the reference materials.     

Evaluation of strontium isotope abundance ratios in combination with multi-elemental analysis as a possible tool to study the geographical origin of ciders

In order to evaluate alternative analytical methodologies to study the geographical origin of ciders, both multi-elemental analysis and Sr isotope abundance ratios in combination with multivariate statistical analysis were estimated in 67 samples from England, Switzerland, France and two Spanish regions (Asturias and the Basque Country). A methodology for the precise and accurate determination of the ⁸⁷Sr/⁸⁶Sr isotope abundance ratio in ciders by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) was developed. Major elements (Na, K, Ca and Mg) were measured by ICP-AES and minor and trace elements (Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Cs, Ba, La, Ce, W, Tl, Pb, Bi, Th and U) were measured by ICP-MS using a collision cell instrument operated in multitune mode. An analysis of variance (ANOVA test) indicated that group means for B, Cr, Fe, Ni, Cu, Se, Cd, Cs, Ce, W, Pb, Bi and U did not show any significant differences at the 95% confidence level, so these elements were rejected for further statistical analysis. Another group of elements (Li, Be, Sc, Co, Ga, Y, Sn, Sb, La, Tl, Th) was removed from the data set because concentrations were close to the limits of detection for many samples. Therefore, the remaining elements (Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba) together with ⁸⁷Sr/⁸⁶Sr isotope abundance ratio were considered for principal component analysis (PCA) and linear discriminant analysis (LDA). Finally, LDA was able to classify correctly 100% of cider samples coming from different Spanish regions, France, England and Switzerland when considering Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba and ⁸⁷Sr/⁸⁶Sr isotope abundance ratio as original variables.     

Determination of heavy metals and other trace elements in lake sediments from a sewage treatment plant by neutron activation analysis

Instrumental neutron activation analysis (INAA) was used to determine metals (Ba, Co, Cr, Cs, Fe, Hf, Rb, Sc, Zn), semi-metals (As, Sb), actinides (U, Th) and rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in bottom sediments from one of the ponds of the Sewage Treatment Plant (STP) in São Paulo, Brazil. The results obtained were compared with the concentration determined in a soil profile and in a rock sample, in natura, representing the lithologies of the region, and indicated that only As, Cr and Zn can have their origin associated with the residues disposed around the pond.     

An innovative Compton suppression spectrometer and its capability of evaluation in multi-elemental neutron activation analysis

A new Compton suppression system was established. A low energy HPGe detector (LO-AX) is used as the analyzing detector. It is completely shielded by a 50%n-type HPGe and two NaI(TI) detectors. Experiments show that a substantial Compton suppression effect is also achieved in the low energy region down to 15 keV. The capability of applying this system in INAA was evaluated for 13 elements (As, Cd, Co, Cr, Hg, Mo, Ni, Sb, Se, Sr, Th, U and Zn) in biological and environmental samples. The benefits and problems of using this Compton suppression spectrometer in INAA are examined for each element.     

Determination of elemental levels in radiopharmaceuticals by instrumental neutron activation analysis

Instrumental neutron activation analysis (INAA) was applied to thedetermination of the concentration levels of Na, Mg, Al, Cl, K, Sc, Ti, V,Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Mo, Ag, Cd, Sb, I, Cs,Ba, La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, Lu, Hf, Ta, Hg, Th and U in three radiopharmaceuticals.The irradiation of the samples was carried out in a 0.5 kW Bariloche RA-6Research Nuclear Reactor and the induced gamma-activity was measured by gamma-spectrometry.INAA proves to be an accurate and precise technique to obtain a quick informationon the concentration levels of several minor and trace components in radiopharmaceuticals.The quantification of heavy toxic elements is required for the registrationof radiopharmaceuticals.     

