Chemical Species of Iodine in Some Seaweeds II. Iodine-Bound Biological Macromolecules

The distribution of iodine in various biological macromolecules in Sargassum kjellmanianum was studied using neutron activation analysis combined with chemical and biochemical separation techniques. The results indicate that iodine is mainly bound with protein, part of iodine with pigment and polyphenol, and little with polysaccharides, such as algin, fucoidan and cellulose. This result is significant for the mechanism of enriching iodine of algae and utilization of alga iodine.     

Distribution of trace elements in the marine sediments along the South China Sea,Malaysia

In order to complete having data base of elemental assessment of the east coast of Peninsular Malaysia marine sediments along the South China Sea coasts, trace elements are analyzed and their distribution in marine sediments is undertaken. The present study is done parallel with pervious study on elemental assessment of heavy metals, rare earth elements and actinides in the marine sediments of the east coast of Peninsular Malaysia. Thirty surface sediment samples were collected in this area, including regions of Kelantan, Terengganu, Pahang, Rompin and Johor Baharu. Multielemental analysis was carried out by instrumental neutron activation analysis and inductively coupled plasma atomic emission spectroscopy. In both cases methodology validation was performed by certified reference material analyses. For the surface elemental distributions the enrichment factor values, average I _geo and mC _d values indicate that the trace elements of the surface sediments are uncontaminated in all sampling stations that are consistent with previous studies results of heavy metals, rare earth elements and actinides.     

Radioactivation analysis of aluminium,vanadium, copper,molybdenum, zinc and uranium in natural water samples using organic coprecipitants

A method is described for the determination of trace metal ions, V, Al, Cu, Mo Zn, and U, in natural water samples by neutron activation analysis, using organic coprecipitation as a preconcentration method. The preconcentration of trace elements was accomplished by converting the dissolved trace metal ions into the oxine chelates atpH 5.2 and extraction of the chelates witho-phenylphenol which is a liquid above 56 °C and solidifies at room temperature. After cooling the extraction system, the fine particles of the organic phase were collected on a millipore filter and the precipitate was air-dried in a clean environment. The solid extract was wrapped up in a sheet of clean polyethylene and subjected to neutron irradiation in a reactor for less than 10 min at a thermal flux of 2·10¹³ n·cm⁻²·sec⁻¹. γ-Ray spectrometry by a coaxial Ge(Li) detector connected to a 1024-channel PHA was performed on the irradiated sample without further chemical separation, and thus the ppb level concentration of the elements in natural water samples could be determined. The fundamental study of the collection of the trace elements is also described.     

Determination of toxic and trace elements in algae by instrumental neutron activation analysis

Instrumental neutron activation analysis has been applied in the determination of toxic and other trace elements in a set of three algae materials provided by the International Atomic Energy Agency, with the aim of environmental preservation through enhanced applications of nuclear analytical techniques. The quality of the analysis method has been evaluated by analyzing a number of biological standard reference materials. By adding mineral nutrients, the cultivation of algae for metals is enhanced, in particular, selected toxic heavy metals such as As, Cd, Cr, Hg, Ni and Pb. It is believed that the level of elemental concentration in algae samples are dependent on environmental conditions due to its biochemical properties. Therefore, algae materials may be useful as an indicator or controller of environmental water pollution.     

Study of the correlation between trace elements, sterols and fatty acids in brown algae from the Saronikos gulf of Greece

Summary In the whole plant of brown algae species Colpomenia sinuosa, Cystoseira compressa, Dictyopteris membranacea, Dictyota dichotoma, Dictyota linearis, Padina pavonica, Sargassum accinarium and Stypocaulon scoparium collected from Saronikos gulf of Greece, the trace elements antimony, cesium, chromium, cobalt, europium, iron, rubidium, scandium, strontium, thorium and zinc were determined by instrumental neutron activation analysis. In the same samples the sterols campesterol, cholesterol, fucosterol stigmasterol and the fatty acids linoleic, linolenic, myristic, oleic, palmitic, palmitoleic and stearic acid were determined by gas-liquid chromatography. Statistical analysis included the calculation of the correlation coefficient and multiple correlation was applied in all analytical data. The results showed that the sterol pattern of Padina pavonica is different from all the other examined species. A high fucosterol content should be accompanied by very low concentrations or absence of a number of other constituents. Linoleic and linolenic acids present a strong linear correlation between them. Stearic acid seems to play a role in the life process of brown algae due to its significant correlation with fucosterol and with strontium. The high content found for the latter must be an evidence for the selective accumulation of this element from brown algae as mentioned in literature. A multiple correlation was found between sterols, saturated fatty acids and other single constituents studied in this work.     

Determination of trace elements by neutron activation analysis using dinonylnaphthalene sulfonic acid as a preconcentrating agent

Dinonylnaphthalene sulfonic acid (HD) has been used as a preconcentrating agent to enrich trace metal ions and to separate the interfering elements such as Na, K, Cl and Br which normally exist in the natural aqueous systems. Experiments were performed by extracting the ions in the aqueous medium with HD in n-hexane and subsequently back-extracted into a minimal volume of acid solution. Factors influencing the extraction efficiency of the ions of interest were investigated. The preconcentration technique developed in this study was applied to the determination of trace elements in biological and natural water samples by neutron activation analysis.     

Instrumental neutron activation analysis of carbonatites from Panda Hill and Oldoinyo-Lengai, Tanzania

Twenty nine (major and trace) elements including nine rare earth elements (REE) in African carbonatite samples were determined by instrumental neutron activation analysis (INAA). The geochemical behavior of trace elements in carbonatites, especially REE pattern (chondrite normalized), and the efficiency of neutron activation analysis compared to other methods are discussed in this study.     

Analyse par activation et numismatique

In this communication we show that two nuclear methods permit a non-destructive determination of major, minor and trace elements in three important “archaeological” metals: gold, silver, copper and alloys. With the first one, neutron activation analysis with a²⁵²Cf neutron source, we can perform a fast and accurate determination of three important elements of the coin's composition, viz. gold, silver and copper. With the second one, proton activation analysis, we can determine trace elements at ppm level in gold, silver and copper metals. Using these two techniques of activation analysis two important numismatic problems can be studied: the evolution of the fineness; characterization or differentiation by the trace elements the metal used to mint the coin. One example of each numismatic problem is also given.      

Some Aspects on Preconcentration for Neutron Activation Analysis

A preconcentration method incorporated with neutron activation analysis was developed for the accurate determination of trace metals in biological and environmental samples. Bismuth diethyldithiocarbamate, thallium diethyldithiocarbarnate, and ammonium pyrrolidinedithiocarbamate were used as the preconcentration agents for three groups of metals. Trace metals were enriched and interfering elements such as Na, Br, P. K. etc. were removed simultaneously during the preconcentration process so that the sensitivity for each metal was greatly improved. Optimal conditions for sample digestion, group preconcentration of trace metals and neutron activation analysis of biological and environmental samples were discussed.     

胎儿和儿童骨中稀土元素与微量元素分析及其生物信息

中子活化法分析了多例胎儿骨，儿童骨和猪脚骨中稀土元素，ＩＣＰ－ＡＥＳ分析了多例胎儿骨中微量元素并讨论了稀土元素透过胎盘屏障进入胎儿人和儿童进行中的累积情况。     

Elemental characterization of coal ash and its leachates using sequential extraction techniques