Application of INAA and XRFA in a comparative environmental study

Environmental monitoring requires reliable and effective analytical techniques for widely different concentration ranges. Two such methods (INAA and XRFA) were applied in a comparative environmental study on air dust filters and grass. The samples were collected during one year at two locations (near Bucharest/Romania and near Stuttgart/Germany) with different levels of air pollution. Seventeen environmentally relevant elements (As, Ba, Br, Ca, Co, Cr, Cu, Fe, K, Mn, Ni, Pb, S, Sb, Se, V, Zn) were determined. The aim was to test the suitability of INAA and XRFA methods for different elements in these kinds of samplesaat realistical pollution levels. The results were statistically compared for 13 elements, which were determined by both analytical techniques. They were also used to characterize the air pollution level and its variation at the two locations, and to compare them. Generally, concentrations in air of the elements studied are higher in Bucharest than in Stuttgart.     

Elemental concentrations in sediments of the Patras Harbour, Greece, using INAA, ICP-MS and AAS

Twenty marine sediment samples, selected downcore from six sediment cores, which were retrieved from the Patras Harbour, were studied for their elemental composition using three analytical techniques: INAA, ICP-MS and AAS. Standard reference materials were used to verify the accuracy of the analysis techniques. In total, the concentrations of 30 major, minor and trace elements were measured. The vertical distribution of most elements in the examined cores could be characterized as relatively uniform. The eastern part of the harbour seems to be more polluted in respect to some elements (Ag, Br, Cd, Cr, Cu, Pb and Zn) compared to the western one. The concentrations of a number of elements (As, Cd, Cr, Cu, Ni, Pb and Zn) determined in the sediment samples of the present work are discussed regarding to those obtained from other harbours in the world and compared against sediment quality guidelines (SQGs) to assess the ecotoxicological significance of the sediment contaminants to benthic biota.     

Measurements of contaminant elements of wines by inductively coupled plasma-mass spectrometry: A comparison of two calibration approaches

The aim of the present work was to develop and validate an accurate method by ICP-MS focalized to the measurement of contaminant elements in wines, in special those with legal importance. In addition, we intended to evaluate the suitability of ICP-MS semi-quantitative methodology in order to reduce the time and cost of analysis. Twenty-six contaminant elements of wine (Li, Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, In, Cs, Ba, Hg, Tl, Pb, Bi and U) were measured using quantitative and semi-quantitative calibration approaches, in diluted white and red wines. In an early step potential interferences caused by Cl and Ca species were evaluated, in order to establish suitable mathematical corrections. For validation of ICP-MS procedures a few elements were determined by flame and electrothermal AAS. Reference wines from 1992 year, with provisional values, were analyzed and the results showed satisfactory agreement. The semi-quantitative calibration provided slightly higher limits of detection than those obtained by the quantitative calibration, and always lower than 0.1 μg l⁻¹, except for Fe and Zn. For most elements the recovery percentages (between 90 and 100%) and precision of the results (R.S.D. (%) < 4) were similar for both modes. Differences lower than 20% of concentration was obtained for most elements. Both methodologies offer valuable alternatives to wine characterization and comparison purposes. For legal requirements control purposes, with reference to the importance of accurate results, quantitative approach is the most suitable alternative.     

Distribution of some major and trace elements in Danube Delta lacustrine sediments and soil

Sediment cores collected from lakes Mesteru and Furtuna (eastern part), Sontea channel and soil samples collected from Caraorman bar, all located in the Danube Delta, were analyzed for 42 elements (Ag, Al, As, Be, Na, Mg, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Y, Mo, Ag, Cd, In, Sn, Sb, Cs, Ce, Hf, Hg, Tl. Pb, Bi, Th. U) by instrumental neutron activation analysis (INAA), thick target proton induced X-ray emission (TT-PIXE) and inductively coupled plasma-mass spectrometry (ICP-MS). The INAA and TTPIXE yielded total concentrations whereas the ICP-MS data reflected the fractions soluble in 14M HNO₃. The ICP-MS data exhibited surface enrichment relative to the lower part of the sediment core of Cu, Zn, As, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb, and Bi, most prominently by Cd and Hg. Their vertical distribution in the investigated cores generally reflected the pollution history of recent sediments in Danube delta, showing a steady increase until the end of the 1980s followed by a slow decrease after 1990. The vertical profiles of most remaining elements were characterized by a relatively uniform distribution along the cores. In some cases, the concentrations of As, Cd, Cu, Cr, Mn, Ni and Pb exceeded minimum thresholds of safety, as defined by the Romanian regulations. The elemental composition of the sediment below 20 cm depth (total concentrations) was similar to that of the upper continental crust (UCC) for most elements. Values distinctly higher than UCC were observed for As, Sb (factor ~5) and Cr, Ni, Cu (factor 2 to 3). The nitric acid soluble element concentrations in the soil samples in some cases showed increased values at the surface as compared to 30 cm depth, either due to air pollution or to the action of plants. In no case a large contribution to the topsoil from atmospheric deposition was evident, indicating that the surface contamination of the sediments was mainly by riverine transport. This revised version was published online in July 2006 with corrections to the Cover Date.     

The complementary use of radioanalytical methods and trace analysis methods for the characterisation of environmental IAEA reference materials

The IAEA laboratories have access to both nuclear analytical methods and conventional instrumental methods for trace analysis for the characterisation of its environmental and biological reference materials. A technical concept integrating the homogeneity data, the recommended test portion mass and the uncertainty on the trace element concentrations is explored using a combination of INAA, XRF, ICP-MS, ICP-AES, and AAS. The above approach is illustrated by selected examples of reference materials currently under evaluation for their trace element content. They include some or all of the following elements Al, As, Br, Ca, Cd, Co, Cr, Cs, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Rb, Se, Sr, Th, U, Zn in environmental biomonitor organisms (lichen, algae) and air dust filters.     

Major elements as possible factors of trace element urban pedochemical anomalies

The relationship between real total contents of the major elements Na, Mg, Al, Si, P, S, K, Ca, Ti, Fe and the trace elements Ag, As, B, Ba, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Sn, V, U, Zn in topsoil from the central part of Vilnius is analysed. The amounts of most elements were determined by energy-dispersive X-ray fluorescence, while amounts of Ag, B, Co were measured by optical atomic emission spectrophotometry. Two factors were distinguished according to major elements: anthropogenic (A) including Ca, Mg, Fe, P, S and clayey (C) including K, Al, Ti. Boron, Mn, Cr and U are significantly correlated with members of both factors, Sb with none of them and other trace elements either with all (Cu, Zn, Pb, Se, Ba, Ni, Co) or with separate (V, Ag, Sn, Mo, As) members of the A-factor. Only B, Mn, Cr, U (partly their additive index Z1) are influenced by the C-factor, while twelve other trace elements (also their additive index Z2) are influenced by the A-factor. The additive index Z of all 17 elements is also affected by the A-factor. Four groups of sites have been distinguished according to normal or higher contents of both factors. The majority of trace element anomalies are related to the sites affected by the A-factor.     

Determination of trace elements in petroleum by neutron activation analysis

Instrumental neutron activation analysis (INAA) and Ge(Li) spectrometry have been used to determine Sc, Cr, Fe, Co, Ni, Zn, As, Se, Sb, Eu, Au, Hg, and U in crude petroleum. The technique involves no chemical separations and no pre-concentration of the samples by ashing is necessary, thus avoiding contamination or loss of volatile elements. The estimated detection limits in ppb for the elements are Sc (0.1), Cr (0.16), Fe (400.0), Co (0.6), Ni (1.1), Zn (200.0), As (6.0), Se (23.0), Sb (1.0), Eu (0.58), Au (0.11), Hg (4.3), U (1.5). Precision values ranged from 0.1% to 15% (relative standard deviation). Interferences in the Co and Fe determinations due to fast neutron reactions (n, p) and (n, α) on Ni isotopes are small and are easily corrected. Losses of As, Se, and Hg due to escape of volatile gases during irradiation are negligible