Over 50 million tons of coal ash are produced annually in North America. Technological improvements in air pollution control have decreased stack emissions but have also increased contaminant concentrations in the ash of coal-fired boiler applications. The leaching of heavy metals and other elements during regulatory tests may cause coal ash ro be classified as hazardous waste, complicating land disposal. The hazardous nature of coal ash remains unclear because current toxicity tests fail to effectively characterize the elemental distribution and chemical solubility of trace metals in the landfill environment. Leaching characteristics of ash samples can be investigated with various laboratory extraction procedures in association with multi-elemental analytical techniques (e.g., neutron activation analysis and inductively coupled plasma-atomic emission spectroscopy). Such methods provide more thorough analyses of coal ash leaching dynamics than the regulatory assessments can demonstrate. Regulatory elements including Ag, As, Ba, Cd, Cr, Hg, Pb, and Se were shown to remain in largely insoluble forms while elements such as B and S leached at higher levels. Experimental results may assist operators of coal-fired boiler industries in selecting coal types and disposal options to curtail the leaching of potentially toxic inorganic contaminants.     

Neutron activation analysis applied to the study of heavy metal marine pollution observed through bioaccumulation in macroscopic algae near El Jadida,Morocco

The heavy metals bio-accumulation ability of algae was studied along the North Atlantic Morrocan coast. Instrumental neutron activation analysis was used, to determine concentrations of various elements. The k ₀ standardization method was used. Some interferences corrections, particularly due to high concentrations of uranium were applied. The quality of the method was checked by using the CRM 140, a Fucus provided by IAEA. Important pollutions appear for several heavy metals from the Morrocan phosphate industry, with respect to the natural background environment.     

Determination of trace elements by INAA in urban air particulate matter and transplanted lichens

Summary Lichens as biomonitors and neutron activation analysis as analytical technique have been employed to evaluate the trace element atmospheric pollution in the metropolitan area of the city of Pavia (Northern Italy). Transplanted lichens (Parmelia sulcata and Usnea gr. hirta) and air particulate matter have been monthly collected and analyzed during the winter 2001-2002. INAA and ET-AAS have been used for the determination of 28 elements in air particulate matter and 25 elements in lichens. Trace metals concentrations as well as the corresponding enrichment factors were evaluated and compared.     

Assessment of metals and trace elements in sediments from Rio Grande Reservoir,Brazil, by neutron activation analysis

The Rio Grande Reservoir, Southeast of the São Paulo Metropolitan Area, supplies water for four counties (about 1.6 million people). It has been seriously affected by urban expansion due to chaotic urban occupation and improper use of the surrounding areas. In this study bottom sediment samples were collected during the dry season and rainy season. Four sampling points were defined and located at the mouth of the Rio Grande and Ribeirão Pires Rivers (points 1 and 2), in the middle of the reservoir (point 3) and near the catchment point of the water supply (point 4). Samples were submitted to instrumental neutron activation analysis and some metals, trace and rare earth elements were determined. The methodology validation according to precision and accuracy was carried out by reference material analyses. The results obtained were compared to earth crust values and also with results already published in the literature. The enrichment factor in relation to earth crust values using Sc as reference element was calculated and a strong enrichment was found for the elements As, Br, Sb, Th, U and Zn. A strong anthropogenic influence was observed for some elements, mainly in the points located in the entrance of the reservoir that receives domestic and industrial effluents from the rivers that reach the reservoir.     

Chemical speciation of trace metals in seawater: a review.

The recent development of the chemical speciation of trace metals in seawater is described. The speciation studies reveal that metal ion complexation is one of the most important processes in seawater; especially, most bioactive trace metals, such as Fe(III) and Cu, exist as complexes with ligands in dissolved organic matter. The organic ligands in seawater are characterized with metal ions selected by the HSAB concept. A strong organic ligand, which originates from marine microorganisms, is classified as a hard base including carboxylates. The free organic ligand concentrations in seawater are buffered by complexation with excess amounts of Ca and Mg in seawater. The chemical equilibrium model suggested that the concentrations of bioactive free metal ions are at an optimal level to activities of marine microorganisms. For chemical speciation, it is important to have a better understanding of the ecological roles of trace metals in seawater.     

Study of a heavy metal biosorption onto raw and chemically modified Sargassum sp. via spectroscopic and modeling analysis

In this study, raw and formaldehyde-modified Sargassum sp. are used for heavy metal removal. A series of experiments shows that the chemical modification by formaldehyde improves biosorption capacity by approximately 20%. Solution pH plays an important role in the metal uptake. According to X-ray photoelectron spectroscopic and Fourier transform infrared spectroscopic analysis, the possible organic functional groups in the metal binding include carboxyl, ether, alcoholic, hydroxyl, and amino functional groups. A new model that includes a series of coordination reactions among a generalized functional group, alkaline earth metal ions and heavy metal ions, is developed for simulation of biosorption process. The model well describes the single- and multiple-species metal biosorption process under different conditions such as pH. The biosorption of heavy metals is due to the ion exchange between the heavy metals and alkaline earth metals and their adsorption onto the free sites of the seaweeds. Slightly more than half of the metal uptake is due to ion exchange. The metal affinity for the functional groups follows a descending order of lead > copper > alkaline earth metal.     

Applications of nuclear analytical techniques in human nutrition research as exemplified by research programmes of the international atomic energy agency

In human nutrition research, nuclear analytical techniques, particularly neutron activation analysis (NAA), are used mainly for thein vitro study of trace elements. According to work sponsored by the IAEA, up to 15 trace elements and 5 minor elements of nutritional interest may be determined in biological materials by NAA with good accuracy and precision. A programme is described in which NAA was used for the determination of 14 trace elements and one minor element in human milk. NAA also plays an important role in the certification of reference materials for nutritional studies.     

Size fractionation techniques combined with INAA for speciation purposes

In natural waters trace elements, especially trace metals may be present in a variety of physicochemical forms. They may be associated with forms ranging from simple ions and molecules via hydrolysis products and colloids, pseudocolloids and organic or inorganic particles. The transition between categories is gradual. The presence of species differing in size, charge and density will influence on the transport, mobility and bioavailability of the trace element in question. Fractionation techniques which do not influence the distribution patterns are therefore required for speciation purposes. In the present work dialysis in situ and large membrane (hollow fibers) ultrafiltration are used for fractionation of low molecular weight species, colloids, pseudocolloids and particles. Due to the presence of foreign components transformation processes influence the distribution patterns of trace elements of interest. Sorption to foreign surfaces, complexation with agents present and aggregation of colloids (e.g., increasing ionic strength) result in a shift towards higher dimensions while desorption and dispersion processes mobilize the trace elements. Information on several components is therefore needed in speciation studies and a multielemental method of analysis having low determination limits must be applied. Instrumental neutron activation is appropriate to this kind of study because of its high sensitivity for simultaneous determination of a great-number of elements. Size fractionation techniques combined with INAA for the characterization of trace element species in natural waters will be discussed.     

Determination of rare earth elements in chloroplasts of Brassia napus by INAA and biochemical separation techniques

Intact chloroplasts were isolated from mesophyll protoplasts of Brassia napus. Concentrations of 8 rare earth elements (REEs) in the chloroplasts were determined by instrumental neutron activation analysis (INAA). The results showed that there were trace amounts of REEs in the chloroplasts, which corresponded to 1 atom of REEs per 2000 chlorophyll molecules. About 30% of the total REEs in the leaves are localized in the chloroplasts and the light REEs were enriched with respect to the heavy elements of the series.     

Determination of trace elements in marine organisms by neutron activation analysis

The content of Na, Sc, Cr, Fe, Co, Zn, As, Br, Sb, Cs, La, Ce, Sm, Eu, Lu and Hf inEunicella cavolinii, Cladocoro cespitosa, Cystoseira barbata, Zostera marina, Posidonia oceanica andUlva lactuca was found to be approximately 3–5 orders of magnitude higher than reported for sea water, as determined by nondestructive neutron activation analysis (NNAA). The relative amounts of these elements in all organisms investigated are very similar and reflect their ratio in the media. Rare earth elements, however, are an exception and their accumulation appears to be specific. Among the organisms investigated,Zostera marina has the highest capacity for accumulation of most elements determined and thus may be used as an “indicator” organisms.